Note: Descriptions are shown in the official language in which they were submitted.
217450~
ENGLISH TRANSLATION
Wo 95/11284 1 PCT/EP94/03351
Binder~ based on oleochemical reaction products
This invention relates to binders based on oleo-
chemical reaction products and to their use for coating,
sealing, casting and binding.
"Binders" in the context of the invention are prod-
ucts which are capable of bonding substrates of the samekind or different kinds or of firmly adhering thereto.
They are generally based on substances or mixtures of
substances which set chemically and/or physically. In
addition to inorganic substances, organic substances
above all play an important role, synthetic high molecu-
lar weight compounds in which the high molecular weight
may even be reached in stages being especially signifi-
cant in this regard. These substances are generally
modified by additives in such a way that they are more
suitable for bonding, coating, sealing and casting.
Corresponding additives are, for example, resins, plasti-
cizers, solvents, fillers, pigments, accelerators,
stabilizers and dispersants. Accordingly, the adhesives,
sealing compounds, coating compounds or casting resins
are based on correspondingly modified binders.
Accordingly, the most important base for binders are
synthetic polymers, for example polyacrylates, polyvinyl
acetates, polyamides, polyisobutene, polyvinyl ethers,
polyurethanes, styrene/butadiene copolymers, ethylene/
vinyl acetate copolymers, polyvinyl chloride, phenolic
resins, etc.
Unfortunately, all the polymers mentioned above are
attended by the disadvantage that they are largely based
on structural elements of petrochemical origin, i.e.
ultimately emanate from petroleum or natural gas. The
multistage reaction steps required for the production of
these structural elements are complicated and represent
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Wo 95/11284 2 PCT/EP94/033Sl
a burden on the environment. Accordingly, corresponding
dispersions contribute towards increased depletion of oil
and gas occurrences and, on account of their poor biode-
gradability, pollute waters and waste disposal sites.
For this reason, efforts have been made to produce
polymers based on fats and oils. Thus, Wo 91/00305
describes polymers obtained by reaction of unsaturated
and/or hydroxyfunctional fatty acids or esters thereof
with bifunctional ester- and/or amide-forming compounds
and subsequent reaction of the difunctional monomer units
obtained with a second bifunctional compound. Since only
bifunctional compounds are produced and used, linear
polymers which can be melted and formed are obtained.
Thus, a film was produced at 200C and used to bond two
plates of glass at 190C.
An aqueous dispersion of polymers based on fats and
oils has also been described, cf. DE 43 05 309. Accord-
ing to this document, an anionic polymer is produced from
polyvalent metal ions and carboxylic acids based on fats
or oils. The carboxylic acids are monobasic to decabasic
and have a molecular weight Mn of preferably more than
400. Carboxylic acids such as these are linked together
by metal ions, such as Ca, Mg, Zn, Zr, Se, Al and Ti, via
ionic bonds in the main chain. These ionic polymers can
also be subsequently processed to aqueous dispersions.
Their disadvantages are: all the properties which are
attributable to a certain dissociation equilibrium of the
ionic groups in the main chain, for example the tendency
of the dried films to flow under load or at elevated
temperature - a property known to the expert as "cold
flow".
Accordingly, the problem addressed by the present
invention was to provide binders based on fats and oils
which would be satisfactory not only by virtue of their
better environmental compatibility, but also by virtue of
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WO 95/11284 3 PCT/EP94/03351
a sufficiently high performance level and competitive
price and, more especially, by virtue of the particularly
high initial tack (or surface tack), the ease of produc-
tion and the ready biodegradability which can be achieved
S with binders of the type in question.
The solution provided by the invention is defined in
the claims. It is distinguished above all by the fact
that the base used for the binders are reaction products
obtained by reaction of A) at least one fatty compound
containing on average 1 to 10 and preferably 1.5 to 6 of
at least one of the following functional groups: -OH,
-SH, -NH2, -C=C-, -COOH, anhydride group or an epoxide
group in the fatty component, the fatty compound contain-
ing at least 1 mole-% of at least trifunctional fatty
compounds, with B) at least one monofunctional or poly-
functional compound which is capable of reacting with the
functional groups of the fatty compounds.
The reaction products have an average molecular
weight Mn (osmotically determined number average) of at
least 1,500, more particularly at least 5,000 and - for
certain applications - preferably at least 8,000. The
molecular weight may be even further increased after the
reaction and before application of the binder, for
example after dispersion of the binder. The increase in
molecular weight can also lead to slight crosslinking,
although the binder remains castable or at least formable
during its application. The binder is applied at temper-
atures of 0 to 250C and, more particularly, at tempera-
tures of 20 to 150C. It is also swellable. The molecu-
lar weight is increased in particular after addition of
reactive systems, for example after addition of radical
initiators, such as benzoyl peroxide, or after addition
of curing agents, such as epoxy resins, polyisocyanates
and polyamines.
"Fatty compounds" in the context of the invention
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are fatty acids, fatty alcohols and derivatives thereof
which contain at least one of the following functional
groups -OH, -SH, -NH2, -C=C-, -COOH, anhydride group or
epoxide groups in the fatty component. The fatty com-
pound is not an individual compound, but rather a mix-
ture. This applies in particular to the functionality.
At least 1% of the molecules of the fatty compound have
at least three functional groups of the same kind or
different kinds, preferably at least 3%. The expert
knows how far he can take the reaction in order still to
achieve only branching of the molecules or at best such
slight crosslinking that the reaction products are still
formable. Fatty compounds with a molecular weight
(number average) above 300 or oligomerized fatty com-
pounds with a molecular weight above 800 are preferablyused. The molecular weight is generally above 200.
The fatty compounds are lipophilic.
"Fatty acids" in the context of the invention are
acids which contain one or more carboxyl groups (COOH).
The carboxyl groups may be attached to saturated, unsatu-
rated, unbranched or branched alkyl groups containing
more than 8 carbon atoms and, in particular, more than 12
carbon atoms. Besides the -OH, -SH, -C=C-, -COOH, amino,
anhydride groups or epoxide groups mentioned above, they
may contain other groups, such as ether, ester, halogen,
amide, amino, urethane and urea groups. However, car-
boxylic acids, such as native fatty acids or fatty acid
mixtures, dimer fatty acids and trimer fatty acids, are
preferred. Specific examples of the fatty acids accord-
ing to the invention besides the saturated types are, in
particular, the monounsaturated or polyunsaturated acids
palmitoleic, oleic, elaidic, petroselic, erucic, ricino-
leic, hydroxymethoxystearic, 12-hydroxystearic, linoleic,
linolenic and gadoleic acid.
In addition to naturally occurring fatty acids,
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polyhydroxy fatty acids may also be used. They may be
obtained, for example, by epoxidation of unsaturated fats
and oils or esters of fatty acids with alcohols, ring
opening with H-active compounds, for example alcohols,
amines and carboxylic acids, and subsequent saponifica-
tion. The fats or oils required as starting material may
be both of vegetable origin and animal origin or may
optionally be synthesized by particular petrochemical
methods.
The fatty acids may also be derived from oil- and
fat-based raw materials obtainable, for example, by ene
reactions, Diels-Alder reactions, transesterifications,
condensation reactions, grafting (for example with maleic
anhydride or acrylic acid, etc.) and epoxidation reac-
tions. Examples of such raw materials are a) epoxides of
unsaturated fatty acids, such as palmitoleic, oleic,
elaidic, petroselic, erucic, linoleic, linolenic, gadole-
ic acid, b) reaction products of unsaturated fatty acids
with maleic acid, maleic anhydride, methacrylic acid or
acrylic acid, c) condensation products of hydroxycar-
boxylic acids, such as ricinoleic acid or 12-hydroxy-
stearic acid, and polyhydroxycarboxylic acids.
Not all the fatty acids mentioned above are stable
at room temperature. If necessary, therefore, deriva-
tives of the above-mentioned fatty acids, such as esters
or amides, may be employed for the use according to the
inventlon .
A preferred embodiment of the invention is charac-
terized by the use of esters or partial esters of the
above-mentioned fatty acids with monohydric or polyhydric
alcohols. "Alcohols" in the context of the invention are
understood to be hydroxyl derivatives of aliphatic and
alicyclic saturated, unsaturated, unbranched or branched
hydrocarbons. Besides monohydric alcohols, these al-
cohols also include the low molecular weight hydroxyfunc-
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tional chain-extending or crosslinking agents known per
se from polyurethane chemistry. Specific examples from
the low molecular weight range are methanol, ethanol,
propanol, butanol, pentanol, decanol, octadecanol, 2-
ethylhexanol, 2-octanol, ethylene glycol, propylene
glycol, trimethylene glycol, tetramethylene glycol, 2,3-
butylene glycol, hexamethylenediol, octamethylenediol,
neopentyl glycol, 1,4-bis-hydroxymethyl cyclohexane,
Guerbet alcohol, 2-methyl propane-1,3-diol, hexane-1,2,6-
triol, glycerol, trimethylol propane, trimethylol ethane,pentaerythritol, sorbitol, formitol, methyl glycoside,
butylene glycol, the dimer and trimer fatty acids reduced
to alcohols. Monophenyl glycol or alcohols derived from
colophony resins, such as abietyl alcohol, may also be
used for the esterification.
Instead of the alcohols, OH-containing tertiary
amines, polyglycerol or partly hydrolyzed polyvinyl
esters may also be used.
The esterification with alcohols may also be carried
out in the presence of added saturated and branched fatty
acids, such as caproic, caprylic, capric, lauric, myris-
tic, palmitic, stearic, isostearic, isopalmitic, arachic,
behenic, cerotic and melissic acid. In addition, poly-
carboxylic acids or hydroxycarboxylic acids may be added
for oligomerization. Examples include oxalic acid,
malonic acid, succinic acid, maleic acid, fumaric acid,
glutaric acid, adipic acid, suberic acid, sebacic acid,
1,11-undecanedioic acid, 1,12-dodecanedioic acid, phtha-
lic acid, isophthalic acid, terephthalic acid, hexahydro-
phthalic ac,id, tetrahydrophthalic acid or dimer fattyacid, trimer fatty acid, citric acid, lactic acid,
tartaric acid, ricinoleic acid, 12-hydroxystearic acid.
Adipic acid is preferably used.
In addition to the partly saponified fats, such as
glycerol monostearate, preferred examples of esters
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Wo 9S/11284 7 PCT/EP94/03351
according to the invention are the natural fats and oils
of rape (new), sunflower, soya, linseed, castor beans,
coconuts, oil palms, oil palm kernels and oil trees and
methyl esters thereof. Preferred fats and oils are, for
example, beef tallow with a chain distribution of 67%
oleic acid, 2% stearic acid, 1% heptadecanoic acid, 10%
saturated C12_l6 acids, 12% linoleic acid and 2% saturated
acids containing more than 18 carbon atoms or, for
example, the oil of new sunflowers (NSf) with a composi-
tion of around 80% oleic acid, 5% stearic acid, 8%linoleic acid and around 7% palmitic acid. The corre-
sponding epoxides and reaction products with maleic
- anhydride, for example, may of course also be used.
Other examples are partly and completely dehydrated
castor oil, partly acetylated castor oil, ring opening
products of epoxidized soybean oil with dimer fatty acid.
Fatty acid esters and derivatives thereof obtainable
by epoxidation are preferably used. Examples of such
fatty acids include soybean oil fatty acid methyl ester,
linseed oil fatty acid methyl ester, ricinoleic acid
methyl ester, epoxystearic acid methyl ester, epoxy-
stearic acid 2-ethylhexyl ester. Preferred glycerides
are the triglycerides, for example rapeseed oil, linseed
oil, soybean oil, castor oil, partly and completely
dehydrated castor oils, partly acetylated castor oil,
soybean oil epoxide, linseed oil epoxide, rapeseed oil
epoxide, epoxidized sunflower oil.
Epoxidized triglycerides of unsaturated fatty acids
ring-opened with nucleophiles may be used in another
preferred embodiment of the invention. Nucleophiles in
the context of the invention are alcohols, for example
methanol, ethanol, ethylene glycol, glycerol or trimethy-
lol propane; amines, for example ethanolamine, diethanol-
amine, triethanolamine, ethylenediamine or hexamethylene-
diamine; or carboxylic acids, for example acetic acid,
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WO 95/11284 8 PCT/EP94/03351
dimer fatty acid, maleic acid, phthalic acid or a mixtureof C6_36 fatty acids.
However, it is best to use fats and oils (triglycer-
ides) both in native form and after thermal and/or
oxidative treatment or the derivatives obtainable by
epoxidation or by the addition of maleic anhydride or
acrylic acid. Specific examples are palm oil, peanut
oil, rapeseed oil, cottonseed oil, soybean oil, castor
oil, partly and completely dehydrated castor oils, partly
acetylated castor oils, sunflower oil, linseed oil, stand
oils, blown oils, epoxidized soybean oil, epoxidized
linseed oil, rapeseed oil, coconut oil, palm kernel oil
and tallows. At least 50% by weight and, more particu-
larly, at least 80% by weight of fatty compounds with the
triglyceride structure should still be present after the
modification.
Amides of the fatty acids mentioned above may also
be used as derivatives. They may be obtained by reaction
with primary and secondary amines or polyamines, for
example with monoethanolamine, diethanolamine, ethylene-
diamine, hexamethylenediamine, ammonia, etc.
"Fatty alcohols" in the context of the invention are
compounds which contain one or more hydroxyl groups. The
hydroxyl groups may be attached to saturated, unsatura-
ted, unbranched or branched alkyl groups containing morethan 8 carbon atoms and, in particular, more than 12
carbon atoms. In addition to the -SH, -C=C-, -COOH,
amino, anhydride or epoxide groups required for the
subsequent oligomerization, they may contain other
groups, for example ether, ester, halogen, amide, amino,
urea and urethane groups. Specific examples of the fatty
alcohols according to the invention are ricinoleyl
alcohol, 12-hydroxystearyl alcohol, oleyl alcohol, erucyl
alcohol, linoleyl alcohol, linolenyl alcohol, arachidyl
alcohol, gadoleyl alcohol, erucyl alcohol, brassidyl
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Wo 95/11284 9 PCT/EP94/03351
alcohol, dimer diol (= hydrogenation product of dimer
fatty acid methyl ester).
Symmetrical and non-symmetrical ethers and esters
with mono- and polycarboxylic acids may be used as
derivatives of the fatty alcohols. Monocarboxylic acids
include formic acid, acetic acid, propionic acid, butyric
acid, valeric acid, caproic acid, oenanthic acid, capry-
lic acid, pelargonic acid, capric acid, undecanoic acid,
lauric acid, tridecanoic acid, myristic acid, pentadecan-
oic acid, palmitic acid, margaric acid, stearic acid,nonadecanoic acid, arachic acid, behenic acid, lignoceric
acid, cerotic acid and melissic acid. Polycarboxylic
acids are, for example, oxalic acid, adipic acid, maleic
acid, tartaric acid and citric acid. At the same time,
the fatty acids described above, for example oleic acid
oleyl ester, may also be used as the carboxylic acid.
The fatty alcohols may also be etherified, more
particularly with the same fatty alcohols or with other
fatty alcohols and also with other polyhydric alcohols,
for example alkyl polyglycosides, dioleyl ethers, dimer
diol ethers, diepoxydistearyl ethers, oleyl butyl ethers.
Mixtures of the above-mentioned fatty compounds may
of course also be added.
In the case of unsaturated fatty compounds, it might
be appropriate to add siccatives in quantities of 1 to 5%
by weight, based on the fatty compound. Specific examp-
les are napthenates, octoates, linoleates or resinates of
Co, Mn, Pb or mixtures thereof.
"Mono- or polyfunctional compounds capable of
reacting with the functional groups of the fatty com-
pounds" (component B) are understood above all to be at
least one of the following compounds: vinyl esters,
(meth)acrylates containing up to 18 carbon atoms in the
alcohol component, ethylene, styrene, butadiene, acrylo-
nitrile, vinyl chloride, polyhydric alcohols, polyamines,
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aminoalcohols, polymercaptans, aminomercaptans, alcohol
mercaptans, amino acids, hydroxy acids, mercaptan acids,
polycarboxylic acids - including those of relatively high
molecular weight, such as dimer fatty acids for example--
anhydrides, polyepoxides and polyacid chlorides, anyaliphatic and aromatic, more especially difunctional,
isocyanates and NCO-terminated short-chain prepolymers
produced therefrom (Mw < 8,000). The molecular weight of
component B) is generally below 2,000 (number average).
The percentage content of component B is at most 80%
by weight and preferably at most 50% by weight, based on
the weight of components A) and B). However, the equiva-
lent ratio of the functional groups of component A) and
component B) is crucial. After thorough mixing, however,
components A) and B) are only reacted to such an extent
that still formable reaction products are initially
obtained and may even be converted into thermoset prod-
ucts by further crosslinking.
The reaction results in the formation of more or
less branched macromolecules or polymers, including
oligomers. The reaction in question is the known reac-
tion used for the synthesis of polymers, i.e. polyaddi-
tions, polycondensations and polymerizations, more
particularly transesterifications, condensation reac-
tions, ene reactions, grafting reactions (for examplewith maleic anhydride and subsequent chain extension with
polyols or polyamines) and ring opening of epoxide
groups. The molecular structure of the triglyceride of
the oils and fats remains largely intact. However, it
may even be partly lost through transesterification or
transamidation or modified as required by such reactions.
It is essential that the polyreaction lead to
reaction products having an average molecular weight MW
of at least 1,500 and, more particularly, at least 5,000
(as determined by GPC). On the other hand, however, the
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Wo ss/li284 11 PCT/EP94/03351
reaction product should still not gel in the melt. This
is because a certain flow behavior is required for the
subsequent application, more particularly for dispersion
in water at elevated temperature. However, this flow
behavior can be improved by addition of external emulsi-
fiers or other additives, for example plasticizers, to
the polymer melt.
The reaction can be accelerated by addition of
stabilizers to such an extent that it takes place in
acceptable times even at room temperature. For example,
the reaction of carboxylic anhydride groups with alcohol
groups can be greatly accelerated by hetero aromatic
amines containing other hetero atoms in the ring.
Corresponding catalysts are derivatives of pyrrole,
indolizine, indole, isoindole, benzotriazole, carbazole,
pyrazole, imidazole, oxazole, isooxazole, isothiazole,
triazole, tetrazole, thiazoles, pyridine, quinoline,
isoquinoline, acridine, phenanthridine, pyridazines,
pyrimidines, pyrazine, triazines and compounds cont~;ning
corresponding structural elements. Particularly suitable
catalysts are l-methyl imidazole, 2-methyl-1-vinyl imida-
zole, 1-allyl imidazole, l-phenyl imidazole, 1,2,4,5-
tetramethyl imidazole, l-(3-aminopropyl)-imidazole,
pyrimidazole,4-dimethylaminopyridine,4-pyrrolidinopyri-
dine, 4-morpholinopyridine, 4-methyl pyridine.
Accordingly, the end of the polyreaction can be
calculated from the average functionality of the fats and
oils on the one hand and the functionality of compound B
reacted therewith and from the ratio in which these two
reactants are mixed. However, a series of tests with
increasing concentrations of compound B and increasing
reaction times is more practical than this estimation by
calculation. It is possible in this way quickly and
reliably to obtain information on the position of the
particular gel point beyond which thermoplastic pro-
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cessing with a corresponding softening range is no longerpossible.
The reaction products are preferably synthesized as
follows; polyfunctional compounds containing 1 to 10 and
preferably 1.5 to 6 functional groups may be used quite
generally instead of the described difunctional com-
pounds.
1.) Reaction products based on fatty or oil epoxides
The production of typical oleochemical epoxides and
oils and fats suitable for this purpose are described in
DE 43 05 309. The fatty or oil epoxides may be both
partly epoxidized and fully epoxidized. The preferred
functionality of the epoxide-ring-opening reaction
products is between 1.5 and 5.0 and, more particularly,
2, diols, diamines and dicarboxylic acids being par-
ticularly suitable for ring opening. To control molecu-
lar weight or to initiate opening of the epoxide ring by
itself, monofunctional amines, alcohols and carboxylic
acids may also be added in small amounts. Fatty or oil
epoxides are ring-opened with polyfunctional alcohols,
amines, aminoalcohols, mercaptans, aminomercaptans,
alcohol mercaptans, carboxylic acids, amino acids,
hydroxy acids, mercaptan acids, etc. However, any
diamines and diols suitable for the production of poly-
urethanes may also be used. Dicarboxylic acids, includ-
ing those of relatively high molecular weight, such as
dimer fatty acid for example, are also suitable for
reaction with the oleochemical epoxides. The OH groups
formed by ring opening and the other OH or NH2 groups may
also be reacted with polyisocyanates, more particularly
diisocyanates. The reaction of isocyanates with amines
and alcohol groups, which are present at the derivatized
or polymerized fatty and oil molecules, may also be
carried out after dispersion in water. Curing with
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WO 95/11284 13 PCT/EP94/03351
radical initiators, such as dibenzoyl peroxide, is also
possible. Both water-insoluble and water-dispersible
isocyanates are suitable for subsequent crosslinking.
2.) Reaction products based on OH and NH2 groups of fats
and oils
Fatty and oil derivatives containing functional OH
and NH2 groups, for example castor oil, the reaction
products of oleochemical epoxides with monoalcohols or
monoamines, may be reacted with reactive multifunctional,
more particularly difunctional, molecules such as, for
example, anhydrides, diisocyanates, diepoxides and diacid
chlorides to form polymers, the number of functional
groups having to be between 1.5 and 5. Any aliphatic and
aromatic, more especially difunctional, isocyanates and
NCO-terminated short-chain prepolymers produced therefrom
(Mn: < 20,000 and, more particularly, < 8,000) are suit-
able for this purpose. In this case, too, the disper-
sions may be subsequently reacted with polyisocyanates,
as described under 1.).
Particularly suitable diepoxides are those used for
two-component reaction adhesives or coatings.
Suitable anhydrides are, for example, the saturated
and unsaturated types used in the synthesis of polyesters
and polyamides.
3.) Reaction products based on unsaturated fats and oils
containing anhydride groups
Unsaturated fats and oils can be grafted with
anhydrides, more especially maleic anhydride, at elevated
temperature. Corresponding reactions are described in DE
43 05 397, for example for rapeseed oil or soybean oil.
The fatty and oil molecules provided with anhydride
groups can be reacted with the compounds already men-
tioned, more particularly difunctional compounds, for
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example diamines, dialcohols (diols), aminoalcohols andtheir mercaptan variants to form polymeric molecules. In
this case, too, the location of the gel point and whether
or not it is reached are determined by the stoichiometry
in dependence upon the functionality of the fatty or oil
molecules, i.e. ultimately by the average number of
anhydride groups attached to a triglyceride molecule.
However, fatty compounds containing C=C double bonds
may also be initially reacted with dienophiles such as,
for example, maleic anhydride, methacrylic acid and
acrylic acid and then further reacted with polyamines,
polyols or aminoalcohols, the average number of function-
al groups preferably being from 1.5 to 5.
Before the grafting or addition reaction, it might
be appropriate to react the fatty compounds containing
C=C double bonds in the presence of oxygen, radical
initiators or at elevated temperature. This may be done
both in the absence and above all in the presence of
radical-polymerizable compounds containing olefinic C=C
double bonds, more especially in the presence of at least
one of the following monomers: styrene, vinyl esters,
vinyl chloride, butadiene, ethylene, acrylic acid,
(meth)acrylates, crotonic acid, acrylonitrile or mixtures
of these monomers.
The reactions may be carried out in solution, in
dispersion or in the melt. The most appropriate form is
determined above all by the application envisaged for the
binder. In general, however, the reaction is advantage-
ously carried out in the melt and the reaction product
subsequently converted into an aqueous dispersion.
The dispersion is generally prepared as follows: the
polymers are heated to 50C to 150C and preferably to
80C to 130C and then dispersed in water with intensive
shearing. Conversely, the water may be introduced into
the melt. Before dispersion, other additives, for
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WO 95/11284 15 PCT/EP94/03351
example polymers, plasticizers, resins, antiagers, etc.,
may be added in quantities of up to at most 50% and
preferably in quantities of up to at most 30%. Depending
on the viscosity of the melt, the water may also be
heated with advantage to around the temperature of the
melt. At mixing temperatures above 95 to 100C, pressure
emulsification is necessary.
Emulsifiers which are either added (external emulsi-
fiers such as, for example, nonionic surfactants and
ether sulfonic acids and also ether carboxylic acids) or
which are already incorporated in the polymer (internal
emulsifiers) are required for dispersion. Internal
emulsifiers may be, for example, NaOH- or amine-neutral-
ized COOH groups (anionic dispersion) which are present
as lateral groups, for example, in method 3.) for the
production of the polymers. Acid-protonated or alkylated
amine groups in the polymer chains (cationic dispersion)
may also perform the function of internal emulsification.
External emulsifiers may be both low molecular weight
compounds and polymers. Corresponding emulsifiers or
surfactants are known to the expert and are described in
numerous reference books (for example Tensid-Taschenbuch,
Dr. Heimut Stache, 2nd Edition, 1981, Carl-Hanser-Verlag,
Munchen/Wien, more particularly pages 771 to 978). In
addition, ionic or nonionic stabilized polymer disper-
sions (for example acrylates or polyurethanes) may also
be added as emulsifiers, their emulsifying effect being
known to increase with increasing hydrophilicity. Pro-
tective colloids of the type used in the preparation of
polymer dispersions (for example polyvinyl acetate), for
example starch, starch derivatives, cellulose deriva-
tives, polyvinyl alcohols, etc., may also be added.
Accordingly, dispersions in which the reaction
product is finely dispersed in water are obtained. The
reaction product can be so finely dispersed that the
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Wo 95/11284 16 PCT/EP94/03351
dispersion is clear in appearance (molecular or colloidal
dispersion). In general, however, the dispersion is
cloudy.
After dispersion, the molecular weight of the
reaction product is best increased using known hardening
agents and/or initiators. Slight crosslinking is also
possible. However, swellability should still be guaran-
teed.
In the oleochemical macromolecules obtained in
accordance with the invention the structural elements are
attached to one another by covalent bonds. This results
in performance properties totally different from those of
the known ionomers based on fats and oils. This applies
in particular to heat resistance and temperature-depen-
dent strength and flow behavior and to behavior towards
water. Despite their high percentage content of fatty
compounds, the binders according to the invention result
in bonds which at least have the strength of contact
adhesives. However, they need not be permanently tacky.
20Accordingly, the binders according to the invention
are suitable for coating, sealing, casting and binding,
more especially for bonding or binding inorganic formula-
tions, such as cement and gypsum.
Depending on the particular application envisaged,
additives, for example waxes, fillers, pigments, disper-
sants, stabilizers, viscosity regulators, preservatives,
solvents and resins, are best added to the binders for
the production of adhesives, casting resins, sealing
compounds or coating compositions. The additives are
known as are the methods by which they are incorporated.
However, the binders according to the invention may
also be added to commercial polymer dispersions or glues
in quantities of 2 to 90% by weight and more particularly
in quantities of up to 50% by weight, based on the
binding polymer in the polymer dispersion or in the glue.
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Wo 95/11284 17 PCT/EP94/03351
The polymer dispersions and the glues are based on the
usual polymers, such as casein, glutin, cellulose ethers,
starch, dextrin, polyvinyl pyrrolidone, polyvinyl al-
cohol, polymethacrylates, polyvinyl chloride, polybutadi-
ene, polystyrene, styrene/acrylate copolymers, styrene/butadiene copolymers, polyvinyl esters and polyurethanes.
These polymer dispersions and glues have a solids content
of 20 to 80% by weight.
The expert knows the rules governing the compatibil-
ity of such mixtures. For example, cationically andanionically stabilized dispersions are generally incom-
patible and a significant displacement in the pH value
can also lead to the coagulation of a dispersion or
mixture of dispersions. Nonionically stabilized disper-
lS sions are normally the least sensitive to variations inpH and addition of ions.
By virtue of their properties, the binders according
to the invention are suitable for the production of
adhesives, adhesive sealing compounds, adhesive casting
resins and coating compositions, more particularly where
less importance is attributed to peak strength values
than to price. They are particularly suitable for
substrates differing in their elastic behavior or thermal
expansion coefficients, as is generally the case with
different substrates. Suitable substrates are wood,
paperboard, paper, wall coverings, such as wallpapers,
cork, leather, rubber, felt, textiles, plastics (more
particularly floor coverings of PVC, linoleum and poly-
olefins either in the form of films or sheet-form tex-
tiles), mineral substrates, such as glass, quartz, slags,rock and ceramics and also metals.
The binders according to the invention are par-
ticularly suitable for the production of dispersion
adhesives, contact adhesives, solvent-based adhesives,
adhesive sticks, plastisols and hotmelt adhesives. They
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WO 95/11284 18 PCT/EP94/03351
are also particularly suitable as jointing compounds, as
adhesive casting resins and as coating compositions for
hard substrates and for textiles and paper.
The invention is illustrated by the following
Examples:
BxamPle~
Example I
29 g of Jeffamin D 2000 (amine-terminated polypropy-
lene glycol, Mn 2000) are added at 80 C to 50 g of the
reaction product of 1 mole of soybean oil with 3 moles of
maleic anhydride (stirred under nitrogen for 6 hours at
240-C and then distilled), the Jeffamin being added
dropwise over a period of 10 minutes. The temperature of
the highly viscous mixture is increased to lOO C and 47.7
g of water containing 3.8 g of sodium hydroxide and
preheated to 50C are quickly added with intensive
mixing. A transparent- to opaque high-tack dispersion
with a viscosity of 10,000 mPa s and a solids content of
65% is formed after cooling for 20 minutes to room
temperature. The dispersion has a pH value of 7.5 and is
stable in storage for at least 3 months.
Example II
Production is carried out as in Example I (stirring
under nitrogen for 6 hours at 200C and then for 4 hours
at 220C, no distillation) except that the 29 g of
Jeffamin 2000 are replaced by the corresponding equimolar
quantity of isophoronediamine and the quantity of sodium
hydroxide used for neutralization during dispersion
remains constant. A dispersion with a solids content of
50% and a pH value of 7.6 is formed. It produces a low-
tack film which becomes transparent on drying.
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W0 95/11284 19 PCT/EP94/03351
Example III
- 50 g of the reaction product of 1 mole of soybean
oil with 2 moles of maleic anhydride are reacted with
stirring for 1 hour at around 150C with 8.6 g of Poly-
diol 200 (polyethylene glycol with a molecular weight Mn
of 200). The temperature of the mixture is then lowered
to 90-C and 65 g of water containing 4.6 g of sodium
hydroxide and preheated to 50~C are quickly added with
intensive mixing. A tacky transparent dispersion with a
solids content of 50~ is formed after cooling to room
temperature. The dispersion is stable in storage for at
least 6 months.
Example IV
50 g of the reaction product of 1 mole of soybean
oil with 2 moles of maleic anhydride are reacted with
12.7 g of polytetrahydrofuran 2000 (Mn = 2000) in the
same way as described in Example III. 65 g of water and
5.1 g of sodium hydroxide are used for dispersion. A
transparent dispersion with a solids content of 50% is
formed. It produces a tacky film which becomes trans-
parent on drying. The dispersion is stable in storage
for at least 6 months.
Example V
50 g of the reaction product of 1 mole of soybean
oil with 2 moles of maleic anhydride are reacted with 8.6
g of Polydiol 600 (polyethylene glycol, Mn = 600) in the
same way as described in Example III. 68 g of water and
8.0 g of sodium hydroxide are used for dispersion. A
transparent dispersion with a solids content of 50% is
formed. It produces a tacXy film which becomes trans-
parent on drying. The dispersion is stable in storage
for at least 6 months.
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Example VI
Soybean oil epoxide is ring-opened with dimer fatty
acid in a molar ratio of 1:1 (stirred for 1 hour at
160-C). 40 g of this oleochemical reaction product are
dispersed with intensive mixing at 90-C with 124 g of
water containing 3.3 g of sodium hydroxide and preheated
to 90-C. A low-viscosity milky dispersion with a solids
content of 25~ is formed after cooling to 20-C. It
produces a transparent low-tack film. The dispersion is
stable in storage for at least 6 months.
Example VII
Castor oil is reacted with phthalic anhydride in a
molar ratio of 1:2 (stirred under nitrogen for 2 hours at
140-C). 40 g of this reaction product are dispersed with
intensive mixing at 90-C with 100 g of water containing
5.2 g of sodium hydroxide and preheated to 90-C. A
medium-viscosity milky dispersion with a solids content
of 31% is formed after cooling to room temperature. It
produces a transparent low-tack film. The dispersion is
stable in storage for at least 6 months.
Example VIII
278.3 g of an adduct of soybean oil with maleic
anhydride (MA) in a molar ratio of 1:2 are heated with
stirring for 1.5 h to 150 - 160-C with 188.1 g of partly
dehydrated castor oil having an OH value of 120. After
cooling to 90 - 95 C, a solution of 3.26 g of 50% NaOH in
20 g of hot water (90C) is added with intensive stir-
ring. Another 480.1 g of hot water are then slowlyadded. 1000 g of a dispersion which dries to form a
high-tack film are obtained after cooling with stirring
to room temperature.
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WO 95/11284 21 PCT/EP94/03351
Example IX
268.1 g of partly dehydrated castor oil (OH value
120), 40.2 g of Desmodur 44 V 10 (technical methylenedi-
phenyl diisocyanate) and 61.7 g of Eumulgin KP 92 (fatty
acid mixture containing 9.2 EO) are heated for 2 h to
50C. 630 g of warm water (60C) are then slowly added
with stirring. Approximately 1000 g of a beige-colored
dispersion are obtained after cooling to room tempera-
ture.
Example X
Reaction of Polyvest C 150 (polycarboxylic anhydride
of butadiene, maleic anhydride and succinic anhydride
manufactured by Huls) with a polyester/polyether polyol
(reaction product of soybean oil epoxide and methanol in
a ratio of 1:6, produced by the dropwise addition method
with a 1 hour after-reaction by Henkel KGaA)
Catalyst: N-methyl imidazole
Component A: Polyvest C 150
Component B: polyester/polyether polyol
Reaction temperature: 20C
Compo- Compo- Cat. Reaction time tdays]
25 nent A nent B % by
[g] [g] weight 1 2 5
23 - Mixture remains highly viscous
23 1 Soft Rubbery Hard
tacky tacky rubbery
1 Soft Rubbery Hard
- tacky tack-free rubbery
1 Soft Rubbery Hard
tacky tacky rubbery
Example XI
Reaction of a reaction product of soybean oil and
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Wo 95/11284 22 PCT/EP94/03351
maleic anhydride (100 g oil : 30 g MA, component A) with
glycerol + 5 E0 (component B) at 20-C
Catalyst: N-methyl imidazole
Compo- Compo- Cat. Reaction time [hours]
nent A nent B % by
[g] [g] weight l 2 5
10 20 4 - Mixture remains highly viscous
20 4 1.4 Rubbery Rubbery Hard
tacky tack-free rubbery
Example XII
Reaction of a reaction product of linseed oil and
maleic anhydride (100 g oil : 20 g MA, component A) with
glycerol + 30 E0 (component B)
Catalyst: 1.6% by weight N-methyl imidazole
Component A: 10 g
Component B: 8 g
Slightly tacky after 60 mins.
Hard after 10 h.
Example XIII
Reaction of a reaction product of linseed oil and
maleic anhydride (100 g oil : 30 g MA, component A) with
glycerol + 30 E0 (component B)
Catalyst: 1.4% by weight N-methyl imidazole
Component A: lO g
Component B: 10.8 g
Surface-dry after 30 mins.
Hard after 3 h.
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The oleochemical reaction products of Examples X to
XIII are suitable for use as a tacky casting resin which
cures even at room temperature.
