Note: Descriptions are shown in the official language in which they were submitted.
PF 70838 CA 02813844 2013-04-05
High-functionality polyetherols and preparation and use thereof
Description
The present invention relates to a process for preparing high-functionality
polyethers having a
Hazen color number of less than 500, measured to DIN ISO 6271, by converting
tris(hydroxyethyl) isocyanurate (THEIC) and one or more difunctional alcohols
and/or modifying
reagents with the aid of acidic catalysts. The present invention further
relates to high-
functionality polyethers having a color number of less than 500, obtainable by
such a process,
and to the use of these high-functionality polyethers as adhesion promoters,
thixotropic agents,
rheology modifiers, as a constituent of printing inks, paints and coatings, or
as units for
preparation of polyaddition or polycondensation polymers.
Polyetherols are typically prepared from the reaction of water, alcohols or
amines by ring-
opening polymerization with alkylene oxides, for example with ethylene oxide,
propylene oxide
or butylene oxide, or mixtures thereof. Of industrial significance are
polyetherols based on
water, glycols, glycerol, trimethylolpropane, pentaerythritol or sugars as the
starter molecule,
which react with ethylene oxide, propylene oxide or ethylene oxide/propylene
oxide mixtures to
give linear diols or polyols of star-shaped structure. Such processes are
explained, for example,
in Becker/Braun, Kunststoff-Handbuch [Polymer Handbook] vol. 7, Polyurethane
[Polyurethanes], Carl-Hanser-Verlag, Munich, 1993, pages 58-67.
For example, Huozhayao Xuebao 2007, 30 (6), pages 13-16, describes the
reaction of THEIC
with various epoxides by ring-opening polymerization by means of boron
trifluoride catalysis to
give polyfunctional polyethers. However, this synthesis is technically complex
and does not lead
to the highly branched polyethers that we have claimed.
The preparation of polyethers by homocondensation of THEIC has likewise been
described. For
example, US 3,293,224 discloses the preparation of high-functionality
polyethers under acidic
catalysis to give oligonneric polyethers. The products thus obtained are
solids which are glassy
at room temperature, which can be converted to powder form by grinding. In
addition to the high
glass transition temperature, the polyethers are insoluble in nonpolar media
and are of limited
solubility in polar media. As a result of these restrictions, the products do
not have wide
usability.
Documents EP 44 872 and US 4,557,949 (= DE 2904979) describe the production of
semipermeable membranes, in which the polycondensation of THEIC, optionally in
combination
with further alcohols, in the presence of acidic catalysts, for example H2SO4,
is applied to a
substrate, for example glass or fabric. The reaction product thus obtained is
crosslinked and
water-insoluble, and is unsuitable for further reactions.
WO 2009/101141 describes the preparation of high-functionality polyetherols by
reacting at
least one trifunctional or higher-functionality alcohol and optionally further
di- and/or
monofunctional alcohols and/or modifying reagents with the aid of acidic
catalysts. THEIC is
2
one trifunctional alcohol mentioned. Especially in the case of use in printing
inks, paints
or coatings, however, the slightly brownish color of the products according to
WO 2009/101141 is noticeably disadvantageous.
It was therefore an object of the present invention to provide an optically
clear,
colorless, uncrosslinked, high-functionality polyether which is soluble in a
wide variety of
different media and is industrially producible by means of a technically
simple and
inexpensive process.
It was a further object to provide a high-functionality polyether which, due
to its defined
structure, combines advantageous properties, such as high functionality, high
reactivity,
low viscosity and good solubility.
It was a further object of the present invention to provide a process for
preparing these
high-functionality polyethers.
Surprisingly, the object is achieved by a process in which THEIC and one or
more
difunctional alcohols and/or modifying reagents are converted with the aid of
acidic
catalysts.
An embodiment of the invention relates to a process for preparing
uncrosslinked, high-
functionality polyethers having a Hazen color number of less than 500, by
converting
tris(hydroxyethyl) isocyanurate (THEIC) and one or more difunctional alcohols
and/or
modifying reagents with the aid of acidic catalysts, wherein the modifying
reagents have
only one alcohol group (monools), at least one acid group, at least one
anhydride
group, at least one isocyanate group, at least one amino group or at least one
phosphonic acid group.
Another embodiment of the invention relates to the process defined
hereinabove,
wherein the uncrosslinked, high-functionality polyether has an average
functionality of 4
to 100.
Another embodiment of the invention relates to the process defined
hereinabove,
wherein the amount of difunctional alcohol, based on the amount of THEIC and
difunctional alcohol, is 1 to 99 mol%.
CA 2813844 2018-04-23
2a
Another embodiment of the invention relates to the process defined
hereinabove,
wherein the difunctional alcohols are selected from the group consisting of
monoethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol,
1,3-
propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-
butanediol, 1,4-
butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,5-pentanediol, hexanediol,
heptanediol,
octanediol, nonanediol, decanediol, dodecanediol, cyclopentanediol,
cyclohexanediol,
cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane, bis(4-
hydroxycyclohexyl)ethane, 2,2-bis(4-hydroxycyclohexyl)propane, difunctional
polyether
polyols based on ethylene oxide, propylene oxide, butylene oxide and mixtures
thereof,
polytetrahydrofu ran, 2-methylpropanediol, neopentyl glycol, 2-
methylbutanediol, 2- or 3-
methylpentanediol, 2-ethyl-1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-
ethyl-1,3-
propanediol and mixtures of two or more of these diols.
Another embodiment of the invention relates to the process defined
hereinabove,
wherein the modifying reagent used is an alcohol containing mercapto groups,
an
alcohol containing amino groups and/or a hydrophobic alcohol.
Another embodiment of the invention relates to the process defined
hereinabove,
wherein the modifying reagent used is a reagent selected from the group
consisting of
compounds containing acid halide groups, compounds containing isocyanate
groups,
anhydride-containing compounds, lactones and alkylene oxides.
Another embodiment of the invention relates to the process defined
hereinabove,
wherein no modifying reagent is used.
Another embodiment of the invention relates to an uncrosslinked, high-
functionality
polyether having a Hazen color number of less than 500, obtained according to
the
process defined hereinabove.
Another embodiment of the invention relates to the use of an uncrosslinked,
high-
functionality polyether as defined hereinabove, in printing inks, paints or
coatings, as
units for preparation of polyaddition or polycondensation polymers, or as a
constituent
of paints, coverings, adhesives, sealants, cast elastomers or foams.
CA 2813844 2018-04-23
,
2b
Another embodiment of the invention relates to a coating material comprising
an
uncrosslinked, high-functionality polyether as defined hereinabove.
Another embodiment of the invention relates to the process defined
hereinabove,
wherein the modifying reagent is selected from the group consisting of
mercaptoethanol, triethanolamine, tripropanolamine, triisopropanolamine, N, N-
dimethylethanolamine, adipic acid, dimethyl terephathalate ester,
caprolactone,
ethylene oxide, propylene oxide and butylene oxide.
In the context of this invention, a high-functionality polyether is understood
to mean a
product which, as well as the ether groups which form the polymer skeleton,
has an
average of at least four, preferably at least five, more preferably at least
six and
especially at least eight functionalities in terminal or lateral positions.
Functionalities are
understood to mean OH groups, and also OH groups which have been reacted with
modifying reagents. The polymer skeleton may be linear or branched. There is
in
principle no upper limit on the number of terminal or lateral functionalities,
but products
with a very high number of functionalities may have undesired properties, for
example a
high viscosity or poor solubility. The high-functionality polyetherols of the
present
invention usually have not more than 100 terminal or lateral functionalities,
preferably
not more than 50 terminal or lateral functionalities. In a particular
embodiment, the
functionalities are OH groups. In addition, the functionalities may, however,
also be all
reaction products of OH groups with modifying reagents, such as the reaction
products
with monoalcohols, amino alcohols, isocyanates or lactones.
In one embodiment, the high-functionality polyethers are high-functionality,
hyperbranched polyethers. Hyperbranched polyethers are understood in the
context of
this invention to mean uncrosslinked polymer molecules which are both
structurally and
molecularly inhomogeneous. On the one hand, they may be formed proceeding from
a
central molecule analogously to dendrimers, but with inhomogeneous chain
length of
the branches. On the other hand, they may also have linear regions with
functional side
groups. For a definition of dendrimers and hyperbranched polymers, see also
P.J. Flory,
J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6,
No. 14,
2499.
CA 2813844 2018-04-23
PF 70838 CA 02813844 2013-04-05
3
''Hyperbranched" in the context of the present invention is understood to mean
that the degree
of branching (DB), i.e. the mean number of dendritic linkages plus the mean
number of end
groups per molecule, divided by the sum of the mean number of dendritic,
linear and terminal
linkages, multiplied by 100, is 10 to 99.9%, preferably 20 to 99%, more
preferably 20-95%.
"Dendrimeric" in the context of the present invention is understood to mean
that the degree of
branching is 99.9-100%. For a definition of the degree of branching see H.
Frey et al., Acta
Polym. 1997, 48, 30.
Color number is understood to mean the Hazen color number, which is determined
in
accordance with the invention to DIN ISO 6271, ASTM D 1209. The calibration
standard used to
determine the color impression is a cobalt platinate solution. In a departure
from DIN ISO 6271
and ASTM D 1209, in the context of the invention, a 50% by weight solution of
the polyether to
be determined is analyzed in dimethylacetamide at 23 C.
As difunctional alcohols can ethylene glycol, diethylene glycol, triethylene
glycol, 1,2- and 1,3-
propanediol, dipropylene glycol, tripropylene glycol, 1,2-, 1,3- and 1,4-
butanediol, 1,2-, 1,3- and
1,5-pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol,
dodecanediol,
cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, bis(4-
hydroxycyclohexyl)methane,
bis(4-hydroxycyclohexyl)ethane, 2,2-bis(4-hydroxycyclohexyl)propane,
difunctional polyether
polyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures
thereof, or
polytetrahydrofuran. It is additionally possible to use branched dials, for
example propylene
glycol, 2-methylpropanediol, neopentyl glycol, 2-methylbutanediol, 2- or 3-
methylpentanediol,
2-ethyl-1,6-hexanediol, 2-ethyl-1,3-hexanediol or 2-butyl-2-ethyl-1,3-
propanediol. It will be
appreciated that it is also possible to use difunctional alcohols in mixtures.
According to the
invention, it is also possible to precondense difunctional alcohols to give OH-
terminated
oligomers and then to add THEIC and optionally the monofunctional alcohol. In
this way, it is
likewise possible to obtain highly branched polymers with linear block
structures.
The ratio of difunctional alcohols to THEIC is determined by the person
skilled in the art
according to the desired properties of the polyether. In general, the amount
of the difunctional
alcohol(s) is 0 to 99 mol%, preferably 1-99 mol%, more preferably 1-80 mol%
and even more
preferably 1-75 mol%, and especially 1 to 70 mol%, based on the total amount
of all alcohols in
moles. By virtue of alternating addition of diols in the course of the
reaction, it is also possible to
obtain block copolyethers, for example diol-terminated polyethers.
The modifying reagents used may be compounds which have groups reactive with
01-I groups.
These can be added to the reaction at any time. For instance, it is possible
to initially charge
THEIC, modifying reagents and optionally difunctional alcohol together and to
condense them
on in one step, but it is also possible to precondense THEIC alone or together
with a
difunctional alcohol and to add the modifying reagent during or only after
completion of the
precondensation.
,
PF 70838 CA 02813844 2013-04-05
,
4
The modifying reagents used may be molecules which have only one alcohol group
(monools),
which have at least one acid group, at least one anhydride group, at least one
isocyanate
group, at least one amino group or at least one phosphonic acid group. The
modifying reagents
are used only in such amounts that crosslinked products are not obtained.
In addition to the groups reactive with 01-1 groups, the modifying reagents
may bear further
functional groups, such as mercapto groups, primary, secondary or tertiary
amino groups, ester
groups, carboxylic acid groups or derivatives thereof, sulfonic acid groups or
derivatives thereof,
phosphonic acid groups or derivatives thereof, silane groups, siloxane groups,
or short- or long-
chain alkyl radicals.
For the modification with mercapto groups, it is possible, for example, to use
mercaptoethanol.
Tertiary amino groups can be obtained, for example, by incorporating alcohols
containing amino
groups, such as triethanolamine, tripropanolamine, triisopropanolamine, N-
methyl-
diethanolamine, N-methyldipropanolamine or N,N-dimethylethanolamine. By adding
dicarboxylic
acids, tricarboxylic acids, dicarboxylic esters, for example adipic acid,
dimethyl terephthalate or
tricarboxylic esters, it is possible to obtain ester groups. In addition, it
is possible to obtain ester
groups by reacting the OH groups with lactones, especially with caprolactone.
By reaction with
long-chain alkanols or alkanediols, it is possible to introduce long-chain
alkyl radicals. The
reaction with alkyl or aryl isocyanates, diisocyanates or oligoisocyanates
generates
corresponding polyethers having urethane groups.
If the modifying reagents are to be added only in a second step after the
precondensation of
THEIC and optionally difunctional alcohol, the modifying reagents used are
preferably
compounds comprising acid, acid halide, anhydride or isocyanate groups, or
lactones such as
caprolactone. In the case of use of lactones, it is possible to control the
length of the ester
chains by the amount of lactone used. In a further embodiment, it is also
possible to use a
plurality of modifying reagents; for example, it is possible to react a
modifying reagent in the first
step together with THEIC and optionally the difunctional alcohol, and then, in
a second step, to
add a further modifying reagent to the reaction product from the first step.
In addition, the precondensates can be converted by reaction with alkylene
oxides, for example
ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, to high-
functionality
polyether polyols comprising linear polyether chains with adjustable polarity.
When the modifying reagents are used for hydrophobization, preference is given
to using
monoalkanols having more than 3 and more preferably more than 6 carbon atoms.
Preferably not more than 200 mol%, more preferably not more than 100 mol% and
especially
preferably not more than 50 mol% of modifying reagent, based on the total
amount of THEIC, is
added.
PF 70838 CA 02813844 2013-04-05
To accelerate the reaction, acidic catalysts or catalyst mixtures are added.
Suitable catalysts
are, for example, acids with a pKa of less than 2.2; particular preference is
given to strong acids.
Examples of acids with a pka of less than 2.2 are, for example, phosphoric
acid (H3PO4),
5 phosphorous acid (H3P03), pyrophosphoric acid (H413207), polyphosphoric
acid, hydrogensulfate
(HSO4-), sulfuric acid (H2SO4), perchloric acid, hydrochloric acid,
hydrobromic acid,
chlorosulfonic acid, methanesulfonic acid, trichloromethanesulfonic acid,
trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid.
Further examples of inventive acidic catalysts are acidic ion exchangers or
ion exchange resins.
"Ion exchangers" is the collective term for solid substances or liquids which
are able to absorb
positively or negatively charged ions from an electrolyte solution while
releasing equivalent
amounts of other ions. Preference is given to using solid grains and particles
whose matrix has
been obtained by condensation (phenol-formaldehyde) or by polymerization
(copolymers of
styrene and divinylbenzene, and methacrylates and divinylbenzene).
The acidic ion exchangers used in accordance with the invention bear, for
example, sulfonic
acid groups, carboxylic acid groups or phosphonic acid groups. It is also
possible to use ion
exchangers which possess a hydrophilic cellulose structure or consist of
crosslinked dextran or
agarose, and bear acidic functional groups, for example carboxymethyl or
sulfoethyl groups. It is
also possible to use inorganic ion exchangers, such as zeolites,
montmorillonites, palygorskites,
bentonites and other aluminum silicates, zirconium phosphate, titanium
tungstate and nickel
hexacyanoferrate(I I). For ion exchangers, see also ROMPP, Chemisches Lexikon
[Chemical
Lexicon], Online Version 3.0, or "Ion Exchangers" by F. De Dardel and T. V.
Arden, published in
Ullmann's Encyclopedia of Industrial Chemistry, Electronic Release 2007.
Acidic ion
exchangers are obtainable, for example, in solid or dissolved form under the
product names
AmberliteTM, AmberseptTM or AmberjetTM from Rohm and Haas.
Particularly preferred inventive catalysts are sulfuric acid, phosphoric acid,
polyphosphoric acid,
chlorosulfonic acid, methanesulfonic acid, trichloromethanesulfonic acid,
trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or
acidic ion
exchangers.
Very particular preference is given to sulfuric acid, methanesulfonic acid,
trifluoromethanesulfonic acid, p-toluenesulfonic acid or acidic ion
exchangers.
The acid is added as a catalyst generally in an amount of 50 ppm to 10% by
weight, preferably
100 ppm to 5% by weight and more preferably 1000 ppm to 3% by weight, based on
the amount
of the alcohol or alcohol mixture used.
When an acidic ion exchanger is used as a catalyst, an amount of 1000 ppm to
30% by weight,
preferably of 1 ¨ 25% by weight, more preferably 1 ¨ 20% by weight, based on
the amount of
PF 70838 CA 02813844 2013-04-05
6
the alcohol or alcohol mixture used, is typically added. It will be
appreciated that the catalysts
can also be used in a mixture.
Moreover, it is possible both by addition of the suitable catalyst and by
selection of a suitable
temperature to control the polycondensation reaction. In addition, it is
possible via the
composition of the starting components and via the residence time to establish
the mean
molecular weight of the polymer and its structure.
The reaction is effected typically at a temperature of 0 to 250 C, preferably
60 to 220 C, more
preferably at 100 to 200 C and most preferably at 130 to 180 C, in bulk or in
solution. In
general, it is possible to use all solvents which are inert toward the
particular reactants. When
solvent is used, preference is given to using organic solvents, for example
decane, dodecane,
benzene, toluene, chlorobenzene, xylene, dimethylformamide, dimethylacetamide
or solvent
naphtha.
In a particularly preferred embodiment, the condensation reaction is performed
initially in the
presence of water as solvent or solubilizer. The water added for
solubilization can be removed
in the course of the reaction from the reaction equilibrium to accelerate the
reaction, together
with the water of reaction additionally released, for example by distillation,
optionally under
reduced pressure.
The inventive high-functionality polyether polyols are prepared usually within
a pressure range
of 0.1 mbar to 20 bar, preferably 1 mbar to 5 bar, in reactors which are
operated in batchwise
operation, semicontinuously or continuously.
Preference is given to performing the reaction in a "one-pot method", in which
THEIC and
difunctional alcohol and/or modifying reagent and optionally solvent are
initially charged in their
entirety and the reaction is carried out in a backmixed reactor. However,
reactions are also
conceivable in a multistage reactor system, for example a stirred tank battery
or a tubular
reactor. In a preferred alternative embodiment of the present invention, the
reaction can be
carried out in a kneader, extruder, intensive mixer or paddle dryer.
The reaction can optionally also be carried out with the aid of ultrasound or
microwave radiation.
There are various ways of stopping the intermolecular polycondensation
reaction. For example,
the temperature can be lowered to a range in which the reaction stops and the
condensation
product is storage-stable.
In addition, the catalyst can be deactivated, for example by adding a basic
component such as
a Lewis base or an organic or inorganic base.
PF 70838 CA 02813844 2013-04-05
7
The aforementioned adjustment of the reaction conditions and optionally the
selection of the
suitable solvent allow the inventive products to be processed further without
further purification
after the preparation.
In a further preferred embodiment, the reaction product is purified by
stripping, i.e. by removing
low molecular weight volatile compounds. For this purpose, the catalyst can be
deactivated after
the desired conversion has been attained. Subsequently, the low molecular
weight volatile
constituents, for example solvents, starting monomers, volatile cleavage
products, volatile
oligomers or cyclic compounds or water are removed by distillation, optionally
with introduction
of a gas, preferably nitrogen, carbon dioxide or air, optionally under reduced
pressure. In a
preferred embodiment, the product is freed of volatile constituents in a thin-
film evaporator.
In a particularly preferred embodiment, in the case of subsequent modification
with modifying
reagent, before the modifying reagent is used, the precondensate obtained from
THEIC and
optionally difunctional alcohol is purified as described above.
Owing to the properties of the starting monomers, ills possible that the
reaction can result in
condensation products with different structures, which have branches and
cyclic units but no
crosslinks. The number of reactive groups arises from the properties of the
monomers used and
the degree of polycondensation, which, according to the invention, should be
selected such that
the gel point is not attained.
The inventive polyether polyols have glass transition temperatures less than
70 C, preferably
less than 50 C, more preferably less than 30 C and especially less than 0 C.
The high-functionality highly branched polyethers formed by the process
according to the
invention dissolve readily in various solvents, for example in water, alcohols
such as methanol,
ethanol, butanol, alcohol/water mixtures, acetone, 2-butanone, ethyl acetate,
butyl acetate,
methoxypropyl acetate, methoxyethyl acetate, tetrahydrofu ran,
dimethylformamide,
dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene
carbonate.
A great advantage of the process according to the invention lies in its
economic viability. Both
the reaction to give the polycondensation product and the reaction of the
condensation products
to give polyethers with other functional groups or elements can be effected in
one reaction
apparatus, which is technically and economically advantageous.
The inventive high-functionality highly branched or high-functionality
hyperbranched
polyetherols can be used in an industrially advantageous manner, inter alia,
as adhesion
promoters, thixotropic agents, rheology modifiers of polymers, in printing
inks or as units for
preparing polyaddition or polycondensation polymers, for example in paints,
coverings,
adhesives, sealants, cast elastomers or foams.
,
PF 70838 CA 02813844 2013-04-05
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8
They are suitable especially for producing printing inks, such as flexographic
printing inks,
gravure printing inks, offset printing inks or screenprinting inks, and for
producing print
varnishes. More particularly, the inventive polyethers are suitable for
producing mobile printing
inks, such as flexographic printing inks or gravure printing inks for
packaging printing. They can
be used for different purposes in printing inks, but especially as binders,
optionally also in a
mixture with other binders. More particularly, the inventive high-
functionality polyethers are
suitable in applications in which discoloring is disruptive, as in lacquers,
coverings and paints.
The inventive polyethers are formulated for this purpose, for example with
suitable solvents,
colorants, further binders and additives typical of printing inks. For further
details regarding the
formulation and production of printing inks with hyperbranched polymers,
reference is made
explicitly to WO 02/36695 and WO 02/26697, especially to the remarks in WO
02/36695,
page 10 line 19 to page 15 line 14, and WO 02/36697, page 7 line 14 to page 10
line 18, and
the examples adduced in said documents.
Printing inks which comprise the inventive polyethers have a particularly good
adhesion which
has been unknown to date on the substrates, especially on metal foils and/or
polymer films, and
exhibit particularly high color brightness.
The printing inks are therefore also very particularly suitable for producing
laminates composed
of two or more polymer films and/or metal foils, in which one film is printed
with one or more
layers of a printing ink and a second film is laminated onto the printed
layer. Such composites
are used, for example, for producing packaging.
In a further preferred embodiment, the inventive high-functionality
polyetherols are used as a
binder component, for example in customary coating materials, such as paints,
optionally
together with other binders having hydroxyl or amino groups, for example with
hydroxy
(meth)acrylates, hydroxystyryl (meth)acrylates, linear or branched polyesters,
polyethers,
polycarbonates, melamine resins or urea-formaldehyde resins, together with
compounds
reactive toward hydroxyl functions and optionally toward carboxyl functions,
for example with
isocyanates, capped isocyanates, epoxides and/or amino resins, preferably
isocyanates,
epoxides or amino resins, more preferably with isocyanates or epoxides and
most preferably
with isocyanates. Such coating materials are described, for example, in
"Polyurethane far Lacke
und Beschichtungen" [Polyurethanes for Paints and Coatings] by Manfred Bock,
Vincentz
Verlag, Hannover 1999.
Isocyanates are for example aliphatic, aromatic and cycloaliphatic di- and
polyisocyanates
having an average NCO functionality of at least 1.8, preferably from 1.8 to 5
and more
preferably from 2 to 4, and also their isocyanurates, oxadiazinetriones,
iminooxadiazinediones,
ureas, biurets, amides, urethanes, allophanates, carbodiimides, uretonimines
and uretdiones.
,
PF 70838 CA 02813844 2013-04-05
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The diisocyanates are preferably isocyanates having 4 to 20 carbon atoms.
Examples of
customary diisocyanates are aliphatic diisocyanates such as tetramethylene
diisocyanate,
hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene
diisocyanate,
decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene
diisocyanate,
derivatives of lysine diisocyanate, trimethylhexane diisocyanate or
tetramethylhexane
diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-
diisocyanatocyclohexane,
4,4'- or 2,4'-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethy1-5-
(isocyanatomethyl)-cyclohexane (isophorone diisocyanate), 1,3- or 1,4-
bis(isocyanatomethyl)cyclohexane or 2,4- or 2,6-diisocyanato-1-
methylcyclohexane, and also
aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate and isomer
mixtures thereof,
m- or p-xylylene diisocyanate, 2,4'- or 4,4'-dlisocyanatodiphenylmethane and
isomer mixtures
thereof, 1,3- or 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylene
diisocyanate, 1,5-
naphthylene diisocyanate, diphenylene 4,4'-diisocyanate, 4,4'-diisocyanato-
3,3'-
dimethylbiphenyl, 3-methyldiphenylmethane 4,4'-diisocyanate,
tetramethylxylylene diisocyanate,
1,4-diisocyanatobenzene or diphenyl ether 4,4'-diisocyanate.
Mixtures of said diisocyanates may also be present.
Useful polyisocyanates include polyisocyanates having isocyanurate groups,
polyisocyanates
having uretdione groups, polyisocyanates having biuret groups, polyisocyanates
having amide
groups, polyisocyanates having urethane or allophanate groups, polyisocyanates
comprising
oxadiazinetrione groups or iminooxadiazinedione groups, carbodiimide- or
uretonimine-modified
polyisocyanates of linear or branched C4-C20 alkylene diisocyanates,
cycloaliphatic
diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates
having a total of
8 to 20 carbon atoms, or mixtures thereof.
The di- and polyisocyanates which can be employed preferably have an
isocyanate group
content (calculated as NCO, molecular weight = 42) of 1 to 60% by weight,
based on the
diisocyanate and polyisocyanate (mixture), preferably 2 to 60% by weight and
more preferably
10 to 55% by weight.
Preference is given to aliphatic and/or cycloaliphatic di- and
polyisocyanates, examples being
the abovementioned aliphatic and/or cycloaliphatic diisocyanates, or mixtures
thereof.
Particular preference is given to hexamethylene diisocyanate, 1,3-
bis(isocyanato-
methyl)cyclohexane, isophorone diisocyanate and
di(isocyanatocyclohexyl)methane, very
particular preference to isophorone diisocyanate and hexamethylene
diisocyanate, and especial
preference to hexamethylene diisocyanate.
Preference extends to
PF 70838 CA 02813844 2013-04-05
1) Isocyanurate group-containing polyisocyanates of aromatic, aliphatic
and/or cycloaliphatic
diisocyanates. Particular preference here goes to the corresponding aliphatic
and/or
cycloaliphatic isocyanato isocyanurates and, in particular, to those based on
hexamethylene diisocyanate and isophorone diisocyanate. The present
isocyanurates
5 are, in particular, tris(isocyanatoalkyl) and/or
tris(isocyanatocycloalkyl) isocyanurates,
which are cyclic trimers of the diisocyanates, or are mixtures with their
higher homologs
containing more than one isocyanurate ring. The isocyanato isocyanurates
generally have
an NCO content of 10% to 30% by weight, in particular 15% to 25% by weight,
and an
average NCO functionality of 2.6 to 4.5.
2) Uretdione diisocyanates containing aromatically, aliphatically and/or
cycloaliphatically
attached isocyanate groups, preferably aliphatically and/or cycloaliphatically
attached, and
in particular those derived from hexamethylene diisocyanate or isophorone
diisocyanate.
Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
The uretdione diisocyanates can be used in the inventive formulations as a
sole
component or in a mixture with other polyisocyanates, especially those
mentioned under
1).
3) Polyisocyanates containing biuret groups and aromatically,
cycloaliphatically or
aliphatically attached, preferably cycloaliphatically or aliphatically
attached, isocyanate
groups, especially tris(6-isocyanatohexyl)biuret or its mixtures with its
higher homologs.
These polyisocyanates containing biuret groups generally have an NCO content
of 18% to
23% by weight and an average NCO functionality of 2.8 to 4.5.
4) Polyisocyanates containing urethane and/or allophanate groups and
aromatically,
aliphatically or cycloaliphatically attached, preferably aliphatically or
cycloaliphatically
attached, isocyanate groups, such as may be obtained, for example, by reacting
excess
amounts of hexamethylene diisocyanate or of isophorone diisocyanate with
monohydric or
polyhydric alcohols, for example methanol, ethanol, isopropanol, n-propanol, n-
butanol,
isobutanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-
octanol,
n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, stearyl alcohol,
cetyl alcohol,
lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, 1,3-
propanediol monomethyl ether, cyclopentanol, cyclohexanol, cyclooctanol,
cyclododecanol, or mixtures thereof. These polyisocyanates containing urethane
and/or
allophanate groups generally have an NCO content of 12 to 20% by weight and an
average NCO functionality of 2.5 to 4.5.
5) Polyisocyanates cornprising oxadiazinetrione groups, derived preferably
from
hexamethylene diisocyanate or isophorone diisocyanate. Polyisocyanates of this
kind
comprising oxadiazinetrione groups can be prepared from diisocyanate and
carbon
dioxide.
. PF 70838 CA 02813844 2013-04-05
11
6) Polyisocyanates comprising iminooxadiazinedione groups, preferably
derived from
hexamethylene diisocyanate or isophorone diisocyanate. Polyisocyanates of this
kind
comprising iminooxadiazinedione groups are preparable from diisocyanates by
means of
specific catalysts.
7) Carbodiimide-modified and/or uretonimine-modified polyisocyanates.
The polyisocyanates 1) to 7) can be used in a mixture, optionally also in a
mixture with
diisocyanates.
The isocyanate groups of the di- or polyisocyanates may also be in blocked
form. Examples of
suitable blocking agents for NCO groups include oximes, phenols, imidazoles,
pyrazoles,
pyrazolinones, triazoles, diketopiperazines, caprolactam, malonic esters or
compounds as
specified in the publications by Z. W. Wicks, Prog. Org. Coat. 3 (1975) 73- 99
and Prog. Org.
Coat 9 (1981), 3 ¨ 28, by D. A. Wicks and Z. W. Wicks, Prog. Org. Coat. 36
(1999), 148 ¨ 172
and Prog. Org. Coat. 41 (2001), 1 - 83 and also in Houben-Weyl, Methoden der
Organischen
Chemie [Methods of Organic Chemistry], vol. XIV/2, 61 if. Georg Thieme Verlag,
Stuttgart 1963.
Capping or blocking agents are understood to mean compounds which transform
isocyanate
groups into blocked (capped or protected) isocyanate groups, which then, below
a temperature
known as the deblocking temperature, do not display the usual reactions of a
free isocyanate
group. Compounds of this kind with blocked isocyanate groups are commonly
employed in dual-
cure coating materials or in powder coating materials which are cured to
completion via
isocyanate curing.
Epoxide compounds are those having at least one, preferably at least two, more
preferably from
two to ten epoxide group(s) in the molecule.
Suitable examples include epoxidized olefins, glycidyl esters (e.g. glycidyl
(meth)acrylate) of
saturated or unsaturated carboxylic acids or glycidyl ethers of aliphatic or
aromatic polyols.
Products of this kind are available commercially in large numbers. Particular
preference is given
to polyglycidyl compounds of the bisphenol A, F or B type and to glycidyl
ethers of
polyfunctional alcohols, such as that of butanediol, of 1,6-hexanediol, of
glycerol and of
pentaerythritol. Examples of polyepoxide compounds of this kind are Epikote
812 (epoxide
value: about 0.67 mo1/100 g) and Epikote 828 (epoxide value: about 0.53
mo1/100 g),
Epikote 1001, Epikote 1007 and Epikote 162 (epoxide value: about 0.61
mo1/100 g) from
Resolution, Riltapox 0162 (epoxide value: about 0.58 mo1/100 g), Rutapox
0164 (epoxide
value: about 0.53 mo1/100 g) and Rütapox 0165 (epoxide value: about 0.48
mo1/100 g) from
Bakelite AG, and Araldit DY 0397 (epoxide value: about 0.83 mo1/100 g) from
Vantico AG.
PF 70838 CA 02813844 2013-04-05
12
Also useful are compounds containing active methylol or alkylalkoxy groups,
especially
methylalkoxy groups, such as etherified reaction products of formaldehyde with
amines, such as
melamine, urea, etc., phenol/formaldehyde adducts, siloxane or silane groups
and anhydrides,
as described for example in US 5,770,650.
Among the preferred amino resins, which are known and widespread industrially,
particular
preference goes to using urea resins and melamine resins, such as urea-
formaldehyde resins,
melamine-formaldehyde resins, melamine-phenol-formaldehyde resins or melamine-
urea-
formaldehyde resins.
Suitable urea resins are those which are obtainable by reacting ureas with
aldehydes and which
may optionally be modified.
Suitable ureas are urea, N-substituted or N,N'-disubstituted ureas, such as N-
methylurea, N-
phenylurea, N,N'-dimethylurea, hexamethylenediurea, N,N'-diphenylurea, 1,2-
ethylenediurea,
1,3-propylenediurea, diethylenetriurea, dipropylenetriurea, 2-
hydroxypropylenediurea, 2-
imidazolidinone (ethyleneurea), 2-oxohexahydropyrimidine (propyleneurea) or 2-
oxo-5-
hydroxyhexahydropyrimidine (5-hydroxypropyleneurea).
Urea resins can optionally be partly or fully modified, by reaction for
example with mono- or
polyfunctional alcohols, ammonia and/or amines (cationically modified urea
resins) or with
(hydrogen)sulfites (anionically modified urea resins), particular suitability
being possessed by
the alcohol-modified urea resins.
Useful alcohols for the modification are C1¨C6 alcohols, preferably C1¨C4
alcohol and especially
methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol and sec-
butanol.
Suitable melamine resins are those which are obtainable by reacting melamine
with aldehydes
and which may optionally be fully or partly modified.
Particularly suitable aldehydes are formaldehyde, acetaldehyde,
isobutyraldehyde and glyoxal.
Melamine-formaldehyde resins are reaction products from the reaction of
melamine with
aldehydes, examples being the abovementioned aldehydes, especially
formaldehyde. The
resulting methylol groups are optionally modified by etherification with the
abovementioned
monohydric or polyhydric alcohols. In addition, the melamine-formaldehyde
resins may also be
modified as described above by reaction with amines, aminocarboxylic acids or
sulfites.
The action of formaldehyde on mixtures of melamine and urea or on mixtures of
melamine and
phenol produces, respectively, melamine-urea-formaldehyde resins and melamine-
phenol-
formaldehyde resins which can likewise be used in accordance with the
invention.
PF 70838 CA 02813844 2013-04-05
13
The stated amino resins are prepared by conventional methods.
Examples cited in particular are melamine-formaldehyde resins, including
monomeric or
polymeric melamine resins and partly or fully alkylated melamine resins, urea
resins, e.g.,
methylolureas such as formaldehyde-urea resins, alkoxyureas such as butylated
formaldehyde-
urea resins, but also N-methylolacrylamide emulsions,
isobutoxymethylacrylamide emulsions,
polyanhydrides, such as polysuccinic anhydride, and siloxanes or silanes, such
as
dimethyldimethoxysilanes, for example.
Particular preference is given to amino resins such as melamine-formaldehyde
resins or
formaldehyde-urea resins.
In addition, the inventive high-functionality polyethers can also be at least
partly esterified or
transesterified with a,r3-ethylenically unsaturated carboxylic acids or
derivatives thereof, for
example (meth)acrylic acid or (meth)acrylic esters, so as to form carbonates
of the hydroxyl-
containing polyesters with the a,13-ethylenically unsaturated carboxylic
acids, which can be
used, for example, as a monomer or crosslinker in radiation-curable coating
materials.
The coating materials in which the inventive high-functionality polyethers,
preferably high-
functionality polyetherols, are usable as binders may be conventional
basecoats, aqueous
basecoats, essentially solvent-free and anhydrous liquid basecoats (100%
systems), essentially
solvent- and water-free solid basecoats (powder coating materials and
pigmented powder
coating materials) or substantially solvent-free, optionally pigmented powder
coating dispersions
(powder slurry basecoats). They may be thermally curable, radiation-curable or
dual-curable,
and may be self-crosslinking or externally crosslinking.
The inventive coating materials are particularly suitable for coating of
substrates such as wood,
paper, textile, leather, fleece, polymer surfaces, glass, ceramic, mineral
building materials such
as cement blocks and fiber cement slabs, and especially metals or coated
metals.
Coating is accomplished typically by coating with the inventive coating
materials in a manner
known per se, then drying to remove any solvents present and curing.
The substrates are coated by customary processes known to those skilled in the
art, by
applying at least one inventive coating material in the desired thickness to
the substrate to be
coated, and removing the volatile constituents. This operation can, if
desired, be repeated once
or more than once. The application to the substrate can be effected in a known
manner, for
example by spraying, troweling, knife coating, brushing, rolling, roller
coating or pouring. The
coating thickness is generally within a range from about 3 to 1000 g/m2 and
preferably 10 to
200 g/m2.
,
PF 70838 CA 02813844 2013-04-05
,
14
The high-functionality polyethers formed by the process according to the
invention have
termination with hydroxyl groups after the reaction, i.e. without further
modification. They have
good solubility in various solvents, for example in alcohols such as methanol,
ethanol, butanol,
alcohol/water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate,
methoxypropyl
acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide,
dimethylacetamide,
N-methylpyrrolidone, ethylene carbonate or propylene carbonate.
The present invention is to be illustrated in detail by the examples which
follow.
Analysis and test methods:
Molecular weights and molecular weight distributions were analyzed by gel
permeation
chromatography with a refractometer as a detector. The mobile phase used,
unless stated
otherwise, was dimethylacetamide; the standard used to determine the molecular
weight was
polymethyl methacrylate (PM MA).
The DSC analysis was effected with a DSC-7 heat flow calorimeter from Perkin-
Elmer. For this
purpose, 5-7 mg of the sample were weighed into an aluminum crucible and
analyzed within a
temperature range from -100 to +100 C at a heating and cooling rate of 10 K
min-1. The glass
transition temperature (Tg) and the melting point (m.p.) were determined from
the second
heating curve.
The OH number (mg KOH/g) was determined to DIN 53240, Part 2.
Example 1 (comparative): Preparation of a polyether polyol based on THEIC
according to
US 3,293,224
The polycondensation was performed in a 2 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 522 g of THEIC, 150 g of
water and 6.4 g of
sulfuric acid (95% by weight) was heated to 80 C and stirred at standard
pressure for 1 h. Then
the internal temperature was increased to 130 C, in the course of which the
first water of
reaction formed and volatile by-products distilled off. The temperature was
then increased
gradually up to 165 C, and distillate passing over was collected. After 2 h of
reaction at 165 C,
the hot reaction mixture was poured into an aluminum dish and cooled.
The product had the following characteristics:
Tg: 53 C
GPC: Mn = 2500, Mw = 20 000 [g/mol]
Example 2: Preparation of an inventive polyether polyol based on THEIC and 1,4-
butanediol
,
PF 70838 CA 02813844 2013-04-05
The polycondensation was performed in a 2 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 261.2 g of THEIC, 90.1 g of
1,4-butanediol,
100 g of water and 1 g of sulfuric acid (95% by weight) was heated to 90 C and
stirred at
standard pressure for 3 h. Then the internal temperature was increased
gradually up to 165 C,
5 the mixture was stirred for 3 h and distillate which passed over was
collected. Thereafter, the
hot reaction mixture was poured into an aluminum dish and cooled.
The product had the following characteristics:
Tg: 30.6 C
10 GPC: Mn = 2000, Mw = 7600 [g/mol]
OH number: 325 mg KOH/g
Example 3: Preparation of an inventive polyether polyol based on THEIC and 1,5-
pentanediol
15 The polycondensation was performed in a 2 I glass flask equipped with
stirrer, feed vessel,
internal thermometer and distillation unit. The mixture of 522.6 g of THEIC,
200 g of water and
1 g of sulfuric acid (95% by weight) was heated to 90 C and stirred at
standard pressure for 1 h.
Then the internal temperature was increased gradually to 150 C and the water
used (200 g)
was collected as the distillate. Thereafter, the temperature was lowered to
100 C and 208.3 g of
1,5-pentanediol were added. The temperature was then increased to 160 C, in
the course of
which further distillate passed over. After 3 h of reaction time, the hot
reaction mixture was
poured into an aluminum dish and cooled.
The product had the following characteristics:
Tg: 15.6 C
GPC: Mn = 1400, Mw = 2700 [g/mol]
OH number: 377 mg KOH/g
Example 4: Preparation of an inventive polyether polyol based on THEIC and
1,10-decanediol
The polycondensation was performed in a 4 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 783.9 g of THEIC, 441 g of
1,10-decanediol,
200 g of water and 3 g of sulfuric acid (95% by weight) was heated to 90 C and
stirred at
standard pressure for 1 h. Then the internal temperature was increased
gradually to 170 C and
the distillate formed was removed. After 11 h of reaction time, the
temperature was lowered to
120 C, and the mixture was neutralized with 50% aqueous NaOH solution, poured
into an
aluminum dish and cooled.
The product had the following characteristics:
T8:-20.1 C
GPC: Mn = 1500, Mw = 16 400 [g/mol]
OH number: 243 mg KOH/g
,
PF 70838 CA 02813844 2013-04-05
16
Example 5: Preparation of an inventive polyether polyol based on THEIC and
diethylene glycol
The polycondensation was performed in a 4 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 1045.2 g of THEIC, 424.2 g
of diethylene
glycol, 300 g of water and 3 g of sulfuric acid (95% by weight) was heated to
90 C and stirred at
standard pressure for 1 h. Then the internal temperature was increased
gradually to 170 C, the
mixture was stirred for 10 h and distillate passing over was collected.
Thereafter, the reaction
mixture was cooled to 120 C, neutralized with 50% aqueous NaOH solution,
poured into an
aluminum dish and cooled.
The product had the following characteristics:
Tg: -4 C
GPC: Mn = 2200, Mw = 63 500 [g/mol]
OH number: 243 mg KOH/g
Example 6: Preparation of an inventive polyether polyol based on THEIC and
polyethylene
glycol (molecular weight 200 g/mol)
The polycondensation was performed in a 2 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 522.6 g of THEIC, 400 g of
polyethylene glycol
(Pluriol E 200, BASF SE), 200 g of water and 1 g of sulfuric acid (95% by
weight) was heated to
90 C and stirred at standard pressure for 1 h. Then the internal temperature
was increased
gradually to 170 C, the mixture was stirred for 3 h and distillate passing
over was collected.
Thereafter, the reaction temperature was lowered to 120 C, and the product was
poured hot
into an aluminum dish and cooled.
The product had the following characteristics:
Tg: -25 C
GPC: Mn = 2900, Mw = 92 000 [g/mol]
OH number: 228 mg KOH/g
Example 7: Preparation of an inventive polyether polyol based on THEIC and
neopentyl glycol
(NPG)
The polycondensation was performed in a 4 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 522.6 g of THEIC, 624.9 g of
NPG, 300 g of
water and 3 g of sulfuric acid (95% by weight) was heated to 90 C and stirred
at standard
pressure for 2 h. Then the internal temperature was increased gradually to 170
C over a period
of 8 h, in the course of which distillate passing over was collected.
Thereafter, the reaction
mixture was cooled to 120 C, neutralized with 50% aqueous NaOH solution,
poured into an
aluminum dish and cooled.
PF 70838 CA 02813844 2013-04-05
17
The product had the following characteristics:
Tg: -19.4 C
GPC: Mn = 900, Mw = 1800 [g/mol]
OH number: 390 mg KOH/g
Example 8: Preparation of an inventive polyether polyol based on THEIC and 2-
butyl-2-ethyl-
1,3-propanediol (BEPD)
The polycondensation was performed in a 2 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 392.0 g of THEIC, 240.4 g of
BEPD, 200 g of
water and 1 g of sulfuric acid (95% by weight) was heated to 90 C and stirred
at standard
pressure for 2 h. Then the internal temperature was increased gradually to 170
C over a period
of 8 h, in the course of which distillate passing over was collected.
Thereafter, the reaction
mixture was cooled to 120 C, neutralized with 50% aqueous NaOH solution,
poured into an
aluminum dish and cooled.
The product had the following characteristics:
Tg: -14.7 C
GPC: Mn = 800, Mw = 1600 [g/mol]
OH number: 335 mg KOH/g
Example 9: Preparation of an inventive polyether polyol based on THEIC and
stearyl alcohol
The polycondensation was performed in a 4 I glass flask equipped with stirrer,
internal
thermometer and distillation unit. The mixture of 1045.2 g of THEIC, 108.2 g
of stearyl alcohol,
300 g of water and 3 g of sulfuric acid (95% by weight) was heated to 90 C and
stirred at
standard pressure for 3 h. Then the internal temperature was increased
gradually to 150 C and
distillate passing over was collected. After 2 h, the reaction mixture was
cooled to 80 C and the
product was poured into an aluminum dish.
The product had the following characteristics:
Tg: 46.6 C, m.p. 61.3 C
GPC: Mn = 1000, Mw = 2100 [g/mol]
OH number: 350 mg KOH/g
Example 10 (comparative): Preparation of a polyether polyol based on
pentaerythritol and
triethylene glycol according to WO 2009/101141.
The polymerization was performed in a 1 I glass flask equipped with a stirrer,
reflux condenser
and a distillation system with vacuum connection. The mixture of 225.9 g of
pentaerythritol
(1.66 mol), 249.1 g of triethylene glycol (1.66 mol) and 4.8 g of p-
toluenesulfonic acid
PF 70838 CA 02813844 2013-04-05
18
monohydrate (1% by weight) was evacuated and heated gradually to 200 C by
means of an oil
bath at a pressure of 12 mbar. On attainment of the reaction temperature, the
reaction mixture
was stirred for 15 h. Thereafter, the reaction mixture was left to cool under
reduced pressure.
The crude product was taken up in 1 I of methanol, and unconverted
pentaerythritol was filtered
off. For neutralization, 10 g of basic alumina (MP ALUMINA B ACTIVITY SUPER I;
04571, MP
Ecochrom) were added to the reaction solution, and the mixture was stirred for
2 h and
incubated at -20 C overnight. After thawing, insoluble constituents were
filtered off through
Celite and the reaction mixture was then concentrated to dryness on a rotary
evaporator at
40 C and a reduced pressure of down to 22 mbar.
To remove unreacted ethylene glycol, the crude product was purified twice by
means of a thin-
film evaporator at an oil temperature of 195 C and a pressure of 1-5t10-2mbar.
This gave 248 g
(52% by weight) of polyether polyol.
The product had the following characteristics:
Tg : -32 C
GPC: Mn = 1100, Mw = 13 000 [g/mol], measured in hexafluoroisopropanol as the
mobile
phase.
OH number: 450 mg KOH/g
Table 1 shows the solubility behavior of in each case 1 g of the inventive
polyether polyols in
100 ml of solvent at room temperature.
Table 1
Polymer
from Ethyl Butyl
Example Water Ethanol 2-Butanone acetate acetate
1 (comp.)
4
7
8
+ : soluble
-: insoluble
The inventive polyether polyols have a much better solubility than comparative
polymer 1
(THEIC homopolymer), which is insoluble in many common solvents such as
ethanol,
2-butanone or ethyl acetate or butyl acetate. In addition, the inventive
polyetherols have a much
lower glass transition temperature (Tg), which leads to much better film
formation in the case of
use in surface coatings.
PF 70838 CA 02813844 2013-04-05
,
19
Table 2 shows the Hazen color numbers of the inventive products, measured as
50% by weight
solution in dimethylacetamide. The Hazen color number was determined to DIN
ISO 6271,
ASTM D 1209. The calibration standard used was a cobalt platinate solution.
For the
measurement, the products were dissolved in 50% by weight solution in
dimethylacetamide,
and the solution, before the color number measurement, was passed by means of
a disposable
syringe through a membrane filter designed as a disposable syringe attachment,
brand:
Sartorius Minisart RC 25 (pore size 0.45 micrometer).
Polymer
from
Example Color number (Hz)
2 29
3 41
4 32
5 96
6 24
7 37
8 71
9 38
(comp.) 820
10 Examples 11 (comparative) and 12: Use of the inventive polyethers in
paint formulations
Production of the paints:
For the production of the paints, the inventive polyether polyol from Example
7 was used to
produce an 80% by weight solution in butyl acetate. The OH number of the
solution was 312 mg
KOH/g.
All paint mixtures were made up with an index of 100 at room temperature, i.e.
a stoichiometric
ratio of isocyanate to hydroxyl groups. The isocyanate used was Basonatg' LR
9046 from BASF
SE, a polyisocyanurate based on hexamethylene diisocyanate with an NCO content
of approx.
23.0% by weight. The viscosity was adjusted by adding butyl acetate to a flow
time of approx.
20 s. The flow time was measured on the basis of ISO 2431 and EN 535 in a DIN
4 cup at room
temperature. What is reported is the time from the commencement of flow until
the breakage of
the liquid thread in seconds.
The paints were knife-coated while wet at room temperature with a 180 pm box-
type coating bar
onto a steel sheet as a substrate. The paint layer thickness after drying was
on average approx.
40 pm.
As Comparative Example 11, a paint which, instead of the polyol from Example
7, comprised
exclusively Joncryl 922 from BASF SE, an 80% by weight solution of a
polyacrylate polyol in
,
PF 70838 CA 02813844 2013-04-05
,
butyl acetate with an OH number of approx. 140 mg KOH/g was considered.
Joncryl 922o is a
commercial paint raw material. In contrast, in Example 12, 50% by weight of
the Joncryl 922
used is replaced by the polyol from Example 7.
5 Table 3 gives an overview of the composition of the inventive example and
of the comparative
paint, and Tables 4 and 5 an overview of the comparative properties.
Table 3:
Example No. 11 (comp.) 12
nonvolatile
fraction solid solid
BasonaP) LR 9046 100.0% 10.94 10.94
38.82 38.82
Polyol from Example 7 80.0% 28.13 22.50
Joncryl 922g) 80.0% 30.00 24.00
28.13 22.50
Butyl acetate 0% 15.50 30.00
Mass of paint [g] 56.44 34.94
125.07 83.82
Nonvolatile fraction (NVF) 61.9% 67.0%
Flow time 20 s 19.7 s
The nonvolatile fraction was determined by drying 1 g of the paint mixture or
of the feedstock in
a forced-air oven at 125 C for one hour. The residual weight, based on the
starting value
(=-100%), indicates the nonvolatile fraction.
Table 4 shows the determination of the paint hardness via the rise in pendulum
damping. For
this purpose, the paint, after application, was dried in a climate-controlled
room at room
temperature (23 C) and 50% relative air humidity over 4 days, and then at 60 C
for 15 h. The
pendulum damping is calculated according to KOnig in number of swings on the
basis of DIN EN
ISO 1522.
Table 4
Example No. 11 (comp.) 12
Layer thickness after drying 35 - 45 pm 35 - 45 pm
Gelation time ( h : min ) 4h 59min 15h 36min
Rise in p.d. 4 h --- --- ---
Rise in p.d. 7 h 14 13 ---
Rise in p.d. 24 h 55 54 35 37
Rise in p.d. 4d 70 69 112 112
4 d + 15 h at
Rise in p.d. 60 C 83 81 119 118
PF 70838 CA 02813844 2013-04-05
21
Table 5 shows the determination of the paint properties after venting, baking
and storage. For
this purpose, the paints are left to vent after application at 23 C and 50%
relative air humidity for
15 min, and then baked at 60 C for 30 minutes. The paints thus produced are
stored at 23 C
and 50% relative air humidity for 5 days and then analyzed. The results are
reported in Table 5.
The acetone double-rub test is effected with an acetone-soaked piece of
cottonwool. This was
rubbed by hand with double rubs on the paint until the paint had rubbed
through to the sheet.
The number of double rubs needed for that purpose is reported. At 100 rubs,
the test was
stopped, i.e. the value 100 indicates that the paint did not rub through in
this test.
The cross-cut adhesion was rated according to DIN 53151; the rating 0
represents the best
rating, i.e. no visible detachment of the paint.
The scratch resistance was determined by the Scotch-Brite test (scratch test).
For this purpose,
a fiber web (Scotchbrite, 7448 type S ultrafine) was attached with double-
sided adhesive tape to
the head of a 500 g fitter's hammer. The hammer was then held at the end of
the shaft by two
fingers and moved back and forth over the paint film in a line with uniform
double strokes,
without tipping and without applying additional pressure. The gloss of the
surface was
measured after 10 and 50 double strokes. After the gloss had been measured,
before further
stressing, the paint was heated at 60 C in a forced-air oven for 60 minutes
(reflow) and then
cooled to room temperature. The gloss was determined transverse to the
direction of abrasion.
The fiber web was renewed after each stress cycle. The gloss was measured with
the Mikro
TRI-Gloss measuring instrument at angles of incidence 20 and 60 .
Table 5
Example No. 11 (comp.) 12
Layer thickness 35 - 45 pm 35 - 45 pm
Cross-cut (Rating) 0 0
Acetone test (Double rubs) 100 100
Scratch test Gloss (60 ) 98.5 101.0
Scratch test 10 DR (60 ) 21.1 35.5
Scratch test 50 DR (60 ) 13.4 32.5
Scratch test Reflow (60 ) 20.2 78.1
Scratch test Gloss (20 ) 92.6 93.6
Scratch test 10 DR (20 ) 5.8 9.2
Scratch test 50 DR (20 ) 3.0 7.5
Scratch test Reflow (20 ) 10.0 61.9
Outcome of the tests:
The use of the inventive polymers leads to an extension in the gel time and
hence in the
processability, and to an improvement in hardness with comparable elasticity
and adhesion in
PF 70838 CA 02813844 2013-04-05
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the cross-cut test. The use of the inventive polymers likewise leads to a
distinct improvement in
the scratch resistance (see Tables 4 and 5).
