U.S. patent number RE29,224 [Application Number 05/701,393] was granted by the patent office on 1977-05-17 for polyurethane urea elastomers based on polycarbonate macrodiols.
This patent grant is currently assigned to Bayer Aktiengesellschaft. Invention is credited to Klaus Konig, Klaus Noll, Josef Pedain, Wilhelm Thoma.
United States Patent |
RE29,224 |
Pedain , et al. |
May 17, 1977 |
Polyurethane urea elastomers based on polycarbonate macrodiols
Abstract
Polyurethane urea elastomers with novel dissolution behavior and
which are synthesized from polycarbonate macrodiols, diisocyanates
and diamines and which can be prepared and dissolved in aqueous
solvents. These elastomers have the advantage of being less of a
physiological hazard, more resistant to common solvents and require
less emulsifiers and dispersion aid.
Inventors: |
Pedain; Josef (Cologne,
DT), Noll; Klaus (Cologne, DT), Konig;
Klaus (Leverkusen, DT), Thoma; Wilhelm
(Bergisch-Neukirchen, DT) |
Assignee: |
Bayer Aktiengesellschaft
(Leverkusen, DT)
|
Family
ID: |
27184391 |
Appl.
No.: |
05/701,393 |
Filed: |
June 30, 1976 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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Reissue of: |
353036 |
Apr 20, 1973 |
03867350 |
Feb 18, 1975 |
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Foreign Application Priority Data
Current U.S.
Class: |
528/61; 8/115.6;
528/44; 528/49; 528/62; 528/64; 528/74; 528/906 |
Current CPC
Class: |
C08G
18/10 (20130101); C08G 18/3834 (20130101); C08G
18/10 (20130101); C08G 18/3225 (20130101); C08G
18/10 (20130101); C08G 18/44 (20130101); C08G
18/75 (20130101); D06M 15/564 (20130101) |
Current International
Class: |
C08G
18/10 (20060101); C08G 18/75 (20060101); D06M
15/37 (20060101); C08G 18/00 (20060101); C08G
18/44 (20060101); D06M 15/564 (20060101); C08G
022/10 (); C08G 018/75 () |
Field of
Search: |
;260/75NK,77.5AM,77.5AN,77.5D,75NH,77.5AT |
References Cited
[Referenced By]
U.S. Patent Documents
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3359242 |
December 1967 |
Seeliger et al. |
3450793 |
June 1969 |
Schnell et al. |
3541183 |
November 1970 |
Kallert et al. |
3639354 |
January 1972 |
Mueller et al. |
3640967 |
February 1972 |
Koenig et al. |
3658746 |
April 1972 |
Rosendahl et al. |
3708453 |
January 1973 |
Thoma et al. |
3711443 |
January 1973 |
Thoma et al. |
3758443 |
September 1973 |
Koenig et al. |
3770681 |
November 1973 |
Witt et al. |
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Foreign Patent Documents
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808,488 |
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Feb 1959 |
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UK |
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917,450 |
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Feb 1963 |
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UK |
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1,224,350 |
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Mar 1971 |
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UK |
|
Primary Examiner: Cockeram; H.S.
Attorney, Agent or Firm: Harsh; Gene
Claims
What is claimed is:
1. Polyurethane urea elastomers corresponding to the formula:
##STR47## in which R represents the group ##STR48## where 40 to 100
percent by weight of A represents
and 0 to 60 percent by weight of A represents --CH.sub.2
--.sub.q
where
p = 2 - 7,
q = 6 or 7,
n = 2 - 40,
R' represents a divalent C.sub.6 -C.sub.14 aromatic, C.sub.4
-C.sub.18 aliphatic or C.sub.5 -C.sub.20 -cycloaliphatic
radical,
R" represents a divalent C.sub.6 -C.sub.14 aromatic, C.sub.4
-C.sub.18 aliphatic or C.sub.5 -C.sub.20 -cycloaliphatic radical,
which may contain nitrogen as heteroatom, or a --NH--CO--NH--.sub.r
R.sup.IV -NH--.sub.s CO--NH-- group
where
R.sup.iv is a C.sub.1 -C.sub.10 aliphatic or C.sub.5 -C.sub.20
cycloaliphatic radical,
r = 0 or 1;
s = 0 or 1,
R"' represents H or a C.sub.1 -C.sub.6 aliphatic radical,
and
k = 0 or 1,
m = 0 - 4,
x = 5 - 200
at least 20 mol % of R' or R" being .[.cycloaliphatic.]. ##STR49##
radicals or at least 20 mol % of both R' and R" being
.[.cycloaliphatic.]. ##STR50## radicals.
2. The product of claim 1 wherein R represents the group ##STR51##
where 60 to 100 percent of A represents
and 0 to 40 percent of A represents (CH.sub.2).sub.q and at least
40 mol percent of R' or R" being .[.cycloaliphatic.]. ##STR52##
radicals or at least 40 mol percent of R' and R" being
.[.cycloaliphatic.]. ##STR53##
Description
This invention relates to polyurethane urea elastomers with novel
dissolution behavior which are synthesized from polycarbonate
macrodiols, diisocyanates and diamines and which can be prepared
and dissolved in aqueous solvents. The invention also relates to
the use of these elastomers for the production of coatings,
coverings, films and lacquers.
The problem which the invention seeks to solve is imposed by the
necessity to keep air and water free from pollution. An object of
the invention is to provide elastomers with valuable properties for
coatings, coverings, films and lacquers which, during processing,
do not give off any physiologically harmful, environment-polluting
solvents. Another object of the invention is further to improve the
high commercial standing of polyurethane and polyurea elastomers in
the aforementioned fields.
Solutions of polyurethane and polyurea elastomers are already being
extensively used for coatings. Although the products do not always
have to be subsequently subjected to a crosslinking reaction, they
generally show favorable resistance to chemicals and reagents of
the kind usually met in daily life. However, it follows from this
that, in general, polymers such as these cannot be processed in
such solvents. It is necessary to use relatively expensive solvents
with high boiling points and high dissolving power such for
example, as dimethyl formamide, dimethyl acetamide and N-methyl
pyrrolidone. The proper use of these solvents necessitates
elaborate recovery or burning installations for the solvents.
Processing regulations have to be strictly observed because some of
the high boiling organic solvents referred to above are also
physiologically harmful.
Polyurea elastomers synthesized from cycloaliphatic isocyanates are
exceptions in the above. They have the advantage of greater light
stability and can also be dissolved in "soft solvents," for
example, in mixtures of aromatic solvents and alcohols (for example
toluene/isopropanol).
Unfortunately, the known products of this kind do not satisfy
modern requirements. Some textile coatings prepared from these
elastomers show only moderate resistance to trichloroethylene and
perchloroethylene, which means that they can only be dry cleaned to
a limited extent, thereby restricting their use. The processing of
solutions containing aromatic hydrocarbons calls for special safety
precautions on account of the unfavorable properties of these
substances, for example their high inflammability and, in some
cases, their toxicity.
The prior art also includes polyurethane dispersions in water which
undoubtedly present no health hazards in processing. However, a
serious disadvantage of these systems is that they require a high
content of emulsifiers or dispersion aids, which results in
inadequate stability of the coatings and films to moisture, and,
above all, to the effects of weather. In the case of ionic
dispersions, the high sensitivity of the products to electrolytes
occasionally results in premature precipitation, a highly
undesirable phenomenon.
Polyurethanes based on polyethylene oxide glycols which are
dissolved in water are described in U.S. Pat. No. 3,189,578. Even
after they have been applied to substrates and dried, these resins
are still soluble in water. Accordingly, they are not suitable for
coatings which are exposed to hydrolytic influences.
The present invention substantially reduces or obviates the
disadvantages referred to above and eliminates undesirable
properties of the products prepared according to the prior art.
The invention relates to polyurethane urea elastomers corresponding
to the formula ##STR1## in which R represents the group ##STR2##
where 40 to 100 percent by weight, preferably 60 to 100 percent by
weight, of A represents
while 0 to 60 percent by weight, preferably 0 to 40 percent by
weight, of A represents --CH.sub.2 --.sub.q
and in which
p = 2 - 7;
q = 6 or 7 and
n = 2 - 40,
R' represents a divalent C.sub.6 -C.sub.14 aromatic, C.sub.4
-C.sub.18 aliphatic or C.sub.5 -C.sub.20 cycloaliphatic
radical,
R" represents a divalent C.sub.6 -C.sub.14 aromatic, C.sub.4
-C.sub.18 aliphatic or C.sub.5 -C.sub.20 cycloaliphatic radical,
which may contain nitrogen as heteroatom.
or a
aliphatic or C.sub.5 -C.sub.20 cycloaliphatic radical,
r = 0 or 1;
s = 0 or 1;
R'", represents H or a C.sub.1 -C.sub.6 aliphatic radical,
and
k = 0 or 1;
m = 0 - 4;
x = 5 - 200;
at least 20 mol percent, preferably at least 40 mol percent, of R'
and/or R" being .[.cycloaliphatic radicals..]. ##STR3##
The invention also relates to a process for the production of
polyurethane urea elastomers from prepolymers with terminal NCO
groups based on dihydroxy polycarbonates, which may in addition
contain monomeric diisocyanates and chain extender containing amino
groups, in which dihydroxy polycarbonates of molecular weight 500
to 6,000, prepared from a diol mixture of 40 to 100 percent by
weight, preferably 60 to 100 percent by weight, of polyethylene
glycols and of 0 to 60 percent by weight, preferably 0 to 40
percent by weight, of 1,6 -hexane diol and/or 1,7-heptane diol and
carbonic acid derivatives, are reacted with diisocyanates to form a
prepolymer preferably with an NCO content of from 1.0 to 10.0
percent by weight, and the prepolymer thus obtained, which may be
dissolved in an inert organic solvent or suspended in water, is
reacted with diamines, hydrazines, dihydrazides or semicarbazides,
preferably dissolved in alcohol (which may be aqueous), with a
molar ratio of active H:NCO of from 0.8:1 to 1:1, accompanied by
chain extension, at least 20 mol percent and preferably at least 40
percent of the diisocyanate and/or of the chain extender being
.[.cycloaliphatic in nature..]. ##STR4##
The invention also relates to the use of the products according to
the invention for the production of textile coatings, films,
sheeting and lacquers.
More particularly, the invention provides polyurea elastomers which
can be used and dissolved in solvent mixtures which, in addition to
water, only contain components of the kind which have an MAK-value
of 900 mg/m.sup.3 and above, according to the "Richlinien fur
chemische Laboratorien" der Berufsgenossenschaft der Chemischen
Industrie, 1969. The MAK-value is the concentration of a gas or
vapor which can be expected daily over a working day of about 8
hours and which, even with repeated ingestion, does not cause any
damage to health.
The main advantage of the invention over the prior art is obviously
embodied in the surprising novel solution properties of the
polyurethane urea elastomers according to the invention. Although
the coatings, coverings, films and lacquers prepared from them are
uncrosslinked and still thermoplastic after application and drying
so that they can also be formed and embossed while still hot, they
do nevertheless show unexpectedly high resistance to attacking
solvents such as toluene or perchlorethylene, which is of
considerable advantage so far as dry cleaning is concerned. On the
other hand, they also show remarkably high resistance to hydrolytic
influences. The products are insoluble both in pure water and in
pure alcohol.
Contact with tap water at 70.degree. C over a period of several
weeks produces hardly any change in their properties.
The products are understandably less resistant to mixtures of water
and alcohols. If resistance to these mixtures is also required, the
polyurethane ureas according to the invention can be crosslinked
surprisingly easily and under mild conditions, by the addition of
formaldehyde or formaldehyde derivatives such as, for example,
formaldehyde-melamine resins or by the addition of polyols whose
OH-groups have been closed with methoxy methyl isocyanate (cf., for
example German Offenlegungsschrift No. 1,644,815). Cross-linking
makes the products according to the invention resistant to
water/alcohol mixtures and also to other solvents such as dimethyl
formamide.
The mechanical properties of the coatings, coverings, films and
lacquers produced with the polyurethane urea elastomers according
to the invention are also surprisingly good. Whereas polyethers
incorporated into polyurethanes are known to lead to soft coatings
which often have a tacky feel and limited strength, coatings
prepared with the polyurethane urea elastomers according to the
invention, although containing ether groups, have a dry feel and
high strength and can be made soft or hard as required.
The polycarbonate macrodiols used in accordance with the invention
are predominantly difunctional, i.e., they contain two hydroxyl
groups in the molecule, and preferably have a molecular weight of
from 500 to 6,000, more preferably from 600 to 3,000.
It is preferred in order to obtain good flexibility properties that
they be prepared from polyether glycols. Suitable polyether glycols
include triethylene glycol, tetraethylene glycol, penta-, hexa-,
hepta- and octa-ethylene glycol, and also mixtures of these
glycols. In addition, however, 1,6-hexane diol and 1,6-heptane diol
can also be used for preparation in quantities of up to 60 percent
by weight, but preferably in quantities of less than 40 percent by
weight, based on diols. Preferred diol components for preparation
of the polycarbonate macrodiols include tri-, tetra-, octa-ethylene
glycols and 1,6-hexane diol.
The polycarbonates are synthesized by methods known per se. The
glycols are condensed either with diaryl carbonates, for example
with diphenyl carbonate, in which case phenol is eliminated, or
with phosgene in which case hydrochloric acid is eliminated, (cf.,
for example, German Offenlegungsschrift No. 1,915,908). The
preparation of a representative macrodiol polycarbonate is
described in the following.
4,365 parts of tetraethylene glycol (22.5 mols) are mixed with
4,280 parts (20 mols) of diphenyl carbonate; the resulting mixture
is fused and gradually heated over a period of 10 hours at 15 Torr
from 150.degree. to 200.degree. C, 3,700 parts of phenol being
distilled off. Thereafter the mixture is stirred for 1 hour at
200.degree. C/1 Torr, another 50 parts of phenol distilling off. A
viscous oil is obtained which crystallizes after a few days.
Softening point approximately 50.degree. C; OH-- number 57.2;
aromatic content:
1. free phenol: 0.03 percent
2. phenyl carbonate terminal groups: 0.01 percent
3. phenol ether groups: 0.01 percent
The polyurea elastomers according to the invention can be prepared
with the low molecular weight diisocyanates known per se in
polyurethane chemistry, such as for example 4,4'-diisocyanato
diphenyl methane, 2,4- and 2,6-toluene diisocyanate and
1,5-naphthalene diisocyanate. It is preferred to use diisocyanate
with aliphatic NCO groups such as, for example, 1,4-xylylene
diisocyanate, 1,3-xylylene diisocyanate, 4,4'-dicyclohexyl methane
diisocyanate, 2,2,4-trimethyl hexane-1,6-diisocyanate,
cyclohexane-1,4- and 1,3-diisocyanate,
3,3'-dimethyl-4,4'-diisocyanato dicyclohexyl methane and
lysine-C.sub.1 -C.sub. 6 -alkyl ester diisocyanates.
Of the aliphatic isocyanates, 1,6-diisocyanato hexane and
1-isocyanato-3-isocyanato-methyl-3,5,5-trimethyl cyclohexane are
particularly preferred.
A prepolymer is initially formed in known manner from the
polycarbonate macrodiols and the diisocyanates. The reaction is
generally carried out at temperatures of from 50.degree. to
150.degree. C, preferably in the melt or in an inert organic
anhydrous solvent, for example in a ketone such as acetone.
NCO-prepolymer formation is generally carried out with an OH:NCO
reaction ratio of from 1:1.5 to 1:5, preferably from 1:1.5 to
1:3.5, the ratio being governed both by the molecular weight of the
polycarbonate macrodiol and by the required properties of the end
products. (With molar ratios of OH to NCO of less than 1:2, the
reacted mixture still contains free monomeric diisocyanate. The
expression "prepolymer" is also intended to cover mixtures of this
kind in the following). In general, the ratio should be such that
the solvent-free prepolymer has an NCO content of from 1.0 to 10.0
percent by weight of NCO.
The prepolymer containing NCO groups is further reacted to form the
polyurethane urea elastomer according to the invention. The
reaction with the diamine, hydrazine or dihydrazide is generally
carried out with cooling at temperatures of from -20.degree. to
+40.degree. C, preferably at temperatures of from 0.degree. to
30.degree. C. Since at this temperature the prepolymers are liquids
of extremely high viscosity which are extremely difficult to stir,
it is preferred to prepare initially a suspension of the prepolymer
in water at 0.degree. to 20.degree. C. The reagent (diamine,
hydrazine or dihydrazide) is then added in alcoholic solution. The
solutions generally have a solids content of from 10 to 60 percent
and water:alcohol ratios of 2:1 to 1:2. If it is not desired to
prepare a solution, but to isolate the solvent-free polyurethane
urea instead, a higher water content will be selected, for example
a water to alcohol ratio 3:1. Although a solution is initially
formed, it clouds or gels on standing. The polyurethane urea is
obtained in the form of a moist powder or granulate which can be
dried.
This procedure cannot be applied where a solvent has been used in
the preparation of the prepolymer. Nor is it of any advantage where
an aromatic diisocyanate or a macrodiol polycarbonate of high
triethylene glycol, 1,6-hexane diol or 1,7-heptane diol content has
been used in the preparation of the prepolymer. In this case, the
chain extender-diamine, hydrazine, or dihydrazide is dissolved in a
mixture of water and alcohol and the resulting solution added to
the prepolymer dissolved in an inert solvent. Preferred solvents
are esters and ketones. The ratio of the water:alcohol mixture
(ratio 1:2 to 2:1), to this solvent is about 1:4 to 4:1.
In both procedures, it is of course also possible to adopt the
reverse procedure, i.e., to add the solution or suspension of the
prepolymer to the solution of the diamine, hydrazine or
dihydrazide. In either case, the chain-extending reaction itself
takes place in homogeneous phase because genuine solutions are
formed when the prepolymer and the dissolved chain extender are
mixed.
In order to avoid possible side reactions an excess of basic groups
should be avoided as far as possible during the reaction. The
diamines, hydrazines or bishydrazides are reacted with the
NCO-prepolymers, preferably in a ratio of 0.8:1 to 1:1. Small
quantities of monoamine can be used in the usual way for chain
termination in the polyaddition reaction.
The aliphatic diamines used as chain extenders can contain primary
or secondary amino groups. Examples of diamines such as these
include piperazine, hexamethylene diamine, ethylene diamine,
1,2-propylene diamine, N-methyl-bis-(3-aminopropyl)-amine, 1,4- (or
1,3) diamino cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethyl
cyclohexane, bis(4-amino cyclohexyl)methane.
Preferred diamines are those which contain cyclohexane rings.
Hydrazine and N,N'-dimethyl hydrazine also represent suitable chain
extenders, as do bishydrazides such as .beta.-semi-carbazido
propionic acid hydrazide, 3-semi-carbazido-propyl-carbazinic
esters, adipic acid dihydrazide and glutaric acid dihydrazide.
Semi-carbazido-3-semi-carbazido methyl-3,5,5-trimethyl cyclohexane
is preferably used.
A mixture of hydrazine hydrate and a diamine containing at least
one cyclohexane ring represents a particularly preferred chain
extender.
In order to obtain products with the required hydrolytic and
mechanical properties and behavior with respect to solvents sought
by the invention, the diisocyanates used for prepolymer formation
and/or the chain extenders should contain at least 20 mol percent,
preferably more than 40 mol percent, of cycloaliphatic
compounds.
In addition to water, solvent mixtures suitable for the
polyurethane ureas contain alcohols, esters and ketones, for
example methanol, ethanol, propanols and butanols, ethylacetate,
butylacetate, methylacetate, isopropylacetate, acetone, methylethyl
ketone and methyl isobutyl ketone. Ethanol, isopropanol,
ethylacetate and acetone are preferably used.
A high-boiling solvent such as, dimethyl formamide, which generally
has to be added to polyurethane solutions in order to obtain
satisfactory film formation during processing, is unnecessary
because the water present in the solution has the same property.
Accordingly, toxicologically unacceptable solvents, such as for
example dimethyl formamide or aromatic hydrocarbons, can be avoided
throughout the entire process for the production and processing of
the products according to the invention.
The polyurethane ureas according to the invention can be used for
the production of films, coatings, coverings and lacquers. Although
they can be used in the form of powders, for example by the
melt-calendering process, they are generally used in the form of
solutions which contain the usual additives such as stabilizers,
antiagers, UV-absorbers, hydrolysis inhibitors, pigments, dyes and
fillers and which are applied for example by casting,
knife-coating, spread-coating, brush-coating and spray-coating. For
the production of coatings, they are applied to substrates such as
leather, artificial leather, plastics, woven and knitted fabrics,
while for the production of lacquers and coverings they are
applied, or bonded in film-form, to wood, glass and metal. They can
also be applied to intermediate substrates, for example release
paper, in which case processing is carried out by the reversal
process.
The invention is illustrated by the following Examples. Unless
otherwise stated, percentages relate to percent by weight.
EXAMPLE 1
A. 1 mol of a polycarbonate macrodiol from tetraethylene glycol
with an average molecular weight of 1,778 is heated for about 5
hours to 90.degree. - 100.degree. C with 2 mols of
1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane. An NCO
prepolymer with an NCO-group content of 3.3 percent which is still
liquid, even at room temperature, is obtained. B. 2,186 parts of
water are added at 0.degree. to 5.degree. C, to 1,000 parts of the
prepolymer obtained as in (A) and the mixture stirred to form an
emulsion. The emulsion is stable and can be stored for several days
at 0.degree. and 10.degree. C without undergoing any change in its
NCO-content. To prepare the polyurethane urea elastomer, 93 parts
of 4,4'-diamino-3,3'-dimethyl-di-cyclohexyl methane are dissolved
in 2,186 parts of ethanol and the resulting solution allowed to
flow slowly into the emulsion of the prepolymer. A clear 20 percent
solution is formed during the actual addition of the amine
solution, reaching its final viscosity of 800 CP after about 1
hour.
To prepare a textile coating, a pigment dye is added to the
solution and the resulting product applied on a pair of rolls to a
release paper. After brief drying at 100.degree. C, a second layer
is applied onto which a roughened textile web is pressed without
drying. The solvent is then evaporated at 100.degree. C and the
release paper removed. The textile material now has an
approximately 60 .mu. thick coating with a very pleasant soft feel
coupled with high mechanical strength.
EXAMPLE 2
A number of tests carried out as in Example 1 are summarized in
this Example (Table 1). In all Examples, the viscosities of the
solutions were measured at 25.degree. C with the Viscotester VT 02
manufactured by Messrs. Gebruder Haake of Berlin.
EXAMPLE 3
A. To one mol of an anhydrous macrodiol polycarbonate of
triethylene glycol and tetraethylene glycol in a molar ratio of 1:1
with a hydroxyl number of 92 and an average molecular weight of
approximately 1,220 are added 1 mol of hexamethylene diisocyanate
and 1 mol of 1-isocyanato-3-isocyanato-methyl-3,5,5-trimethyl
cyclohexane and the resulting mixture is stirred in the absence of
a solvent for 3 hours at about 100.degree. C. The NCO content is
determined to be 5.1 percent NCO. The prepolymer is a highly
viscous liquid at room temperature.
B. 2,000 parts of the prepolymer obtained in (A) are dissolved in
1,250 parts of ethylacetate and a solution of 107 parts of
4,4'-diamino dicyclohexyl methane and 26 parts of hydrazine hydrate
in a mixture of 1,250 parts of water and 2,500 parts of ethanol are
added to the resulting solution with stirring at 10.degree. C. A
clear solution of an elastomer with a viscosity of 20,000 cP is
formed in an exothermic reaction during which the temperature rises
to 25.degree. C. The solution is coated onto glass plates and dried
for 5 minutes at 120.degree. C. A colorless, glossy lacquer is
obtained which is completely unchanged after 600 hours exposure to
the light of a UV-lamp.
EXAMPLE 4
The preparation of further polyurethane urea elastomers is
summarized in Table 2. In each case, the procedure is as in Example
3.
TABLE 1 Type of macrodiol Preferred application of of polycarbonate
Properties of the the polyurethane urea used Diisocyanate(s) NCO:OH
ratio Diamine(s) NCO:NH.sup.2 -ratio Solvent elastomer solution
elastomers I Based on tetra-ethylene glycol:average molecularweight
approx.1.780. ##STR5## ##STR6## ethanol:water1:1. Solids content
20% viscosity7,000 cp.:colorless clear. Textile-coating agent.
NCO:OH=2:1. NCO:NH.sub.2 =1:0.95. II As I As I 1,12-nonadecane
diamine NCO:NH.sub.2 =1:0.93 As I Solids content 20% viscosity Soft
adhesive layer for 3,000 cp.:colorless slightly hazy. textile
coating. III As I As I H.sub.2 NNH.sub.2. H.sub.2 ONCO:NH.sub.2
=1:0.87 As I Solids content 50% viscosity Lacquer of high light
40,000 cp.: colorless, clear. stability for plastics. IV As I
OCN(CH.sub.2).sub.4NCO NCO:OH=2:1. ##STR7## Ethanol:water 1.5:1.
Solids content 25% viscosity 25,000cp. colorless, clear. Elastic
light stable and weather-resistant films.NCO:NH.sub.2 =1:0.90. V As
I ##STR8## ##STR9## Ethanol:water 1:1. Solids content 20%,
viscosity100,000 cp.; colorless, clear. Paper-coating agent.
NCO:OH=2.3:1. NCO:NH.sub.2= 1:1VI As I As V ##STR10## Ethanol:water
1.4:1. Solids content 32%, viscosity30,000 cp.; colorless, clear.
Paper-coating agent. NCO:NH.sub.2= 1:0.80 VII As I As V N.sub.2
NCH.sub.2 . CH.sub.2NH.sub.2 NCO:NH.sub.2 =1:0.99 Ethanol Solids
content 30%, viscosity For very soft coatings and water 1.2. 10,000
cp.; colorless, clear. for priming leather. VIII As I As V H.sub.2
NNH.sub.2 H.sub.2 O Ethanol: Solids content 51%, viscosity For
stoving lacquers in NCO:NH.sub.2 =1:0.88. water 1:1. 60,000 cp.;
colorless, clear. combination with for- maldehyde resins. IX As I
As V ##STR11## Ethanol:water 1:1. Solids content 30%,
viscosity25,000 cp.; colorless, slightlyhazy. As VIII. H.sub.2
NNH.sub.2 . H.sub.2 O in a molar ratio of 1:1 NCO:NH.sub.2 =1:0.90.
X As I ##STR12## H.sub.2 NNH.sub.2 . H.sub.2 ONCO:NH.sub.2 =1:0.90.
Ethanol:water 1:1. Solids content, viscosity 9.000 c.p.;colorless,
clear. For coating polyamidfabrics. OCN(CH.sub.2).sub.6NCO in a
molar ratio of 1:1 NCO; OH=2:1 XI As I ##STR13## H.sub.2 NNH.sub.2
. H.sub.2 ONCO:NH.sub.2 =1:0.90. Ethanol:water 1:1. Solids content
30%, viscosity15,000 c.p.; colorless, clear. For soft textile
coatings. OCN(CH.sub.2).sub.6NCO in a molar ratio of 3:1 NCO:
OH=2.1. XII As I ##STR14## H.sub.2 NNH.sub.2 . H.sub.2
ONCO:NH.sub.2 =1:0.90. Ethanolwater 1:1. Solids content 20%
viscosity20,000 c.p.; colorless, clear. For extremely soft
textilecoatings (light stable).in a molar ratio of 1:3 NCO:OH=2:1.
XIII As I As XII ##STR15## Isopropanol:water 1.1. Solids content
15%, viscosity1,000 cp.; colorless , slightlyhazy. For very soft
textilecoatings. NCO:NH.sub.2 =1:0.9. XIV As I ##STR16## H.sub.2
NNH.sub.2 . H.sub.2 ONCO:NH.sub.2 =1:0.9. Isopropanol:water 1:1.
Solids content 30%, viscosity5,000 cp.; colorless, clear. For
coating leather. ##STR17## in molar ratio of 1:2 NCO:OH=3:2. XV As
I As XIV ##STR18## Isopropanol:water 1:1. Solids content 30%,
viscosity15,000 cp.; colorless clear. For coating leather.
NCO:NH.sub.2 =1:0.9. XVI Tetraethyleneglycol poly-carbonate witha
hydroxyl numberof 121. ##STR19## ##STR20## methanol:water 1:1.
Solids content 33%, viscosity 5,000cp.; colorless, clear. For
lacquering plastics. NCO:OH=2:1. H.sub.2 N NH.sub.2 . H.sub.2 O
molar ratio 1:1 NCO:NH.sub.2 =1:0.9 XVII As XVI ##STR21##
NH.sub.2NH.sub.2 . H.sub.2 ONCO:NH.sub.2 =1:0.88. Ethanolwater 1:1
Solids content 20%, initially clearsolution which turns intopaste
on standing. Application as a spread-able paste for
coatingtextiles. OCN(CH.sub.2).sub.4NCO molar ratio 5:1
NCO:OH=18:1. XVIII As XVI ##STR22## NHNH.sub.2 . H.sub.2
ONCO:NH.sub.2 =1:0.9. Ethanolwater 1:1. Solids content 25%, clear
solutionwhich turns into a paste onstanding. Applicati on as a
spread-able paste for textilecoatings. OCN (CH.sub.2).sub.6NCO and
##STR23## molar ratio 2:1:1 NCO:OH=2:1. XIX As XVI ##STR24##
NHNH.sub.2 . H.sub.2 O andHN(CH.sub.2CH.sub.2OH).sub.2 molar ratio
10:1NCO:NH.sub.2 =1:1. Ethanolwater 1:1. Solids content 30%,
viscosity 5,000cp.; clear, colorless. ##STR25##
TABLE 2 Diisocyanate(s) Diamines(s) Properties of the elastomer
Preferred Macrodiol polycarbonate NCO:OH ratio NCO:OH ratio Solvent
solution application I Polycarbonate of octaethylene gly-col and
1,6-hexane diol in a molarratio of 1:3.4 with an OH-num-ber of 76.4
##STR26## ##STR27## Water:ethyl acetate etha- nol 1:2:3. Solids
content 30%, vis-cosity 70,000 cp. Textile coating agent:
par-ticularly suitable as a finish. II Polycarbonate of
tetraethyleneglycol and 1,6-hexane diol in a molar ratio of 5:2
with a hy-droxyl number of 90.4. ##STR28## ##STR29##
Water:ethanol:ethylacetate 1:2:1. Solids content 20%, vis- cosity
50,000 cp. Textile coating agent. and ##STR30## (1:1) NCO:OH = 2:1.
III Tetraethylene glycol poly carbon-ate with a hydroxyl number
of63. ##STR31## ##STR32## Water:isopropanol:ethylacetate 2:1:1.
Solids content 25%, vis-cosity 30,000 cp. Stoving lacquer and
tex-tile coating agent of high light stability. NCO:OH= 2:1.
NCO:NH.sub.2 = 1:0.90. IV As III ##STR33## ##STR34##
Water:ethanol:methylethyl ketone 1:2:2. Solids content 25%, vis-
cosity 30,000 cp. Coating of high elasticity.
EXAMPLE 5
A. A prepolymer containing NCO groups (NCO content 1.86 percent) is
prepared from 1 mol of a tetraethylene glycol polycarbonate with a
hydroxyl number of 28 and an average molecular weight of 4,000 with
2 mols of diphenyl methane-4,4'-diisocyanate by heating the
components for 2 hours to 70.degree. C. and is dissolved on heating
to form a 50 percent solution in methyl ethyl ketone.
B. 900 parts of the solution of the prepolymer obtained in (A) are
cooled to 0.degree. to 10.degree. C and then poured slowly onto a
solution, cooled to the same temperature, of 15 parts of 1
-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane and 0.4 parts of
dimethyl amine in a mixture of 450 parts of water and 180 parts of
isopropanol. A clear viscous solution (viscosity 28,000 cP) is
formed. A textile coating prepared with this solution is totally
resistant to perchlorethylene.
EXAMPLE 6
496 parts of a polycarbonate from triethylene glycol with an OH
number of 226 were dehydrated in vacuo (12 mm Hg) at 80.degree. to
100.degree. C, followed by the addition of 444 parts of
1-isocyanato-3-isocyanato methyl-3,5,5-trimethyl cyclohexane. The
reaction was terminated after the NCO content had fallen to
slightly below the value of 8.95 percent.
After cooling to room temperature, the prepolymer was a viscous,
but still stirrable mass. 800 parts of water were introduced with
vigorous stirring into this mass, resulting in the formation of a
hazy, low-viscosity mixture. A prepared solution of
1-amino-3-amino-methyl, 3,5,5-trimethyl cyclohexane in 945 parts of
ethanol and 200 parts of i-butanol were added to this mixture
quickly, but not too quickly, with vigorous stirring. Towards the
end of the addition there was a marked increase in the viscosity
and the further introduction of amine solution was stopped when a
viscosity of approximately 25,000 cP had been reached.
The completed solution was applied to a release paper
(approximately 0.3 mm thick) and, after the solvent had been
evaporated off, gave a clear, hard colorless film.
If the i-butanol is replaced by ethanol, the film clouds until it
is milky white in appearance following the evaporation of the
alcoholic fraction of the solvent. After the water has been
evaporated, the cloudiness disappears and the film becomes
clear.
EXAMPLE 7
A. 1,400 parts of a polycarbonate from triethylene glycol with an
OH-number of 80 were dehydrated in vacuo (12 mm Hg) at 80.degree.
to 100.degree. C, followed by the addition of 252 parts of
1,6-diisocyanato hexane. Formation of the prepolymer was regarded
as complete after the NCO-content had fallen to slightly below the
value of 2.54 percent. The viscous reaction mass was diluted with
420 parts of ethylacetate. 111 parts of 1-isocyanato-3-isocyanato
methyl-3,5,5-trimethyl cyclohexane were slowly added to 50 parts of
hydrazine hydrate in 1,680 parts of isopropanol. The finished
solution was diluted with 1,680 parts of water and the solution of
the prepolymer added gradually with vigorous stirring. Towards the
end of the addition, there was a marked increase in the viscosity
and the introduction of amine solution was stopped after a
viscosity of approximately 30,000 cP had been reached. The finished
solution was applied to a release paper (approximately 0.3 mm
thick) and, after evaporation of the solvent, gave a soft, clear
colorless film. B. 100 parts of the solution prepared as described
above were stirred with 1.5 parts of a reaction product of
1,3-butane diol, methoxy methyl isocyanate and 0.3 parts of maleic
acid, the resulting mixture was processed in the same way to form a
film. If the dry film is heated for 40 - 60 seconds to 130.degree.
- 150.degree. C, it is completely resistant after this treatment
both to aqueous alcohol and also to water or alcohol.
C. A textile material was coated as follows with the solution
prepared in accordance with B:
100 parts of the solution were mixed with 1.5 to 3 parts of a 50
percent paste obtained by grinding a conventional
cellulose-acetobutyrate-modified pigment in methyl ethyl ketone,
and the resulting mixture was applied to a release paper in a wet
layer thickness of 100 .mu.. Following the evaporation of the
solvent, a second coat was applied, again in a wet layer thickness
of 100 .mu., and the textile fabric, which was mechanically napped
on one side, was placed with its napped side on the still wet
coating, followed by uniform pressing by passage through a 0.5 to 1
mm wide roller gap. Following the evaporation of the solvent, the
entire assemblage was exposed to a temperature of 130.degree. to
150.degree. C for from 40 to 60 seconds and the coated fabric
subsequently separated from the release paper which was
reusable.
The following modified procedures are also possible:
1. Following its application, the first coat is subjected to a heat
shock (40 to 60 seconds at 130.degree. - 150.degree. C).
2. An unpigmented solution according to (B) is used as the second
coat.
3. The only heat shock or, in the case of modification 1, the
second heat shock (40 to 60 seconds at 130.degree. - 150.degree.
C.) can also be applied after separation of the coated textile
material from the release paper.
EXAMPLE 8
1,680 parts of a polycarbonate from triethylene glycol with an
OH-number of 66.6 were dehydrated in vacuo at 80.degree. -
100.degree. C. followed by the addition of 444 parts of
1-isocyanato-3-isocyanato methyl-3,5,5-trimethyl cyclohexane.
Formation of the prepolymer was regarded as complete after the NCO
content had fallen to slightly below the value of 3.92 percent. The
viscous reaction mass was diluted with 930 parts of acetone. 210
parts of 4,4'-diamino dicyclohexyl methane were dissolved in 1,400
parts of water and 2,300 parts of acetone and added quickly, but
not too quickly, to the acetone prepolymer solution. Towards the
end of the addition, there was a marked increase in the viscosity
and the introduction of amine solution was stopped after a
viscosity of 45,000 cP had been reached.
The completed solution was applied to a release paper
(approximately 0.3 mm thick) and, after evaporation of the solvent,
gave a soft, clear colorless film which showed outstanding
resistance to the effect of light and hydrolysis.
EXAMPLE 9
1,940 parts of a polycarbonate from triethylene glycol with an
OH-number of 56.8 were dehydrated in vacuo (12 mm Hg) at 80.degree.
- 100.degree. C, followed by the addition of 444 parts of
1-isocyanato-3-isocyanato methyl-3,5,5-trimethyl cyclohexane.
Formation of the prepolymer was regarded as complete after the
NCO-content had fallen to slightly below the value of 3.53 percent.
A solution of 210 parts of 4,4'-diamino-3,3'-dimethyl dicyclohexyl
methane in 1,410 parts of water and 3,240 parts of ethyl alcohol
was added in one addition to the prepolymer mass which was viscous
at room temperature. The prepolymer began to react with the diamine
with increasing dissolution. After a homogeneous mixture had been
obtained the viscosity of the solution was 850 cP.
EXAMPLE 10
2,685 parts of a polycarbonate from triethylene glycol with an
OH-number of 41.8 were dehydrated in vacuo (12 mm Hg), followed by
the addition of 444 parts of 1-isocyanato-3-isocyanato
methyl-3,5,5-trimethyl cyclohexane. Formation of the prepolymer was
regarded as complete after the NCO-content had fallen to slightly
below the value of 2.69 percent. The viscous reaction mass was
diluted with 1520 parts of ethylacetate, followed by stirring for
15 minutes with 3 parts of butyl amine. A solution of 152 parts of
1-amino-3-amino methyl-3,5,5-trimethyl cyclohexane in 3,040 parts
of water and 3,040 parts of isopropanol was then added to this
solution over a period of about 30 minutes. After stirring for
another 30 minutes, the viscosity remained constant at
approximately 10,000 cP.
The completed solution was applied to a release paper
(approximately 0.3 mm thick) and, following evaporation of the
solvent and removal of the release paper, gave a very soft, clear
colorless film.
EXAMPLE 11
1,015 parts of a polycarbonate from triethylene glycol and with an
OH-number of 110.4 were dehydrated in vacuo (12 mm Hg) at
80.degree. - 100.degree. C, followed by the addition of 666 parts
of 1-isocyanato-3-isocyanato methyl-3,5,5-trimethyl cyclohexane.
Formation of the prepolymer was regarded as complete after the
NCO-content had fallen to slightly below the value of 10.0 percent.
The viscous reaction mass was diluted with 920 parts of
ethylacetate. 304 parts of 1-amino-3-amino methyl-3,5,5-trimethyl
cyclohexane were dissolved in 1,860 parts of water and 3,360 parts
of isopropanol and the resulting solution added over a period of 30
to 60 minutes to the thoroughly stirred and cooled prepolymer
solution. Towards the end of the addition, there was a marked
increase in the viscosity and the introduction of amine solution
was stopped after a viscosity of about 30,000 cP had been
reached.
The completed solution was applied to a release paper
(approximately 0.3 mm thick) and, following evaporation of the
solvent, gave an extremely hard, clear and high-gloss film with
outstanding resistance to the effect of light and hydrolysis.
Following dilution with an H.sub.2 O:alcohol mixture (1:2) to a
viscosity of around 1,000 cP, the solution is suitable for the
application of a finish by conventional methods (spraying,
knife-coating, roll-coating, pressing etc.) A coating of 5 .mu. of
solid substance is sufficient to obtain a smooth, dry feel, even on
an extremely soft substrate (coated leather, textile or web).
Further Examples are set out in Table 3. The procedure of Example 7
was adopted for numbers 2, 3, 5, 8, 9, 10, 11, 12, 14, 15 and 17
and 18 and the procedure of Example 9 for numbers 1, 4, 6, 7, 13
and 16.
TABLE 3 Preferred application of the Type of macrodiol poly-
Diisocyanate(s ) (NCO:OH Solvent (proportions in Properties of the
elastomer polyuretha ne poly urea carbonate used ratio) Diamine(s)
(NCO:NH.sub.2 ratio) percent by weight) solution elastomer 1 Basis:
triethylene glycol,molecular weight 500. ##STR35## H.sub.2
NNH.sub.2 . H.sub.2 O (1:1) H.sub.2 O, 50; ethanol
40;.iota.-butanol, 10. Solids content 40%; colorless,slig htly
hazy. Finish for textile coatings. 2 As 1 (MW 1,020) As 1 (2:1) As
1 (1:1) H.sub.2 O, 40; ethanol, 10; Solids content 35%; clear, low-
" acetone, 50. viscosity solution. 3 As 1 (MW 1,180) " ##STR36##
H.sub.2 O, 40; isopropanol, 50; ethylacetate, 10. Solids content
30%; slightlyhazy solution; .eta.:30,000 cp. Hard textile coating,
plasticsand rubber lacquer. 4 As 1 (MW 1,440) " ##STR37## H.sub.2
O, 30; ethanol, 70. Solids content 30%; clear solution. Surface
layer for textile coating. 5 " OCN(CH.sub.2).sub.6NCO (1.5:1)
##STR38## H.sub.2 O, 45; isopropanol, 45;ethylacetate, 10. Solids
content 30%; clear highlyviscous solution. Soft adhesive layer for
textilecoatings. 6 " As 1 (2:1) H.sub.2 N(CH.sub.2).sub.6NH.sub.2
(1:1) H.sub.2 O 46 ethanol 41 Solids content 44%; .eta.: 6,000 cp.;
Elastic weather-resistan t films. .iota. butanol 13 clear solution.
7 " As 1 H.sub.2 N(CH.sub.2).sub.2NH.sub.2 (1:1) H.sub.2 O 50
ethanol 40 Solids content 50%; clear solution; Soft adhesive layer
for textile .iota. butanol 10 .eta.: 6,000 cp. coatings. 8 "
OCN(CH.sub.2).sub.6NCO(2:1) ##STR39## H.sub.2 O, 45; isopropanol,
40;ethylacetate, 10. Solids content 30%; clear highlyviscous
solution. Textile coating; paper coating. 9 " As 8 (2:1) As 8 plus
H.sub.2 NNH.sub.2 . H.sub.2 O ratio 9:1 (1:1) H.sub. 2 O, 40;
isopropanol, 40; Solids content 30%; solution gels Lacquering
metals. ethylacetate, 20. on standing. 10 " ##STR40## H.sub.2
NNH.sub.2 . H.sub.2 O(1:1). H.sub.2 O, 40; ethanol,
35;.iota.-butanol, 15; ethylace-tate, 10. Solids content 50%; clear
colorlesssolution. Lacquer for plastics. 11 As 1 (MW 1,690) As 1
(2:1) ##STR41## H.sub.2 O, 35; ethanol, 15:iso-propanol, 35
methylethylketone, 15. Solids contet 40%; slightly hazysolution;
.eta.:7,000 cp. Soft textile coating. 12 " " ##STR42## H.sub.2 O,
42; isopropanol, 44:ethylacetate, 14. Solids content 28.5%;
slightly hazysolution; I: 13,000 cp. " 13 " " H.sub.2 NNH.sub.2 .
H.sub.2 O (1:0.98) H.sub.2 O, 40; ethanol, 35; .iota.- Solids
content 43%; clear solution; Adhesive layer for soft textile
butanol 15. 1:15,000 cp. coatings. 14 " " H.sub.2
N(CH.sub.2).sub.6NH.sub.2 (1:1) H.sub.2 O, 40; ethanol, 35; .iota.-
Solids content 50%; .eta.: 45,000 cp. Elastic films of outstanding
light butanol, 15; ethylacetat e, stability. 10. 15 " ##STR43##
##STR44## H.sub.2 O. 35; isopropanol, 35;ethylacetate, 30. Solids
content 30%; clear colorless solution; .eta.: 22,000 cp. Textile
coating of outstandin glight stability. 16 As 1 (MW 1,940) As 1
(2.5:1) ##STR45## H.sub.2 O, 30; ethanol, 70 Solids content 50%;
slightly hazysolution; .eta.:40,000 cp. Textile coating with
highresistance to hydrolysis. 17 As 1 (MW 2,685) As 1 (2:1) As 16
plus CH.sub.3(CH.sub.2).sub.3NH.sub.2,ra tio 99:1 (1:0.9) H.sub.2
O, 40; isopropanol, 40; Solids content 30%; clear Adhesive layer
for very soft ethylacetate, 20. solution; .eta.: 10,000 cp. textile
coatings. 18 Same as above Same as above ##STR46## H.sub.2 O, 40;
isopropanol, 35;ethylacetate, 25. Solids content 30%; .eta.:35,000
cp.Very soft light-stable textilecoating.
* * * * *