Note: Descriptions are shown in the official language in which they were submitted.
~~o~.v~~
OLEFINICALLY UNSATURATED COMPOUNDS A PROCESS FOR THE
PRODUCTION OF COPOLYMERS CONTAINING ISOCYANATE
GROUPS. THE COPOLYMERS THUS OBTArNED AND
COATING COMPOSITIONS OR SEALING COMPOUNDS
CONTAINING THE COPOLYMERS
This inventian relates to olefinically unsaturated
compounds containing isocyanate groups attached to tertiary
carbon atoms, to a process fox the production of copolymers
using these compounds, to the corresponding copolymers and
to coating compositions or sealing compounds containing the
copolymers as binder component.
BACKGROUND OF THE INVENTION
Copolymers containing free isocyanate groups and their
use as binder component in Two-cor.~.ponent ccating composi
tions are known.
Thus, DE-OSS 3 245 294, 3 245 295 and 3 245 298 for
example describe isocyanate-functional copolymers which are
produced using vinyl isocyanate as unsaturated NCO-func-
tional monomer, while US-PS 3,004,527, 4,219,632, 4,401,
794 and 4,510,298 describe isocyanate-functional copolymers
which are produced using isocyanatoethyl methacrylate as
NCO-functional monomer. Where these two NCO functional
monomers are used for the production of copolymers, the
copolymers obtained contain primary isocyanate groups.
However, these primary isocyanate groups are too reactive
to the nitrogen-containing crosslinking agents commonly
used, such as for example polyketimines or polyoxazolanes,
so that the pot lives obtained where the copolymers are
used in two-component coating systems are not long enough.
Copolymers containing chemically incorporated, ter
tiary aliphatic isocyanate groups are described, for ex-
ar.~le, in US 4 754 011, CA 1 246 783, J 61 120-667-A
(C.A. 105 192 987), J 61 120-862-A (C.A. 105 192 967), J 61
126-177-A (C.A. 105 192 991) or J 61 126-178-A (C.A. 105
Le A 26 444 1
r
~~0~:~~3
192 992). In these cases, the isocyanate group is intro-
duced through the use of m-isopropenyl-a, a-dimethylbenzyl
isocyanate as the isocyanate-functional copolymerizable
monomer. However, where this monomer is used for radical
copolymerization with other unsaturated monomers, such as
for example esters of (meth)acrylic acid or styrene, rel-
atively large quantities of residual monomers are always
found because the quasi-a-methyl styrene structure of the
m-isopropenyl-a, a-dimethylbenzyl isocyanate copolymerizes
only inadequately with the other monomers mentioned above
on account of unfavorable copolymerization parameters.
Even corresponding reactivation with additional quantities
of radical initiators fails to produce any significant in-
crease in the monomer conversion, i.e. any real reduction
in the residual monomer content. Large amounts of residual
monomers in binders for coating purposes are of course
harmful to health, so that binders are unsuitable for this
application.
Japanese specification 54 419 as laid open (C. A. _100 211 228).
2 0 describes copolymers
containing isocyanate groups which have been produced using
reaction products of hydroxyethyl acrylate with diisocyan-
atotoluene or with diisocyanatohexane. These copolymers
are intended to be used for the production of adhesives.
Quite apart from the problems involved in the production of
olefinically unsaturated monomers from hydroxyethyl acryl-
ate and diisocyanates containing isocyanate groups of the
same or substantially the same reactivity (the reaction of
the starting materials mentioned generally always leads to
large quantities of unwanted 2:1 adducts),~the isocyanate
groups present in the copolymers of this prior publication
are those of comparatively high reactivity which are
unsuitable for the production of two-component lacquers in
combination With nitrogen-containing crosslinking agents on
account of the inadequate pot lives.
Le A 26 444 2
i~~~~.~~a~
Basically the same observations apply to the copoly-
mers according to Japanese specification 267 523 as laid
open (C.A. 106 157 585) which are also intended for the production of
adhesives and in the production of which reaction products
of isophorone diisocyanate with hydroxyethyl acrylate are
used as the monomers containing isocyanate groups.
Accordingly, the object of the present invention is to
provide new, olefinically unsaturated isocyanates suitable
as isocyanate-functional monomers and also copolymers
containing them as constituents which are not attended by
the disadvantages of the prior art.
This object is achieved by the provision of the ole
finically unsaturated monoisocyanates described in detail
hereinafter and the copolymers produced with them.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to olefinically unsat
urated compounds having a molecular weight in the range
from 252 to 800, characterized by
(i) a content of 7 to 24% by weight of urethane groups and
(ii) a content of 5 to 17% by weight of isocyanate groups
which are attached to tertiary carbon atoms which in
turn are part of a cycloaliphatic ring.
The present invention also relates to a process for
the production of copolymers containing isocyanate groups,
which have a weight average molecular weight of 1,000 to
100,000, by radically initiated copolymerization of ole-
finically unsaturated monomers free from isocyanate groups
with olefinically unsaturated monoisocyanates in such a
quantity that the resulting copolymers contain from 0.1 to
13% by weight of chemically incorporated isocyanate groups
for an average NCO functionality of the copolymers of at
least 2, characterized in that unsaturated compounds of the
type according to the invention are used as the olefinic-
T~ A 2f 444
~~D1.U(~~
ally unsaturated monoisocyanates.
The present invention also relates to copolymers con-
taining isocyanate groups having a weight average molecular
weight of from 1,000 to 100,000 of olefinically unsaturated
compounds, characterized by an average NCO functionality of
at least 2 and a content of 0.1 to 13% by weight of iso-
cyanate groups attached to tertiary carbon atoms which, in
turn, are part of a cycloaliphatic ring.
Finally, the invention also relates to coating compo
sitions and sealing compounds containing as binder a two
component system of a polyisocyanate component and a poly
amine component containing blocked amino groups, character
ized in that the polyisocyanate component consists of co
polymers of the last-mentioned type.
DETAILED DESCRIPTION OF THE INVENTION
The olefinically unsaturated compounds according to
the invention are monoolefinically unsaturated monoisocyan-
ates which preferably have a molecular weight of from about
252 to 800, i.e. an NCO content of 5 to 17% by weight, and
a content of 7 to 24% by weight of urethane groups. The
isocyanate group in the compounds according to the inven-
tion is attached to a tertiary carbon atom which, in turn,
is part of a cycloaliphatic ring.
The olefinically unsaturated compounds according to
the invention are prepared by reaction of special starting
diisocyanates, which contain one aliphatically bound pri
mary isocyanate group and one cycloaliphatically bound
tertiary isocyanate group, with hydroxyl-functional, ole
finically unsaturated compounds in such a way that one
molecule hydroxyl compound is used per mol diisocyanate.
Polymerization inhibitors, such as for example 2,6-di-
tert.-butyl-4-methylphenol or hydroquinone monomethyl
ether, may optionally be added.
The starting diisocyanates are aliphatic-cycloali-
phatic diisocyanates having an NCO content of from 20 to
50% by weight and preferably from 30 to 48% by weight
_4_
T '. T '1 C A A A
n s~~~.~~~
which, in addition to a sterically unhindered, aliphatic-
ally bound isocyanate group, may contain a sterically hin-
dered isocyanate group attached to a tertiary carbon atom
which, in turn, is part of a cycloaliphatic ring. Suitable
starting diisocyanates are those corresponding to formula
(I) or mixtures of those corresponding to formula (I)
R1 \ / NCO
C
RZ\ ~ R3 (I)
C
Ro / ~ ( R5 ) n-CHZNCO
in which
R1 is an alkyl radical containing 1 to 4 carbon atoms,
preferably a methyl radical,
RZ and R3 are the same or different and represent a difunc-
tional, linear or branched saturated hydrocarbon radi-
cal containing 1 to 4 and preferably 1 to 3 carbon
atoms, the sum of the carbon atoms in these radicals
preferably being from 3 to 6 and more especially 4 or
5,
R4 represents hydrogen or an alkyl radical containing 1
to 4 carbon atoms, preferably hydrogen or a methyl
radical,
RS is a difunctional, linear or branched, saturated ali-
phatic hydrocarbon radical containing 1 to 4 and more
especially 1 to 3 carbon atoms and
n = 0 or 1.
Particularly preferred diisocyanates are, for example,
1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane,
which is generally present as a mixture of the 4- and 3-
isocyanatomethyl isomers, 1-isocyanato-1-methyl-4-(4-iso-
cyanatobut-2-yl)-cyclohexane or 1-isocyanato-1,2,2-trime-
thyl-3-(2-isocyanatoethyl)-cyclopentane. However, other
Le A 26 444 5
suitable diisocyanates are, for example, 1-isocyanato-1-n-
butyl-3-(4-isocyanatobut-1-yl)-cyclopentane, 1-isocyanato-
1-ethyl-4-n-butyl-4-(4-isocyanatobut-1-yl)-cyclohexane or
1-isocyanato-1,2-dimethyl-3-ethyl-3-isocyanatomethylcyclo-
pentane.
The corresponding diisocyanates are described in de-
tail in EP-A-0 153 561 and may be produced by the processes
described therein.
Suitable hydraxyfunctional, olefinically unsaturated
l0 compounds are any organic compounds containing an alcoholic
hydroxyl group and an olefinic double band. These com
pounds preferably have a molecular weight of 58 to 600.
Suitable compounds of this type are, for example, hydroxy
ethyl acrylate, 2- and 3-hydroxypropyl acrylate, 2-, 3- and
4-hydroxybutyl acrylate, hydroxyethyl methacrylate, 2- and
3-hydroxypropyl methacrylate, hydroxyethyl vinyl ether,
2-, 3- and 4-hydroxybutyl vinyl ether, allyl alcohol, reac-
tion products of unsaturated carboxylic acids, such as
acrylic acid for example, with epoxides, reaction products
of the hydroxyfunctional, olefinically unsaturated monomers
mentioned by way of example above with E-caprolactone, bu-
tyrolactone, ethylene oxide or propylene oxide.
The reaction of the special diisocyanates with the hy
droxyfunctional, olefinically unsaturated monomers mention
ed by way of example above is best carried out in such a
way that 1 mol hydroxyl compound is used per mol diisocyan-
ate.
The reaction may be carried out both in the presence
and in the absence of a solvent inert to isocyanate and hy-
droxyl groups. The reaction temperature is in the range
from 0 to 100°C and preferably in the range from 20 to
80°C. In addition, catalysts such~as, for example, ter-
tiary amines, organic zinc or tin compounds or other com-
pounds which catalyze a urethanization reaction, may also
be added in small c3uantities. The reaction products ob-
he A 26 444 6
s~~~~.~~.~
tained are generally monoadducts of the special starting
diisocyanates and the particular hydroxyfunctional, ole-
finically unsaturated compounds used which may be used
without additional working up or purification processes for
the production of the isocyanate-functional copolymers ac-
cording to the invention.
The monomers Free from isocyanate groups which are co-
polymerized with the olefinically unsaturated monoisocyan-
ates according to the invention in the process according to
the invention are the usual, preferably monoolefinically
unsaturated monomers which are already used as monomers in
the process according to the prior art mentioned above.
Typical examples are esters of acrylic and methacrylic
acid, such as methyl acrylate, ethyl acrylate, n-butyl
acrylate, isobutyl acrylate, tent-butyl acrylate, 2-ethyl
hexyl acrylate, cyclohexyl methacrylate, methyl methacry-
late, n-butyl methacrylate, isobutyl methacrylate or 2-
ethyl hexyl methacrylate: aromatic vinyl compounds, such as
for example styrene, vinyl toluene, a-methyl styrene, cx-
ethyl styrene, nucleus-substituted diethyl styrenes op-
tionally representing isomer mixtures, isopropyl styrenes,
butyl styrenes and methoxystyrenes; vinyl ethers, such as
for example ethyl vinyl ether, n-propyl vinyl ether, iso-
propyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl
ether; vinyl esters, such as for example vinyl acetate,
vinyl propionate and vinyl butyrate.
Mixtures of the monomers mentioned by way of example
may of course be used to carry out the copolymerization.
The copolymers are produced, i.e. the process accord-
ing to the invention is carried out, by copolymerization of
the monomers mentioned by way of example, the olefinically
unsaturated monoisocyanates essential to the invention
being used in such a quantity that the resulting copolymers
contain from 0.1 to 13% by weight and preferably from 1 to
10% by weight of free isocyanate groups. In practice, this
Le A 26 444
~o~~~~~
means that, in general, the ratio by weight of monomers
containing isocyanate groups to monomers free from isocyan-
ate groups of the type mentioned by way of example is from
0.01:1 to 24:1. The copolymerization is carried out by
standard radical polymerization processes, such as for ex-
ample bulk or solution polymerization. The monomers are
copolymerized at temperatures in the range from 60 to 200 ° c
and preferably at temperatures in the range from 80 to
160°C in the presence of radical formers and, optionally,
molecular weight regulators.
The copolymerization is preferably carried out in
inert solvents at solids contents of 30 to 95% by weight.
Suitable solvents are, for example, aromatic hydrocarbons,
such as benzene, toluene, xylene; esters, such as ethyl
acetate, butyl acetate, methyl glycol acetate, ethyl glycol
acetate, methoxypropyl acetate: ethers, such as tetrahydro-
furan, dioxane, diethylene glycol dimethyl ether; ketones,
such as acetone, methyl ethyl ketone, methyl isobutyl ke-
tone.
The copolymerization may be carried out continuously
or discontinuously. Normally, the monomer mixture and the
initiator are introduced uniformly and continuously into a
polymerization reactor and the corresponding quantity of
polymer is continuously removed at the same time. It is
thus possible with advantage to produce chemically sub-
stantially uniform copolymers. Chemically substantially
uniform copolymers may also be produced by allowing the re-
action mixture to run at a constant rate into a stirred
vessel without removal of the polymer.
It is also possible, for example, initially to intro-
duce part of the monomers, for example in solvents of the
type mentioned, and to add the remaining monomers and aux-
iliaries either separately or together to the monomers ini-
tially introduced at the reaction temperature.
In general, the polymerization is carried out at an
Le A 26 444 8
i~~~~.~~a~
excess pressure of 0 to 20 bar. The initiators are used in
quantities of 0.05 to 15% by weight, based on the total
quantity of monomers.
Suitable initiators are standard radical initiators
such as, for example, aliphatic azo compounds, such as azo
diisobutyronitrile, azo-bis-2-methyl valeronitrile, 1,1'
azo-bis-1-cyclohexane nitrile and 2,2'-azo-bis-isobutyric
acid alkyl ester; symmetrical diacyl peroxides, for example
acetyl, propionyl or butyryl peroxide, bromine-, vitro-,
methyl- or methoxy-substituted benzoyl peroxides, lauryl
peroxides; symmetrical peroxydicarbonates, for example
diethyl, diisopropyl, dicyclohexyl and also dibenzoyl per-
oxydicarbonate: tart.-butyl peroctoate, tart.-butyl per-
benzoate or tart.-butyl phenyl peracetate, and also peroxy-
carbonates such as, for example, tart.-butyl-N-(phenylper-
oxy)-carbonate or tart.-butyl-N-(2-,3- or 4-chlorophenyl-
peroxy)-carbonate; hydroperoxides, such as for example
tart.-butyl hydroperoxide, cumene hydroperoxide; dialkyl
peroxides, such as dicumyl peroxide, tart.-butyl cumyl
peroxide or di-tart.-butyl peroxide.
To regulate the molecular weight of the copolymers,
standard regulators may be used during their production,
including for example tart.-dodecyl mercaptan, n-dodecyl
mercaptan or diisopropyl xanthogene disulfide. The molec-
ular weight regulators may be added in quantities of from
0.1 to 10% by weight, based on the total quantity of mono-
mars.
In addition, the copolymers have a molecular weight
(weight average), as determined by gel permeation chroma-
tography, of from 1,000 to 100,000, preferably from 1,500
to 75,000 and more preferably from 2,000 to 50,000.
The solutions of the copolymers obtained during the
copolymerization reaction may be used in accordance with
the invention without further working up. However, it is
of course also possible to free the copolymers from any
Le A 26 444 9
residues of unreacted monomers still present and from
solvent by distillation and to use the copolymers obtained
as distillation residue in accordance with the invention.
Two-component systems of a polyisocyanate component A)
and a hardener B) are present as binder in the coating com
positions or sealing compounds according to the invention.
The polyisocyanate component A) is one of the isocyanate
functional copolymers according to the invention. The
hardener component B) is an organic polyamine containing
blocked amino groups. °'Blocked amino groups" are under-
stood to be groups which react with water with release of
primary and/or secondary amino groups. Particularly pre-
ferred blocked polyamines B) are compounds which contain
aldimine, ketimine, oxazolane, hexahydropyrimidine and/or
tetrahydroimidazole groups and which, at the same time, may
also contain several of these groups.
The blocked polyamines B) have a weight average molec-
ular weight in the range from 86 to 10,000 and preferably
in the range from 250 to 4,000 and, on a statistical aver-
age, contain from 1 to 50, preferably from 2 to 10 and more
preferably from 2 to 4 structural units corresponding to
the following general formulae
~ ~~Re I R ~ C NLRB and/or R ~C=N--
> > >
(II) (III) (IV)
in which
R6 and R~ may be the same or different and represent hydro-
gen, aliphatic hydrocarbon radicals containing from 1
to 18 carbon atoms, cycloaliphatic hydrocarbon radi-
cals containing from 5 to 10 carbon atoms, araliphatic
hydrocarbon radicals containing from 7 to 18 carbon
Le A 26 444 10
~oo~:oo~
atoms or phenyl radicals; the two substituents Rs and
R~ may also form a 5-membered or 6-membered cycloali
phatic ring together with the adjacent carbon atom
and, preferably, at most one of these substituents is
hydrogen, and
R8 is a difunctional aliphatic hydrocarbon radical con-
taining 2 to 6 carbon atoms, with the proviso that 2
or 3 carbons are arranged between the twa nitrogen
atoms.
The molecular weights mentioned may be determined by
the method of gel permeation chromatography (molecular
weights above 1,000) or from the stoichiometry of the
starting materials used for the production of the compounds
(molecular weights up to 1,000).
Components B) preferably used are, for example, those
containing hexahydropyrimidine or tetrahydroimidazole
structures corresponding to general formula (II), in which
Rs and R~ may be the same or different and represent ali-
phatic hydrocarbon radicals containing 2 to ZO carbon
atoms; one of these substituents may also be hydrogen and
R~ may be an optionally alkyl-substituted ethylene or tri-
methylene radical.
The blocked polyamines of the type mentioned are pro
duced in known manner by reaction of corresponding alde
hydes or ketones with the corresponding polyamines.
Aldehydes or ketones suitable for the production of
the compounds B) containing hexahydropyrimidine or tetra-
hydroimidazole groups are, for example, those corresponding
to the following general formula:
Rs
C=O
R~
which preferably have a molecular weight of from 72 to 200
Le A 26 444 11
~r~~~~o~
(ketones) or from 58 to 250 (aldehydes).
Examples of such aldehydes and ketones are acetone,
methyl ethyl ketone, methyl propyl ketone, methyl isopropyl
ketane, methyl-n-butyl ketone, methyl isobutyl ketone,
methyl-n-amyl ketone, methyl isoamyl ketone, methyl heptyl
ketone, diethyl ketone, ethyl butyl ketone, ethyl amyl ke-
tone, diisopropyl ketone, diisobutyl ketone, cyclohexanone,
isophorone, methyl-tert.-butyl ketone, 5-methyl-3-hepta-
none, 4-heptyl ketone, 1-phenyl-2-propanone, acetophenone,
methyl nonyl ketone, 3,3,5-trimethyl cyclohexanone, formal-
dehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-
butyraldehyde, trimethyl acetaldehyde, 2,2-dimethyl propan-
al, 2-ethyl hexanal, 3-cyclohexene-1-carboxaldehyde, hexan-
al, heptanal, octanal, valeraldehyde, benzaldehyde, tetra-
hydrobenzaldehyde, hexahydrobenzaldehyde, acrolein, croton-
aldehyde, propargylaldehyde, p-tolylaldehyde, 2-methyl pen-
tanal, 3-methyl pentanal, phenyl ethanal, 4-methyl pen-
tanal.
Aldehydes and ketones preferably used for the produc-
tion of the compounds containing hexahydropyrimidine or
tetrahydroimidazole groups are butyraldehyde, isobutyral-
dehyde, trimethyl acetaldehyde, 2,2-dimethyl propanal, 2-
ethyl hexanal, hexanal, 3-cyclohexane-1-carboxaldehyde,
heptanal, octanal, hexahydrobenzaldehyde, 2 -methyl pentan-
al, cyclohexanone, cyclopentanone, methyl isopropyl ketone,
acetone, 3,3,5-trimethyl cyclohexanone and methyl cyclo-
hexanone.
It is of course also possible to use mixtures of dif
ferent ketones and aldehydes and also mixtures of ketones
with aldehydes to obtain special properties.
The polyamines used for the production of the com-
pounds containing hexahydropyrimidine or tetrahydroimidaz-
ole groups are, in particular, organic compounds containing
at least two primary and/or secondary amino groups.
Suitable polyamines are, for example, those corre-
Le A 26 444 12
sponding to the following general formula
R9-NH-R8-NH-Rlo
in which
RB is as defined above and
Ra and Rlo may be the same or different and represent hydro-
gen, aliphatic hydrocarbon radicals containing from 1
to 10 and preferably from 1 to 4 carbon atoms, cyclo-
aliphatic hydrocarbon radicals containing from 5 to 10
and preferably 6 carbon atoms or aromatic hydrocarbon
radicals containing from 7 to 15 and preferably 7 car-
bon atoms, the hydrocarbon radicals mentioned, partic-
ularly the aliphatic hydrocarbon radicals mentioned,
optionally containing heteroatoms, such as oxygen,
nitrogen or sulfur in the form of ether, ester, amide,
urethane, oxirane, ketone, lactam, urea, thioether,
thioester or lactone groups; the radicals may also
contain reactive hydroxyl or amino groups.
Particularly preferred polyamines are those in which
R9 and Rxo may be the same or different and represent hydro-
gen and/or C1-Cs alkyl radicals, such as methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, n-pentyl
or n-hexyl radicals, or in which at least one of the sub-
stituents Rg and R9 is a group of the type obtained by
addition of an amine hydrogen atom onto an olefinically
unsaturated compound. Olefinically unsaturated compounds
suitable for the production of modified polyamines such as
these are, for example, derivatives of (meth)acrylic acid,
such as esters, amides, nitriles or, for example, aromatic
vinyl compounds, such as styrene, a-methyl styrene, vinyl
toluene or, for example, vinyl esters, such as vinyl ace-
tate, vinyl propionate, vinyl butyrate or, for example,
vinyl ethers, such as ethyl vinyl ether, polyvinyl ether,
butyl vinyl ether, or monoesters and diesters of fumaric
Le A 26 444 13
acid, malefic acid or tetrahydrophthalic acid.
Rs and/or Rlo may also represent an aminoalkyl or hy-
droxyalkyl radical containing, for example, 2 to 4 carbon
atoms.
Especially preferred polyamines are ethylenediamine,
1,2-propylenediamine, 1,3-propylenediamine, 1,2- and 1,3-
butylenediamine, diethylenetriamine and derivatives of
these polyamines.
Compounds containing oxazolane groups of general
formula (III) suitable for use as component B) are pref
erably those in which Rs and R~ may be the same or differ
ent and represent hydrogen or aliphatic hydrocarbon radi
cals containing 1 to 18 and more especially 1 to 8 carbon
atoms, or in which the substituents Rs and R~, together with
the carbon atom of the heterocyclic ring, form a cycloali-
phatic ring containing in all from 4 to 9 carbon atoms,
more especially a cyclohexane ring, with the proviso that
at most one of the substituents Rs and R, is hydrogen, and
Rs is an alkenyl radical containing 2 to 4 and preferably 2
to 3 carbon atoms, with the proviso that at least 2 carbon
atoms are arranged between the oxygen atom and the nitrogen
atom.
The oxazolane-containing component B) is produced in
known manner by reaction of corresponding aldehydes or ke-
tones having the following formula
Rs
C=O
R~
with suitable hydroxyamines of the type mentioned in more
detail hereinafter.
Basically, suitable aldehydes or ketones are those of
the type already mentioned by way of example in the fore
going. Preferred aldehydes or ketones in this case are
~e A 26 444 14
butyraldehyde, isobutyraldehyde, trimethylacetaldehyde,
2,2-dimethyl propanal, 2-ethyl hexanal, 3-cyclohexene-1-
carboxaldehyde, hexahydrobenzaldehyde, cyclopentanone, cy-
cloh:exanone, methyl cyclopentanone, methyl cyclohexanone,
3,3,5-trimethyl cyclohexanone, cyclobutanone, methyl cyclo-
butanone, acetone, methyl ethyl ketone and methyl isobutyl
ketone.
It is of course also possible to use mixtures of dif-
ferent ketones and aldehydes and also mixtures of ketones
with aldehydes to obtain special properties.
Hydroxyamines are, in particular, organic compounds
which contain at least one aliphatic amino group and at
least one aliphatically bound hydroxyl group. The hydroxy-
amines generally have a molecular weight in the range from
61 to 500 and preferably in the range from 61 to 300.
Suitable hydroxyamines are, for example, bis-(2-
hydroxyethyl)-amine, bis-(2-hydroxypropyl)-amine, bis-(2-
hydroxybutyl)-amine, bis-(3-hydroxypropyl)-amine, bis-(3-
hydroxyhexyl)-amine, N-(2-hydroxypropyl)-N-(2-hydroxy-
ethyl)-amine, 2-(methylamino)-ethanol, 2-(ethylamino)
ethanol, 2-(propylamino)-ethanol, 2-(butylamino)-ethanol,
2-amino-2-methyl-1-propanol,2-amino-2-ethyl-1-propanol,2
amino-2-propyl-1-propanol, 2-amino-2-methylpropane-1,3
diol, 2-amino-3-methyl-3-hydroxybutane, propanolamine,
ethanolamine.
Particularly preferred hydroxyamines are bis-2-hy-
droxyethyl)-amine, bis-(2-hydroxypropyl)-amine, bis-(2-hy-
droxybutyl)-amine, bis-(3-hydroxyhexyl)-amine, 2-(methyl-
amino)-ethanol, 2-(ethylamino)-ethanol, 2-amino-2-methyl-
1-propanol, 2-amino-2-ethyl-1-propanol, propanolamine and
ethanolamine.
Preferred compounds containing aldimine or ketimine
groups are those which contain structural units having the
following general formula
Le A 26 444 15
~~~.~.~~,3
R6 a '
c=rr- ( Iv)
R~
in which
Rs and R~ may be the same or different and represent hydro-
gen or aliphatic hydrocarbon radicals containing 1 to
8 carbon atoms which may also be attached together
l0 with the carbon atom to form a cycloaliphatic ring,
more especially a cyclohexane ring.
In principle, the aldehydes or ketones already men-
tioned by way of example in the foregoing are suitable for
the production of these compounds. Preferred aldehydes or
ketones in this case are butyraldehyde, isobutyraldehyde,
trimethyl acetaldehyde, 2,2-dimethyl propanal, 2-ethyl
hexanal, 3-cyclohexene-1-carboxaldehyde, hexahydrobenz-
aldehyde and, in particular, ketones which have a boiling
point below 170°C and which show high volatility at room
temperature, including for example methyl isobutyl ketone,
methyl isoprapyl ketone, diethyl ketone, diisobutyl ketone,
methyl tert.-butyl ketone.
It is of course also possible to use mixtures of dif
ferent ketones or aldehydes and also mixtures of ketones
with aldehydes to obtain special properties.
The polyamines used for the production of component B)
containing ketimine or aldimine groups are, in particular,
organic compounds containing at least two aliphatically
and/or cycloaliphatically bound primary amino groups. How-
ever, the use of polyamines containing aromatic amino
groups is also possible, although less preferred. The
polyamines generally have a molecular weight of from 60 to
500 and preferably from 88 to 400, although it is also
possible to use relatively high molecular weight, amino-
terminated prepolymers as the polyamine component in the
~e A 26 444 16
production of component B).
Particularly preferred polyamines are diprimary ali-
phatic or cycloaliphatic diamines such as, for example,
tetramethylenediamine, hexamethylenediamine, isophorone-
diamine, bis-(4-aminocyclohexyl)-methane, bis-aminomethyl
hexahydro-4,7-methanoindane, 1,4-cyclohexanediamine, 1,3-
cyclohexandiamine, 2-methyl cyclohexanediamine, 4-methyl
cyclohexanediamine, 2,2,5-trimethyl hexanediamine, 2,2,4-
trimethyl hexanediamine, butane-1,4-diol bis-(3-aminopro-
pyl)-ether, 2,5-diamino-2,5-dimethyl hexane, bis-amino-
methyl cyclohexane, bis-(4-amino-3,5-dimethylcyclohexyl)-
methane or mixtures thereof.
Tetramethylenediamine, hexamethylenediamine, isophor
onediamine, bis-aminomethyl cyclohexane, 1,4-cyclohexane
diamine, bis-aminomethyl hexahydro-4,7-methanoindane and
bis-(4-aminocyclohexyl)-methane are particularly preferred.
In addition tp these preferred diamines, prepolymers
terminated by primary amino groups, i.e. compounds contain
ing at least two terminal amino groups and having a molec
ular weight of from 500 to 5,000 and preferably from 500 to
2,000, may also be used for the production of the aldimines
or ketimines. These compounds include, for example the
aminopolyethers known per se from polyurethane chemistry,
of the type described for example in EP-A 0 081 701, or re-
action products - for example containing amide, urea, ure-
thane or secondary amino groups - of at least difunctional
carboxylic acids, isocyanates or epoxides with diamines of
the type mentioned by way of example above, these reaction
products also containing at least two primary amino groups.
Mixtures of such relatively high molecular weight poly-
amines with the low molecular weight polyamines mentioned
may also be used.
Aromatic polyamines which, in principle, are also
suitable, but less preferred, for the production of the
aldimines or ketimines include, for example, 2,4- and 2,6-
Le A 26 444 17
W~Q~.~fl;~
diaminotoluene, 1,4-diaminobenzene or 4,4'-diaminodiphenyl
methane.
Component B), which may contain aldimine, ketimine,
oxazolane, hexahydropyrimidine or tetrahydroimidazole
groups, is prepared by reaction of the starting components,
generally in such quantitative ratios that the amino com-
pounds are present in a 1 to 1.5-fold molar excess, based
on the carbonyl groups, according to the particular reac-
tion required. Catalytic quantities of acidic substances,
such as for example p-toluenesulfonic acid, hydrochloric
acid, sulfuric acid, aluminium(III) chloride, tin com-
pounds, may optionally be used to accelerate the reaction.
The reaction is generally carried out at a temperature
in the range from 60 to 180°C, the reaction being carried
out in the presence of an entraining agent to remove the
water of reaction until the calculated quantity of water
has been eliminated or until no more water is eliminated.
The entraining agent and any unreacted starting mater-
ials present axe then removed by distillation. Suitable
entraining agents are, for example, toluene, xylene, cy
clohexane, octane. The crude products thus obtained may be
used without further purification as component B) for the
production of the binder combinations. Where the purity of
component B) has to meet particularly stringent require
ments, it is also possible to obtain components B) in pure
form, for example by distillation.
The preferred, blocked polyamines of component B) also
include those which contain 2 to 10 structural units corre-
sponding to general formula (II), (III) or (IV) and which
are obtained by linkage of different compounds containing
such structural units to form, for example, ester, ether,
amide, urea and/or urethane bonds.
The compounds containing structural units correspond
ing to the above formulae, which are to be linked to one
another in this way, must contain at least one primary or
Le A 26 444 18
secondary amino group or at least one hydroxyl group in
non-blocked form. Suitable modifying agents, which are
suitable for linking the compounds mentioned, are for
example, polyisocyanates, polyepoxides, polycarboxylic
acids and polyacryloyl compounds.
Polyisocyanates suitable for this modification reac-
tion are, for example, aliphatic, cycloaliphatic, arali-
phatic, aromatic and heterocyclic polyisocyanates of the
type described, for example, by W. Siefken in 5ustus
Liebigs Annalen der Chemie, 562, pages 75 to 1346, for
example 1,4-tetramethylene diisocyanate, 1,6-hexamethylene
diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-
diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-
1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyan-
atomethyl cyclohexane, 2,4- and 2,6-hexahydrotolylene di-
isocyanate, hexahydro-1,3- and -1,4-phenylene diisocyanate,
perhydro-2,4'- and/or -4,4'-Biphenyl methane diisocyanate,
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,
2,4-toluyene diisocyanate, 2"6-toluylene diisocyanate, di-
phenyl methane-2,4°- and/or -4,4'-diisocyanate, naphthy-
lene-1,5-diisocyanate, mixtures of these and other polyiso-
cyanates, palyisocyanates containing carbodiimide groups
(for example DE-OS 10 92 007), polyisocyanates containing
allophanate groups (for example GB-P 944,890), polyiso-
cyanates containing isocyanurate groups (for example DE-PS
10 22 789, DE-PS 12 22 067), polyisocyanates containing
urethane groups (for example US-P 3,394,164) or polyiso-
cyanates obtained by reaction of at least difunctional hy-
droxy compounds with excess, at least difunctional iso-
cyanates, polyisocyanates containing biuret groups (for
example DE-PS 11 01 394) and prepolymers or polymers con-
taining at least two isocyanate groups.
Representatives of these compounds, which may be used
in accordance with the invention, are described, for ex
ample, in High Polymers, Vol. XVI, "Polyurethanes, Chem
Le A 26 444 19
~D(~~.~~~
istry and Technology", Interscience Publishers, New York/
London, VoI. I, 1962, pages 32 to 42 and 45 to 54 and Vol.
II, 1964, pages 5 - 6 and 198 - 199 and in Kunststoff Hand-
buch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag,
Miinchen, 1966, pages 45 to 72.
Polyepoxides suitable for the modification reaction
mentioned above are, for example, aliphatic, cycloalipha-
tic, araliphatic, aromatic and heterocyclic compounds con-
taining at least two epoxide groups, such as for example
epoxidized esters of aliphatic, polybasic acids with un-
saturated monohydric alcohols, glycidyl ethers of poly-
hydroxy compounds, glycidyl esters of polycarboxylic acids,
copolymers containing epoxide groups.
Polycarboxylic acids suitable for the modification
reaction are, for example, aliphatic, cycloaliphatic, aral
iphatic, aromatic and heterocyclic compounds containing at
least two carboxyl groups, such as for example adipic acid,
dimeric fatty acid, phthalic acid, terephthalic acid, iso
phthalic acid, fumaric acid, malefic acid, succinic acid,
trimellitic acid, pyromellitic acid, copolymers containing
(meth) aczylic acid, acidic polyesters or acidic polyamides.
Instead of the acids mentioned by way of example, it
is also possible to use the corresponding anhydrides (pro
viding the acids in question form intramolecular anhy
2S Brides) or the corresponding simple alkyl esters, particu
larly methyl esters, fox the modification reaction.
Compounds containing at least two olefinic double
bonds of the type mentioned above, which are suitable for
the modification reaction, are in particular derivatives of
acrylic acid or methacrylic acid, such as far example
hexanediol-bis-(meth)acrylate, trimethylolpropane tris-
(meth)acrylate, gentaerythritol tetra-(meth)acrylate, OH-
functional polyesters or polyacrylates esterified with
acrylic acid, diethylene glycol dimethacrylate, reaction
products of polyisocyanates with hydroxyalkyl (meth)acry-
Le A 26 444 20
i~~~~.~~a~
late.
zn the modification reaction to produce components B)
of relatively high functionality, it is also possible to
use mixtures of different blocked amines which contain at
least one free hydroxyl or amino group reactive to the
modifying agent.
Polyamines containing ketimine or aldimine groups,
which still contain at least one free primary or secondary
amino group or a free hydroxyl group, are obtained, for
example, by reaction of at least difunctional amines with
ketones and/or aldehydes in such equivalent ratios that at
least one amino group remains free.
Even where, for example, polyamines containing at
least one secondary amino group in addition to primary
amino groups are used, the reaction with aldehydes or
ketones results in the formation of aldimines or ketimines
which contain at least one free secondary amino group
(where an equivalent ratio of primary amino groups to car-
bonyl groups of 1:1 has been used) or which contain free
primary amino groups in addition to at least one secondary
amino group (where the carbonyl compounds have been used in
less than the equivalent quantity, based on the primary
amino groups). Primary/secondary polyamines such as these
are, for example, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, dipropylenetriamine, tripropylene
tetramine.
Compounds containing oxazolane groups, which also have
at least one reactive primary or secondary amino group or
a hydroxy group, are obtained for example by reaction of
hydroxyamines containing at least one other hydroxy group
and/or primary or secondary amino group in addition to a
hydroxy group and a secondary amino group or by reactian of
suitable hydroxyamines containing a hydroxy group and a
primary amino group in suitable equivalent ratios with ke-
tones and/or aldehydes of the type described, for example,
Le A 26 444 21
in the foregoing. Suitable hydroxyamines are, for example,
bis-2-hydroxyethyl)-amine, bis-(2-hydroxypropyl)-amine,
bis-(2-hydroxybutyl)-amine, bis-(3-hydroxyprapyl)-amine,
bis-(3-hydroxyhexyl)-amine, N-(2-hydroxypropyl)-N-(6-hy-
droxyhexyl)-amine, 2-amino-2-methyl-1-propanol, 2-amino-2-
methylpropane-1,3-diol, 2-amino-3-methyl-3-hydroxybutane,
aminoethanol.
The hydroxyamines containing oxazolane groups, which
also have at least one free primary or secondary amino
group or a hydroxy group, are prepared by reaction of the
starting components mentioned in such an equivalent ratio
of amino or hydroxy groups to aldehyde or ketone groups
that at least one primary or secondary amino group or a hy-
droxy group is not blocked and is available for the subse-
quent reaction with the reactant used as modifying agent.
Compounds containing hexahydropyrimidine or tetrahy-
droimidazole groups, which also have at least one reactive
primary or secondary amino group or a hydroxy group, are
obtained for example by reaction of hydroxyamines contain-
ing two secondary amino groups in addition to at least one
hydroxy group, such as for example N-methyl-N'-4-hydroxy-
tetramethylenediamine, or by reaction of polyamines con-
taining at least one primary amino group or at least two
other secondary amino groups in addition to at least one
secondary amino group, such as for example N-methyl-1,3-
diaminoethane, N-methyl-1,3-diaminopropane, N-methyl.-1,3-
diaminobutane, diethylenetriamine, N-methyl diethylenetri-
amine, N,N-bis-(3-aminopropyl)-amine, N,N'-dimethyl di-
ethylenetriamine.
The compounds containing hexahydropyrimidine or tetra-
hydraimidazole groups, which also have at least one free
primary or secondary amino group or a hydroxyl group, are
prepared by reaction of the starting compounds mentioned in
such an equivalent ratio of amino or hydroxy groups to al-
dehyde or ketone groups that at least one primary or sec-
Le A 26 444 22
x:.~~~.~~a'~
ondary amino group or a hydroxyl'group is-not blocked and
is available for the subsequent reaction with the reactant
used as modifying agent.
The following structural units, which are suitable for
the synthesis of relatively high molecular weight compon
ents B) of the type in question containing ester, ether,
amide, urethane, urethane bonds, are mentioned by way of
example for the purposes of further illustration:
- bisketimine of diethylenetriamine and acetone
H
CH °CsN CH2-CH2-N-CH2-CN2-N= 'CH3
3 CH3
- aldimine of isophoronediamine and isobutyraldehyde
,H
H3 H2-N=C~H H3
H~, ~CN3
C"3 2
- oxazolane of diethanolamine and isobutyraldehyde
HO-CHZ-CHZs%
HOC-CH-CH3
- hexahydropyrimidine of N-methyl-1,3-diaminopropane and
cyclohexanone
H-N N-CH3
he A 26 444 23
If the modifying agents mentioned by way of example
above are reacted With hexahydropyrimidines or tetrahydro-
imidazoles containing free primary or secondary amino or
hydroxyl groups, hexahydropyrimidines or tetrahydroimida-
zoles of higher functionality are formed. The same applies
to the modification of aldimines or ketimines and to the
modification of oxazolanes.
However, if the modifying agents are reacted with mix
tures of hexahydropyrimidines, tetrahydroimidazoles, ald
imines, ketimines and/or oxazolanes containing free primary
or secondary amino or hydroxyl groups, crosslinking compon-
ents B) are formed in which hexahydropyrimidines, tetra-
hydroimidazoles, ketimines, aldimines and/or oxazolanes are
chemically linked to one another.
Accordingly, various compounds suitable as component
B) may be obtained by these modification or crosslinking
reactions.
The modification reaction is normally carried out in
a solvent of the type mentioned by way of example above at
reaction temperatures of 30 to 180°C, optionally using a
water separator.
In general, an equivalent ratio is selected between
reactive groups of the blocked polyamines and the reactive
groups of the "modifying agent". However, it is also
possible to use the "modifying agents" in a sub-
stoichiometric quantity, for example in 0.75 to 0,99 times
the equivalent quantity.
Polyamines suitable as component B), which may be ob
tained by the modification reactions mentioned, are for ex
ample compounds corresponding to the following formulae:
O b
CH3N~~~~ C' -~- ( CHZ ) 6-NH-CI CH3
Tie A 26 444 24
0
CH3~~~CI-Nfi-CH
1/ltiH-C-
I~ II
-C-AIH-(CH2)6-NH-C-0(CHZ)2-N~~O
polyol ~ II i~ .cH2cH2-N=c.
0-C-Nti- ( CH2 ) 6-Nti-C-N
~CHZCH2-N=C~
a~ n
( ~HZ)6_~_C_ _CH3
nII
-c-HN- c cH2 a 6 I! n
/~ (CH2)b-NH-C-0-(CH2)2s~
0
CH3-CH2-CH-CH2-CH2-CH2-CH3
CH3- ~ -CHZ-CH-CH2- a ~ZCH-CHZ-NH-tCH2)6-NeC~
I
OH OH
~Le A 26 444 25
f
H~~~~H2CH2-O-C-tCH2)6-C-OCHZCH2-H~~ ,.
~Fi
II I' i H2CH2-N=CY
CH3-N~-CH2CH2-C-O-tCH2)6-O-C-CH2GHZ-
,H
CH2CH2-N=CY
In addition to the essential components A) and B), the
binders according to the invention may optionally contain
auxiliaries and additives of various kinds as further com-
ponents C). These various auxiliaries and additives in-
clude, for example, solvents and diluents, levelling aids,
antioxidants, fillers, pigments and W absorbers.
The binders or binder combinations according to the
invention are prepared by mixing the starting components A)
and B) and, optionally, the additives and auxiliaries C)
with one another. Where solvents or diluents are used as
component C), they may already have been added to one or
more of the individual components or,. alternatively, may be
added to the mixture of components A) and B). In one pos-
sible embodiment in particular, the solvents or diluents
are actually present during the preparation of one or more
starting components, as described for example in the fore-
going with reference to the production of the copolymers.
The solvents or diluents should be substantially anhydrous
to ensure an adequate pot life of the mixtures. Solvents
or diluents are generally used in the quantities necessary
to establish suitable processing viscosities of the combin-
ations according to the invention. The solvent content of
the binders according to the invention to be used in ac-
~~e A 26 444 26
Y ~~~~.~~a~
cordance with the invention is generally between 14 and 800
by weight.
However, it is also possible in principle by using
suitable, comparatively low molecular weight copolymers A)
to reduce the solvent or diluent content even further or to
eliminate the need to use such auxiliaries altogether.
In one preferred embodiment, compounds B) which con-
tain no groups reactive to isocyanate groups in the absence
of moisture and of which the blocked amino groups consist
solely of hexahydropyrimidine, tetrahydroimidazole, ald-
imine, ketimine and/or oxazolane groups of the type men-
tioned are used as sole blocked polyamines. The preferred
combinations according to the invention produced in this
way contain 40 to 90 parts by weight of copolymers A) and
10 to 60 parts by weight of compounds B) containing hexa-
hydropyrimidine, tetrahydroimidazole, ketimine, aldimine or
oxazalane groups.
The quantitative ratios in which components A) and B)
are used are generally selected in such a way that, for
every blocked amino group of component B), there is a total
of 0.2 to 8 and preferably 0.5 to 4 isocyanate groups of
component A). In general, a larger excess of the groups
just mentioned within the ranges mentioned will be selected
when the other components contain reactive groups which re-
act with isocyanate groups in the absence of moisture.
Groups such as these include in particular primary or sec-
ondary amino groups which may be present in component B),
for example in addition to the blocked amino groups, and
also alcoholic hydroxyl groups which may be present in com-
ponent B) in addition to the blocked amino groups. In gen-
eral however, alcoholic hydroxyl groups are substantially
inert to tertiary isocyanate groups under the prevailing
conditions (room temperature), so that the hydroxyl groups
only have to be considered when they are used in the form
of substantially involatile alcohols which do not evaporate
Le A 26 444 27
~:00~.003
during the use of the combinations according to the inven-
tion and may be considered as reactant for component A),
for example at relatively high temperatures of the type
prevailing during the hardening of coatings.
Complex mixtures containing urea groups (through re-
action of the isocyanate groups with amino groups) are
formed where the binders according to the invention are
produced by mixing of the individual components, partic-
ularly when compounds containing free primary or secondary
amino groups in addition to the blocked amino groups are
used as component B). Accordingly, the expression "bind-
ers" in the context of the invention encompasses not only
pure mixtures of the individual components A) and B) , as
mentioned above, but also systems in which reaction prod-
ucts of this type are present in addition to the individual
components or which essentially consist solely of such re-
action products. In all variants of the production of the
binders according to the invention by mixing of the indi-
vidual components, the type of individual components and
the quantitative ratios between them are preferably selec-
ted in such a way that the molar ratio of tertiary isocyan-
ate groups to blocked amino groups on completion of the re-
action, which may take place spontaneously, between isocy-
anate groups on the one hand and primary or secondary amino
groups on the other hand is from 0.2:1 to 8:1 and more es-
pecially from 0.5:1 to 4:1, in which case an excess of iso-
cyanate groups should again be considered where the indi-
vidual components used contain alcoholic hydroxyl groups
which may be considered in addition to the blocked amino
groups as reactant for the isocyanate groups in the use
according to the invention.
Tn addition, in the context of the invention. "blocked
polyamines B) containing hydrogen atoms reactive to terti-
ary isocyanate groups°' are understood to be not only
blocked polyamines of the type mentioned which contain re-
Le A 26 444 28
~~o~.c~~;~
active hydrogen atoms in chemically bound form, but also
those which are present in admixture with excess polyamine
or hydroxylamine used for their production.
So far as the suitability of the binder combinations
according to the invention is concerned, it is largely im
material whether the possibly spontaneous reaction between
the copolymers A) and the groups reactive to tertiary iso
cyanate groups has already come completely to an end. Tf
desired, however, it is also possible to terminate this re
action before the use according to the invention by brief
heating to 40 to 100°C. For the rest, the binders accord-
ing to the invention are preferably produced at room tem-
perature.
The binders according to the invention are generally
liquid at room temperature (often because of the presence
of solvents), show adequate stability in storage in the
absence of water and, after application to a substrate,
generally harden rapidly in the presence of atmospheric
moisture.
In general, crosslinked films are obtained even at
room temperature. The basically very rapid hardening pro-
cess may be further accelerated by drying at higher tem-
peratures. Drying times of 10 to 30 minutes at temper-
atures of 80 to 130°C are advantageous.
Where blocked amino groups particularly stable to
hydrolysis are used, this forced drying at elevated tem-
peratures may be necessary to obtain the optimal property
spectrum.
The coating compositions and sealing compounds con
taming the binders according to the invention may contain
the auxiliaries and additives normally used in lacquers, in
cluding for example pigments, fillers, levelling aids, an
tioxidants or UV absorbers.
These auxiliaries and additives should be largely
anhydrous and are preferably incorporated in the starting
Le A 26 444 29
components, generally in component A), before the produc-
tion of the binders.
The lacquers and coating compositions containing the
products according to the invention as binders generally
have a pot life of 3 to 48 hours in the absence of mois
ture. However, the pot life may be corrected upwards or
downwards as required through the choice of suitable re-
actants. The coating compositions (lacquers) and sealing
compounds may be applied to any, optionally pretreated,
substrates, including for ~2xample metals, wood, glass,
ceramics, stone, concrete, plastics, textiles, leather,
cardboard or paper, by spray coating, spread coating, dip
coating, flood coating, casting, roll coating, trowelling.
In the following Examples, all parts and percentages
are by weight, unless otherwise stated.
EXAMPLES
I) General procedure for the production of the olefin-
ically unsaturated compounds al to a3 containing ter-
tiary isocyanate groups:
The starting components are introduced under nitrogen
into a 2-liter reaction vessel equipped with a stirrer,
cooling and heating system and stirred at 40°C until the
theoretical isocyanate content is reached.
The compositions of the starting components are shown
in Table d together with the isocyanate content of the iso-
cyanate-functional monomers obtained,
Le A 26 444 30
~tl~~.U~3
Table 1 (Quantities in g)
Starting components al az as
1-Isocyanato-1-methyl-4(3)-iso-970 970 970
cyanatomethyl cyclohexane
Hydroxyethyl acrylate 580 - -
4-Hydroxybutyl acrylate - 720 -
Hydroxyethyl methacrylate - - 650
2,6-di-tert.-butyl-4-methylphenol0.8 0.8 0.8
Isocyanate content (%) 13.7 12.5 13.1
Color value (APHA) 10 10 10
II) General procedure for the production of the copolymers
A1 to AB containing tertiary isocyanate groups
Part I is initially introduced into a 3-liter reaction
vessel equipped with a stirrer, cooling and heating system
and is heated to the reaction temperature. Part II and
part III are then added at the same time in a nitrogen at
mosphere over a total period of 2 hours and 2.5 hours, res
pectively. The mixture is then stirred for 2 hours at the
reaction temperature.
The reaction temperatures and the compositions of
parts I to III are shown in Table 2 together with the char-
acteristic data of the copolymers obtained.
Le A 26 444 31
e~r~~~.~~~
d' M
O d' t0 O O tn N O
ei~ O
V'
O
00 CO O t0 N 10 N e-1
O CO
CO
CO
iQ', 1D M v-1 (~
M
~i
M
N
O~ O~
O 10 t0 O 01 01 N O
v0 vp
10
CO
CO M ~O N In Op N
M l~
M
10
R~, 1p N e-I M
N
N
d'
d
H
00 O ~O N O d' M O
N O
CO
d'
.p ~ CO t~ O1 N 1p r-1
ll1 In
N
O
M e-I r-i
N
ri
If1
ri
I~ O
V' O N ~0 O 01 M O
V' I'~
~O
00
00 1D f~ t'y N d'
c0 t11 00
M
CO
~0 H ri lC7
d'
d'
d'
01 er
N 1D ~D O tf1 V' O
10 O O
O
~ 1f1 O Il1 N
10
R,' 00 N M
N
H
V' M
N d V' CO O tn d' O N
O d~
N
O
en 00 e-1 \O I~ O !n M
IWC cr
In
dC f~ N r1 t~
v-1
~
H
M N
N O V~ O O In M O
s~ t~
dW
D
N ~D CO ip O O In d'
tf7 ri
tn
CO
le N rl e-I
rl a1'
e-i
d'
r~
tf'f O~
CO O 00 O O 01 M O
O ~
'd' 01 l11 O fn e-I M
01 ei
R', CO M -1 ri N
tW
ri
dP
O
ro " I
O
~-
l
il N 1 r-1
~
a~ +~ to cn
ro o
e'
d o ~, ro
ro~rt
U ~ dP ~
~ ~
rlrorof~roal o
+
H
~
1~ N i~ QI Li .1-~
N N M U W
1-'I
>'I
~'1
ro
~
ro N .aJ O r1 ~ f~ O O :~
+~ ro ro O
U
1..~
.~
~
+~ ~ E3 '~ .1.~ rl
ro U M
ro
U
U
IJ
a ro ~-1,-~ ~ ro ~ ~ cu
U N +~
.~
ro
ro
a~
x
~
la
s~
ro +~ ~ ~ ro ~
l O ,~ x s~
~ ~ a~
a~ a~
a~
~
~
a N + i, U t~ U rl ~r
.6. O ?~
5r.~ f~ U
f~ ~
d! U U U .-1 H U -.-1 to ' d'
~., Q1 "~f' U i-~
N r-I ~
x O O
O
N fC H H ft) I-1 dP 'J tr
C1 ,Q rl j'-a
ro
ro
',~1
I~.
~s
'?r
W-i
./',
~""
~',
H GI N H 47 Vl
1:." 1 N O
.1.7 O
rl
.1.7
,i;
,'sy
O
O
O
d ~--I .~"., N .t:'.r1 G) ~.1 tp
~-i .-d 'Cf O
r-1 U
O
,fir
r-1
r-1
~~1
O
.4"'
.(~.~
~-.
L.'
r-I O d.' 1~ ~.1 .i.l '~, ,~y C: O N
O ',!~ +! ~1 rl
'J~ '?r N U
.G~
.~,'
'fir
'fir
.Ll
r-1
.1.!
.O , Sd S.~?,.L', I-1 .~ .-I O r~1
f-I , .1..1 i-~ ~ r-I
.l.l O rl Ul O
-6~
.4'
.1->
O
U
W
O
O
O
it O ro ro ro I O
?a ~ 4l
~ i~ >r
O O
Ul O
O i.~
.W O
O ri
Ul U
>r
1
U
U
U
H U G.~SCPC1WcnWCGH~;WGpHUNZ"~,~ t~aE-~>CWW rt3t4D'.~~U
III) Preparation of components B) capable of crosslinking
B1
513 g cyclohexane and 456 g isobutyraldehyde are
introduced under nitrogen into a 2-liter reaction vessel
equipped with a stirrer, cooling and heating system. 529.8
g 1-amino-3-methylaminopropane are added dropwise at 10°C
(ice bath cooling), after which the mixture is stirred far
1 hour at 10'C and then heated at the reflux temperature
until no more water is eliminated. Cyclohexane and excess
isobutyraldehyde are then distilled off and the hexahydro-
pyrimidine crosslinker B1 is obtained.
B2
In a 3-liter reaction vessel equipped with a stirrer,
cooling and heating system, 680 g isophoronediamine, 1000
g methyl isobutyl ketone and 560 g toluene are refluxed
under nitrogen on a water separator until the theoretical
quantity of Water has been eliminated (144 g) or until no
more water is eliminated. Toluene and excess methyl iso-
butyl ketone are then distilled off and the bisketimine
crosslinker BZ is obtained.
B3
a) 1050 g diethanolamine and 615 g cyclohexane are intro
duced under nitrogen into a 4 liter reaction vessel equip
ped with a stirrer, cooling and heating system. 1408 g 2
ethyl hexanal are then added dropwise at room temperature,
the temperature slowly rising. The mixture is then kept at
the reflux temperature until the separation of water is
complete. Cyclohexane and excess 2-ethyl hexanal are then
distilled off. An oxazolane, the intermediate stage B3a),
is obtained.
b) Preparation of B3
200.6 g of an isocyanurate polyisocyanate based on
Le A 26 444 33
~~1.~~~
hexamethylene diisocyanate, consisting essentially of
N,N',N"-tris-(6-isocyanatohexyl)-isocyanurate, and 207 g
butyl acetate are introduced under nitrogen into a reaction
vessel equipped with a stirrer, cooling and heating system
and heated to 60°C. After the dropwise addition of 286.7
g of the oxazolane intermediate stage B3a), the mixture is
kept at 70°C for 10 hours. A 70% solution of the cross-
linker B3, containing 3 oxazolane groups on a statistical
average, is obtained.
IV) Preparation of the binder combinations according to
the invention
The components A) containing tertiary isocyanate
groups and the polyamine components B) are mixed together
at room temperature and adjusted to a processible viscos
ity, optionally by addition of more auxiliaries C).
The films are coated onto metal test plates using a
film drawing tool (wet film thickness 180 ~,m). The films
applied and stored at room temperature were all tack-free
after 60 minutes at the longest. After ageing, i.e. 24
hours at room temperature, clear, crosslinked, solvent-
resistant films characterized by excellent mechanical
properties and very good optical properties are obtained.
The lacquer mixtures prepared all had a pat life of
several hours.
The compositions of the binder combinations and the
solvent resistances (degree of crosslinking) are shown in
Table 3 below.
Solvent resistance is tested by a wiping test using a
cotton wool plug impregnated with methyl isobutyl ketone
(MIBK). The number of double wipes for which the film re-
mains visibly unchanged is shown. No film was subjected to
more than 200 double wipes.
he A 26 444 34
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