Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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METHOD FOR PRODUCING VINYL COMPOUNDS
The invention relates to a process for preparing vinyl
compounds, especially vinyl ether compounds, to vinyl
compounds preparable by this process, to formulations
comprising them and to their use.
Compounds containing vinyl groups have developed into
important, key products in industrial chemistry owing
to their particular reactivity and diverse
possibilities for use. Consequently, there exists a
large number of processes for preparing substances and
mixtures of substances which contain vinyl groups.
Because of the diverse possibilities for use of
vinyl-containing compounds there is great interest in
new kinds of vinyl compounds which can be used to give
products having new and/or improved properties.
It is an object of the present invention to provide a
Process for preparing novel vinyl compounds, vinyl
compounds preparable by such a process, formulations
comprising such vinyl compounds, and for the use of
these vinyl compounds or of formulations comprising
them.
We have found that this object is achieved by a process
for preparing vinyl compounds where aminovinyl
compounds are reacted, but maintain their vinyl groups,
with substances reactive with the aminovinyl compounds.
By aminovinyl compounds here are meant compounds
containin at least one nitro en-basic
g g group and at
least one vinyl group in the molecule . The vinyl group
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in these compounds is generally not linked directly to
the amino group.
The vinyl compounds preparable by the process of the
invention feature extremely high sensitivity to W
light. When compounds of the invention or formulations
comprising them are cured there is no oxygen inhibition
of the surface.
The reaction of the aminovinyl compounds with
substances reactive with them takes place at the amino
group or groups. This means that the aminovinyl
compounds are able to react singly or multiply with
substances reactive with the nitrogen-basic group of
the aminovinyl compounds. The resultant bonds may be
ionic bonds, covalent bonds or forms intermediate
between ionic and covalent bonds. The formation of
covalent bonds is preferred.
The aminovinyl compounds may have further reactive
groups. The reaction with substances reactive with the
aminovinyl compounds may therefore take place at the
amino group or groups and/or at the reactive groups.
It is therefore possible to obtain compounds which may
carry numerous functional groups and may be employed in
a large number of industrial fields.
The aminovinyl compounds employed in the process of the
invention are preferably aminovinyl ether compounds.
Such compounds may contain one or more vinyl ether
groups.
The vinyl ether compounds are compounds which in
addition to at least one nitrogen-basic group have at
least one vinyl ether group in the molecule. In general
they include vinyl ethers of primary, secondary and
tertiary alkanolamines, of cycloalkanolamines, of
arylalkanolamines and open-chain and cyclic amides.
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Particular preference is given to the use of
aminopropyl vinyl ether, and ethyleneurea monovinyl
ether and very particular preference to the use of
diethanolamine divinyl ether.
Through the process of the invention the vinyl
compounds can be prepared in the form of monomers,
oligomers, polymers or mixtures thereof. As a result it
is possible to prepare suitable vinyl compounds in
accordance with the field of use.
Preferably, the aminovinyl compounds are reacted with
substances containing functional groups selected from
epoxide groups, isocyanate groups, carboxyl groups,
carbonyl groups, halogens and groups able to enter into
a Michael reaction with the amino groups.
These substances may be in monomeric or polymeric form
and one or more functional groups may be present.
Preferred epoxy substances are known and commercially
available epoxy monomers and epoxy resins such as, for
example, of the bisphenyl A type (e. g. Araldite,
Epicote) and copolymers incorporating glycidyl
(meth)acrylate monomers.
In the reaction of the aminovinyl compounds with the
epoxy compounds it is possible in order to establish
desired properties to allow further substances, such as
carboxyl compounds, amino compounds without vinyl
groups, aromatic and/or aliphatic hydroxy compounds, to
react as well. The sequence of the reaction is open in
such cases and in specific cases must be decided on in
accordance with rules known to the skilled worker. For
example, if carboxyl compounds are to be reacted, it is
judicious to react the carboxyl compound first with the
epoxy compound in order to avoid the formation of salts
between carboxyl and aminovinyl compounds and in order
to avoid acid-catalyzed polmerizations.
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Preferred isocyanate substances are known and
commercially available polyfunctional isocyanates.
In these cases too, it is possible in addition to add
substances reactive with the isocyanates. Examples are
mono- and polyfunctional hydroxyl compounds and/or
their alkoxylation products, and mono- and
polyfunctional amino compounds. As a result it is
possible to utilize the known polyurethane chemistry in
order to obtain novel, highly reactive vinylurethane
compounds.
Preferred carboxyl substances are monofunctional and
polyfunctional monomeric and polymeric carboxylic acids
or their anhyrides. They are, for example, linear,
branched substituted and unsubstituted aromatic and
cycloaliphatic carboxylic acids or anhyrides thereof,
and various fatty acids deriving from natural oils and
fats, such as linseed oil fatty acid, polymerized
linseed oil fatty acid, oleic acid and tall oil fatty
acid.
Substances of particular industrial interest are those
which are derived from acidic polyesters and can be
functionalized with aminovinyl compounds. In this way
it is possible to obtain highly reactive,
vinyl-modified substances. The synthesis of suitable
polyesters, and the control of the basic properties,
are known to the skilled worker. In this context, the
aminovinyl compounds can be added to the polyesters
right at the beginning of the polycondensation. It is
preferred first to carry out the polycondensation to
give the acidic polyesters and then to react the
aminovinyl compounds with said polyesters.
It is also possible to employ polycarboxylic acids,
such as (meth)acrylate polymers with fractions of
polymerizable carboxylic acids, such as (meth)acrylic
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acid, malefic acid, et cetera. In this way, polyacrylate
binders of extremely high UV activity can be obtained.
In the case of the reactions of aminovinyl compounds,
5 especially aminovinyl ethers, with carboxyl substances
it is preferred to initially introduce the aminovinyl
ether compound and then to add the acidic carboxyl
substance in a stoichiometric amount.
By initial introduction of the aminovinyl ether
compound is meant that the total amount of the
aminovinyl ether compound to be reacted is introduced
before the beginning of the reaction (= initially
introduced) into an appropriate apparatus. The carboxyl
substance is added gradually to the total amount of
aminovinyl ether compound. This procedure, and the
addition of a stoichimetric amount of the carboxyl
substance, prevents acid-catalyzed polymerization of
the aminovinyl ether compound.
The carboxyl groups can be attached to the aminovinyl
compounds by way of a condensation reaction (amide
groups) and/or by way of an ionic bond (by
protonation).
Carbonyl substances employed with preference are
derived from polyfunctional keto compounds. Examples of
these are copolymers of carbon monoxide and ethylene,
or acrylate polymers with carbonyl comonomers, such as
diacetoneacrylamide. Primary or secondary aminovinyl
compounds can be added on to these keto polymers to
form ketals.
If the aminovinyl compounds are reacted with substances
containing halogens as reactive groups, then the
attachment of the halogen substances to the aminovinyl
compounds can take place by way of a covalent bond
and/or by way of an ionic bond.
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The reaction of the aminovinyl compounds with
substances reactive with them takes place preferably by
adding the aminovinyl compound to the corresponding
reactive substances or mixtures of substances at a
temperature of in general from 25 to 250°C, preferably
from 50 to 150°C and, with particular preference, from
60 to 90°C.
Following the addition of the aminovinyl compound
stirring is continued at a temperature of in general
from 25 to 250°C, preferably from 50 to 200°C, with
particular preference from 80 to 100°C and, with very
particular preference, at 100°C for in general from 2
to 20 hours, preferably from 4 to 8 hours and, with
particular preference, from 5 to 6 hours.
It is a further object of the present invention to
provide compounds preparable by the process of the
invention and formulations comprising them.
The present invention therefore additionally provides
vinyl compounds preparable by the process described,
using aminovinyl compounds, and formulations which
comprise at least one such vinyl compound.
The vinyl substances of the invention are curable by
cationic polymerization and/or, if further
copolymerizable double bonds are present, by
free-radical polymerization with the addition of
appropriate initiators. For the purposes of this
invention curing means the crosslinking of the vinyl
substances of the invention.
The present invention therefore additionally provides
formulations which in addition to the vinyl compounds
of the invention comprise further ionic and/or
free-radically co-reactive substances selected from
monomeric, oligomeric and/or polymeric epoxy, allyl,
(meth)acrylic and/or vinyl ether compounds.
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The present invention provides, furthermore, for the
use of the vinyl compounds or formulations of the
invention for free-radically and/or sonically initiated
crosslinking or curing.
Cationic polymerization is also possible in combination
with free epoxy groups. The cationic initiators can be
added to multi-component systems or, preferably, to
single-component systems. Particular preference is
given to single-component systems in which the cations
required for crosslinking are released with the aid of
the admixed initiators by means of heat and/or
high-energy radiation, e.g. W light.
Free-radical polymerization is possible with substances
having copolymerizable double bonds, such as acrylic,
allyl, malefic, fumaric and/or itaconic groups.
Particular preference is given to unsaturated polyester
resins functionalized with vinyl groups in the manner
of the invention. Depending on the polyester components
selected and degree of condensation established, these
resins can be either in liquid form or in solid form,
and constitute outstanding binders, for example, for
coating materials including powder coating materials.
Particular preference is given to the free-radical
polymerization of the vinyl compounds of the invention
in combination with free-radically co-crosslinkable
substances. Co-crosslinkable substances employed with
preference are unsaturated polyester resins,
monofunctionally and polyfunctionally, acrylically or
vinylically unsaturated monomers and/or polymers,
monofunctional and polyfunctional allyl esters, allyl
ethers and vinyl esters.
Preferred free-radical initiators are those employed
for thermal and/or UV curing. Suitable initiators for
thermal curing are peroxides, azo compounds and
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C-C-labile substances, of the pinacole type, for
example. Suitable initiators for UV curing are
photoinitiators of Norrish types I and II.
Furthermore, it is also possible to employ two-stage
curing systems in which cationic and free-radical
curing are combined.
The substances of the invention are extremely sensitive
to UV light, and on irradiation with UV light there is
no oxygen inhibition of the surface. After curing they
prove to be highly resistant to organic solvents, such
as acetone, and exhibit a hard, tack-free surface
layer.
The present invention therefore additionally provides
for the use of the vinyl compounds of the invention, or
of formulations comprising at least one vinyl compound
of the invention, in coating materials, adhesives,
printing inks and UV-curable or daylight-curable
exterior paints, and also in coatings, in potting
compounds, casting compositions and impregnants for
electronics and electrical engineering, and in
fiber-reinforced materials and prepregs.
Preference is given here to 100 systems, which in
order to regulate the viscosity, reactivity or
properties of the cured substances may include further
co-reactive substances, such as reactive diluents,
examples being styrene, vinyl toluene, vinyl ethers,
vinyl esters, acrylates, allyl ethers and allyl esters.
Also provided by the present invention are sheetlike
and/or shaped articles produced using the vinyl
compounds of the invention or formulations comprising
at least one such vinyl compound.
The following examples additionally illustrate the
invention.
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Example 1
Substance of the invention based on epoxy resins.
380 g of bisphenol A glycidol ether (Araldite GY 2600)
having an epoxide equivalent weight of 190 are
initially introduced into a stirred flask with feed
vessel and heating bath and this initial charge is
heated to 90°C under a gentle stream of nitrogen. Then
314 g of diethanolamine divinyl ether are added
dropwise over one hour and stirring is continued at
100°C for 5 hours. The result of cooling is a viscose
yellowish resin.
Example 2
Vinyl compound based on a polyacrylate.
A flask with heating bath, reflux condenser
stirred and
two feed
vessels
is
charged
with
200 g of butyl acetate
50 g of methyl methacrylate
g of glycidyl methacrylate
25 20 g ethylhexyl
acrylate
1 g of mercaptoethanol (regulator)
2 g of tert-butyl peroctoate (initiator)
and this initial charge is heated with stirring to
30 115°C. Then the following feeds are run in
simultaneously over one hour.
Feed I: a mixture of
150 g of methyl methacrylate
90 g of glycidyl methacrylate
60 g of ethylhexyl acrylate
3 g of mercapto ethanol (regulator)
Feed II: a mixture of
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6 g of tert-butyl peroctoate (initiator)
66 g of butyl acetate
The mixture is subsequently stirred at 120°C for 3
hours and then cooled to 60°C, after which
5 132 g of diethanolamine divinyl ether
0.8 g of tert-butylcresole
0.8 g of hydroquinone monomethyl ether
0.1 g of phenothiazine
are added.
The mixture is then stirred at 100°C for 6 hours. The
result is a viscose yellowish resin solution.
Testing of the vinyl compounds:
A 100 g of Laromer PO 33 F (unsaturated acrylate
resin from BASF)
30 g of resin of Example 1
3.9 g of benzil dimethyl ketal
B 100 g of Laromer PO 33 F (unsaturated acrylate
resin from BASF)
g of resin of Example 2
3.9 g of benzil dimethyl ketal
C Comparative Example
100 g of Laromer PO 33 F (unsaturated acrylate
resin from BASF)
3 g of benzil dimethyl ketal
The test coating materials were prepared and the test
panels produced in a UV-protected laboratory. The
components of the test coating materials were premixed
in glass flasks with a stirring spatula and these
mixtures were stored in a drying cabinet at 50°C for 1
hour and stirred thoroughly again. Cooling to room
temperature resulted in all cases in clear, viscose
solutions.
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The solutions were then drawn down onto degreased
bright steel panels using a coater bar having a gap
height of 60 mm. The test panels were then irradiated
under a mercury vapor W lamp having an emission
maximum at about 365 nm and an energy output of
19 mJ/cm2 in the exposure plane until the films were
not attacked by 10 minutes of exposure to a cotton pad
wetted with acetone. If surface inhibition of the films
was observed, a non-crosslinked, acetone-soluble layer
present was first of all wiped off and the swellability
of the underlying layer was assessed. Surface
inhibition means that the layers are acetone-insolubly
crosslinked beneath a tacky or tack-free surface layer
which remains uncrosslinked and acetone-soluble.
Results:
Coating Result after UV irradiation
Material
A 2 s: acetone-resistant, hard, no surface
inhibition
5 s: acetone-resistant, hard, no surface
inhibition
10 s: acetone-resistant, hard, no surface
inhibition
B 2 s: acetone-resistant, hard, no surface
inhibition
5 s: acetone-resistant, hard, no surface
inhibition
10 s: acetone-resistant, hard, no surface
inhibition
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C 5 s: slightly tacky, acetone-resistant below
detachable layer (surface inhibition)
s: tack-free, soft, acetone-resistant
below detachable layer (surface inhibition)
s: tack-free, hard, acetone-resistant
below detachable layer (surface inhibition)
These examples show that the examples in accordance
with the invention achieve extremely high sensitivity
5 to UV light and avoid oxygen inhibition of the surface.
