Note: Descriptions are shown in the official language in which they were submitted.
CA 02230024 1998-02-19
H 1759 PCT
23.08. 1 995
A Gypsum-Containing Composition and its Use
This invention relates to a gypsum-based composition containing
special oleochemical additives and to the use of this composition for the
production of gypsum components and for special building plasters, gypsum
plasters and grouting compounds.
By virtue of its ability to set with water, gypsum in the form of the
anhydride or hemihydrate has long been a valued raw material with many
interesting properties, for example minimal shrinkage, fire resistance and a
neutral pH value during curing. Today, large quantities of gypsum are also
formed in the desulfurization of waste gases and need to be put to an
ecologically safe use.
However, one disadvantage of set gypsum mortars, screeds and
coatings is the relatively poor water resistance of these systems. The exterior
use of gypsum, for example as a plaster, still remains an unsolved problem.
It is already known that gypsum can be hydrophobicized by addition of
special polysiloxanes in quantities of up to 2% by weight. However, this is a
disadvantage insofar as the addition of polysiloxanes causes serious harm to
the environment due to their biological non-degradability and their unfavorable
ecobalance. In addition, correspondingly modified gypsums are not of
sufficient quality for exterior applications.
DE-OS 32 38 390 describes a ready-made mortar which contains
gypsum or cement as binder and, in addition, a quantity of 0.5 to 1% by
volume, based on the volume of the ready-made mortar, of a mixture of 60 to
88% of a C,0 20 paraffin hydrocarbon mixture and/or a glycerol ester, a higher
fatty acid or a fat and 12 to 40% of a surfactant as emulsifier. The mixture in
question has hydrophobicizing properties so that the mortar shows better
heat-insulating properties and frost resistance.
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H 1759 PCT 2
JP-A-82/61648 describes a dispersant for gypsum which contains a
condensate of an (alkyl) naphthalene sulfonic acid and formaldehyde, a
silicon dioxide powder and optionally an oil selected from mineral oils,
synthetic lubricating oils and natural oils. The gypsum disperses thoroughly
in water until its sets by reacting with water. The separation of water from themixture of gypsum and water, i.e. the gypsum suspension, is reduced during
the setting process and the cured gypsum is obtained in a high quality.
JP-A-73/73427 describes both fire-resistant and water-resistant plaster
mortar walls containing cellulose ethers which are obtained by reacting a
suspension of calcined gypsum together with a water-containing cellulose
resin, asbestos or glass fibers in a mold in the presence of a metal salt of a
higher fatty acid and applying heat to drive out the water.
JP-A-79/10974 describes building boards with improved resistance to
water which are obtained by adding a higher fatty acid or a salt thereof in a
relatively large quantity to a hydraulic material, such as cement or calcined
gypsum.
Belgium patent application 873812 describes a solidified gypsum
concrete which is obtained by thoroughly mixing gypsum and water, the
gypsum being partly replaced by a substantially insoluble metal salt of a fatty
acid. A calcium, aluminium, barium, lead, magnesium, zinc, copper or nickel
salt of stearic acid, oleic acid, palmitic acid or similar acids is used for
hydrophobicization.
JP-A-82/3751 describes water-resistant, set gypsum moldings which
are obtained by reacting a hydrophobicizing agent with calcium oxide hemi-
hydrate, adding water, molding and heating in an atmosphere containing
carbon dioxide. The hydrophobicizing agent is used in a quantity of 0.5 to
12% by weight in the form of a higherfatty acid, such as stearic acid, palmitic
acid, oleic acid, coconut oil fatty acids, etc. and alkali/alkaline earth metal
salts thereof.
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H 1759 PCT 3
JP-A-83/41750 describes a material for boards which is obtained by
reacting a hydraulic material, such as cement, a mixture of cement, granu-
lated slag and gypsum, etc., an inorganic fiber-containing material, such as
rock wool, glass fibers, etc., a viscosity-increasing material, such as methyl
cellulose, polyethylene glycol, etc., and a metal salt of a higher fatty acid, for
example sodium stearate, potassium stearate, sodium oleate, potassium
oleate, etc.
JP-A-83/36955 relates to mortar compositions in which granulated
blast-furnace slag of very high uniform quality is used as aggregate. The
mixtures in question contain 10 parts by weight of calcium sulfate monohy-
drate and 50 to 200 parts by weight of granulated blast-furnace slag as
aggregate, 0.03 to 3 parts by weight of phosphate,0.03 to 3 parts by weight
of a protein-based retarder and, if necessary, additives including inter alia a
fatty acid salt.
JP-A-82/175764 describes a water-repellent board of an inorganic
material which is obtained, for example, by adding an aqueous solution of an
aluminium salt of a fatty acid to a suspension containing a hydraulic inorganic
material, for example cement or gypsum, a fibrous material and an aggregate.
This mixture is introduced into a mold and set and is then dried by heat
treatment until the internal temperature is above 80~C. The addition of the
aluminium salt of the fatty acid prevents overheating and also fracture and the
flaking of layers.
It is known from EP-A-321816 that ethoxylated C12-22 fatty alcohols with
an HLB value of 4.5 to 11 can be added as surfactant components to
gypsum-based compositions to which hydroxyalkylated methyl cellulose is
optionally added. The compounds thus produced may be used as mortars,
fillers, etc. The addition of the ethoxylated fatty alcohols prevents the
composition from forming lumps when it is mixed with water.
Gypsum additives based on fatty alcohols containing at least 10
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H 1759 PCT 4
carbon atoms are described in "ConChem Journal" Vol. 2 (1994), page 23.
JP-A-90/296780 relates to a low-density gypsum product obtained by
foaming a gypsum suspension using a sulfonate of a C,016 fatty acid alkyl
ester as foaming agent.
EP-A-54175 describes mortar mixtures based on cement, gypsum
and/or calcium hydroxide, standard fillers and auxiliaries, in which 0.05 to
0.5% of a water-soluble nonionic cellulose ether and 0.01 to 0.05% of an
ethylene oxide adduct of a fatty alcohol and/or a fatty acid or an amide thereofis added to the water-free mortar mixture. These mortar mixtures are used
in the production of an air-entraining mortar, gypsum and calcium-hydroxide-
containing adhesive mortars, for example for laying roof tiles and mosaics,
and for air-entraining Portland cement based on a mortar binder.
DE 2908271 describes the subsequent coating of gypsum plaster-
boards, for example, with water-based wax, paraffin and resin dispersions.
The problem addressed by the present invention was to provide a
gypsum-based composition which uses a special oleochemical additive or
mixtures of different additives to modif,v the properties of the gypsum.
Property modifications in the present context include, in particular,
hydrophobicization, control of the setting times, rheology and water retention
capacity and also elasticization.
This problem has been solved by the characterizing features of claim
1.
Accordingly, the present invention relates to a gypsum-based
composition which is characterized in that, based on the dry mixture as a
whole, it contains 0.1 to 30% by weight of at least one oleochemical additive
selected from
- at least one fatt,v compound containing at least one carboxyl group and
at least 8 carbon atoms and/or a salt thereof with a molecular weight of
143 to 20,000,
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H 1759 PCT 5
at least one fatty compound containing at least one hydroxyl group and
at least 8 carbon atoms with a molecular weight of 130 to 20,000,
at least one fatty compound containing at least one ester group, the acid
component and/or the alcohol component containing at least 8 carbon
atoms, with a molecular weight of 158 to 20,000,
at least one fatty compound containing at least one ether group, at least
one of the two ether groups containing at least 8 carbon atoms with a
molecular weight of 144 to 20,000,
at least one fatty compound containing at least one amino group or at
least one quaternary ammonium salt, at least one of the three or four
groups arranged around the nitrogen atom containing at least 8 carbon
atoms, with a molecular weight of 129 to 20,000,
at least one fatty compound containing at least one amide group, the acid
component of the amide containing at least 8 carbon atoms, with a
molecular weight of 157 to 20,000,
at least one fatty compound containing at least one epoxide group and
at least 8 carbon atoms with a molecular weight of 128 to 20,000,
at least one fatty compound containing at least one anhydride group and
at least 8 carbon atoms with a molecular weight of 210 to 20,000,
at least one organophosphorus fatty compound containing at least 8
carbon atoms with a molecular weight of 193 to 20,000,
at least one organoboron fatty compound containing at least 8 carbon
atoms with a molecular weight of 174 to 20,000,
at least one organosulfur fatty compound containing at least 8 carbon
atoms with a molecular weight of 164 to 20,000,
at least one fatty compound containing at least one urethane group and
at least 8 carbon atoms with a molecular weight of 213 to 20,000 and/or
at least one fatty compound containing at least one keto group and at
least 8 carbon atoms with a molecular weight of 130 to 20,000,
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H 1759 PCT 6
- with the proviso that a higher fatty acid or salt thereof is not used on its
own as the at least one fatty compound containing at least one carboxyl
group, with the further proviso that a fatty alcohol or ethoxylated fatty
alcohol is not used on its own as the at least one fatty compound
containing at least one hydroxyl group, with the further proviso that a
natural fat or oil is not used on its own as the at least one fatty compound
containing at least one ester group,
- with the further proviso that a sulfonate of a C,O ,~ fatty acid alkyl ester is
not used on its own as the organosulfur fatty compound and
- with the proviso that an ethylene oxide adduct of a fatty acid amide is not
used as the at least one fatty compound containing at least one amide
group.
The main component of the gypsum-based composition according to
the invention is a gypsum in the form of the anhydride or hemihydrate,
including all the chemical modifications (o~- and ~-hemihydrate, anhydrite 1, Il,
Ill), based on natural gypsum, synthetic gypsum or gypsum from the desul-
furization of waste gases. In principle, these hydraulically setting versions
based on CaS04 may be present both in pure form and also in the form of
mixtures.
The natural gypsum used is normally a ~-gypsum of the type obtained
in the kiln process or in the kettle process. A corresponding multiphase
gypsum is obtained by the travelling grate process while an a-gypsum is
obtained by the autoclave process.
In the case of the gypsums used in the form of synthetic gypsums, the
~-gypsum is obtained by the Knauf kiln process, by the Knauf kettle process
and by the kettle process without recrystallization. A corresponding
multiphase gypsum is obtained as synthetic gypsum by the Knauf aggregate
calcination process while an oc-gypsum is obtained by Giulini autoclave
process.
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H 1759 PCT 7
Today, however, large quantities of gypsum come from the desulfur-
ization of waste gases, for example by the Bischoff process, by the Saarberg-
Holter process and also by the mining research process. In 1990, for
example, around 2 million tonnes of residual gypsum were produced. The a-
hemihydrate from WGDP gypsum (WGDP = waste gas desulfurization plant)
has acquired particular significance in this regard.
In the gypsum-based compositions, gypsum from the provenances
mentioned above is present as the principal product in quantities of 50 to
99.9% by weight and preferably in quantities of 70 to 98% by weight, based
on the inorganic binder component of the dry mixture.
Fatty compounds in the context of the present invention are fatty acids,
fatty alcohols and derivatives or secondary products thereof obtainable from
natural oils, more especially vegetable and animal oils.
In nature, they occur in the form of natural mixtures of various fatty
acid glycerol esters, for example in the form of palm oil, palm kernel oil, palmstearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil,
peanut oil, linseed oil, lard oil, fish oil, fish train oil or lard.
It can be of particular advantage to start out from coconut oil, palm
kernel oil or beef tallow by virtue of their high natural content of saturated fatty
acids.
In addition to these fatty mixtures, the corresponding individual
substances may also be used.
Examples of saturated fatty acids containing 8 to 26 and preferably 12
to 22 ca,rbon atoms are caproic, caprylic, capric, lauric, myristic, palmitic,
stearic, arachic, behenic, cerotic, pentadecanoic, margaric, tridecanoic and
lignoceric acid. Examples of unsaturated fatty acids containing 8 to 26 and
preferably 12 to 22 carbon atoms are myristoleic, palmitoleic, oleic, elaidic,
petroselic, erucic, linoleic, linolenic, arachidonic, clupanodonic, docosa-
hexaenoic, eicosapentaenoic and gadoleic acid.
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H 1759 PCT 8
Examples of saturated fatty alcohols containing 8 to 26 and preferably
12 to 22 carbon atoms, which are industrially synthesized by reduction
(hydrogenation) of fatty acid methyl esters, are caproic alcohol, caprylic
alcohol, pelargonic alcohol, capric alcohol, lauric alcohol, myristic alcohol,
cetyl alcohol, stearyl alcohol, gadoleyl alcohol and behenyl alcohol.
Fatty compounds derived from the above-mentioned structural
elements and functionalized in accordance with the required effect in the
gypsum are used in accordance with the invention. Derivatives with a
molecularweight of > 129 to 20,000, as determined by GPC, or oligomerized
fatty compounds with a molecular weight of > 1,000 and polymeric fatty
compounds with a molecular weight of > 2,000 are preferably used.
Since these substances are generally complex mixtures, the fatty
compounds according to the invention are characterized in the following by
the most important functional groups present in them.
In a first preferred embodiment, the oleochemical additive is at least
one fatty compound containing a carboxyl group selected above all from
oxidation products of Guerbet alcohols. Guerbet alcohols may be obtained,
for example, by autocondensation of fatty alcohols in the presence of alkalis
(Soap, Cosm. Chem. Spec. 53 (1987)). Examples include 2-hexyl decanoic
acid, 2-octyl dodecanoic acid, 2-decyl tetradecanoic acid, 2-dodecyl
hexadecanoic acid, 2-tetradecyl octadecanoic acid, 2-hexadecyl eicosanoic
acid, etc. Mixtures of technical Guerbet alcohols may optionally be used.
The fatty compound containing at least one carboxyl group may also
be selected from adducts of unsaturated fatty acids with dieneophiles such
as, for example, acrylic acid, maleic acid, fumaric acid, acetylene dicarboxylicacid, styrene, cyclopentadiene and o~-olefins.
Reference is also made in this regard to the polymerization of fatty
acids by radical polymerization or heat treatment. The fatty acids may also
be obtained by polymerization of fatty acid esters and subsequent hydrolysis
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H 1759 PCT 9
of the ester group. Examples include dimer and trimer fatty acids and also
the branched fatty acids formed as secondary dimerization products, for
example isostearic acid and isopalmitic acid.
Other suitable fatty compounds containing at least one carboxyl group
are fatty acids obtained by hydrolysis of blown and oxidized triglycerides.
Examples include fatty acid mixtures of blown fish oil and blown rapeseed oil.
Finally, this definition also encompasses undecylenic acid as a
secondary product of the pyrolysis of ricinoleic acid methyl ester.
In a first preferred embodiment, the fatty compounds used are in
particular those which contain at least one hydroxyl group in addition to at
least one carboxyl group. Examples of such fatty compounds are ricinoleic
acid, 12-hydroxystearic acid and 11-hydroxyundecanoic acid as an inter-
mediate product in the synthesis of Nylon-11, reaction products of epoxidized
fatty acid esters with water, for example 9,1 0-dihydroxystearic acid or
9,10,12,1 3-tetrahydroxystearic acid.
In addition, after the first class of fatty compounds, the oleochemical
additive preferably contains at least one hydroxy group in addition to at least
one carboxyl group. Examples of this class of oleochemical additives are
partial esters of polybasic carboxylic acids or anhydrides with fatty com-
pounds containing several hydroxyl groups. Examples of such products are
partial esters of citric acid with C8 26 fatty alcohols or castor oil, semiesters of
maleic acid with dimer alcohol or semiesters of phthalic anhydride with castor
oil.
Also suitable are reaction products of epoxidized C8 100 fatty acid esters
with an excess of polybasic carboxylic acids, for example the reaction product
of epoxidized soybean oil with adipic acid.
Finally, reaction products of fatty compounds containing ester and
hydroxyl groups (for example castor oil) with a"B-unsaturated acids, such as
acrylic acid, itaconic acid, fumaric acid or maleic acid using radical initiators
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H 1759 PCT 10
may also be used.
In another preferred embodiment, the first class of fatty compounds
consists of compounds which contain at least one carboxyl function, at least
one hydroxyl function and at least one ether group. Fatty compounds of this
class include reaction products of epoxidized fatty acid esters with monohy-
dric or polyhydric alcohols in which the ester group is subsequently
hydrolyzed . Examples are hydroxymethoxystearic acid and hydroxybutoxy-
stearic acid.
In another preferred embodiment, the first class of fatty compounds
contain both at least one ester group and at least one carboxyl group.
Examples of such fatty compounds are addition products of unsaturated fatty
acid esters with dieneophiles, such as acrylic acid, maleic acid, fumaric acid
and acetylene dicarboxylic acid and addition products of unsaturated C826
fatty acids with the corresponding esters.
Reaction products of maleicized fatty acid esters with monohydric and
higher alcohols to semiesters are also suitable. The products may be
oligomeric or polymeric in character.
It is also possible to use carboxyl-terminated esters of fatty acids,
polyhydric alcohols and polybasic carboxylic acids, as described in "Resins
for Surface Coatings", Volume lll, Edited by Dr. P Oldring & G. Hayward,
SITA Technology (London), 1987, page 188. Corresponding products may
also be obtained by transesterification of fatty acid esters with polyhydric
alcohols and subsequent esterification with polybasic carboxylic acids.
Finally, esters of hydroxyfunctional fatty compounds with polybasic
carboxylic acids in excess may also be used.
Another class of substances within the first group of fatty compounds
are those which contain at least one ester group and at least one ether group
in addition to at least one carboxyl group. Examples of such fatty compounds
are carboxyl-terminated polyesters of ring-opening products of epoxidized
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H 1759 PCT 1 1
fatty acid esters with monohydric and polyhydric alcohols with subsequent
reaction with a molar excess of polybasic carboxylic acids. Reaction products
of methanol-ring-opened epoxidized rapeseed oil with phthalic anhydride are
mentioned as an example of such fatty compounds. Another subclass of fatty
compounds belonging to the first class comprises fatty compounds which
contain at least one ester group and at least one anhydride group in addition
to at least one carboxyl group. Adducts of fatty acid esters with maleic
anhydride partly reacted with water or monohydric or polyhydric alcohols
belong to this other subclass of fatty compounds of the first class. Partial
reaction products of maleicized soybean oil with butanol are mentioned as
examples.
Another subgroup of fatty compounds belonging to the first class are
those which contain at least one anhydride group in addition to at least one
carboxyl group. This other subgroup includes reaction products of unsatu-
rated fatty acids with maleic anhydride. The reaction may be carried out both
thermally and also radically. Representative examples of this other subgroup
include maleicized linoleic acid and maleicized oleic acid. The second class
of oleochemical additives according to the invention includes fatty com-
pounds which contain at least one hydroxyl group. They are obtained by
guerbetization of saturated and unsaturated fatty alcohols. Examples of such
Guerbet alcohols are 2-hexyl decanol, 2-octyl dodecanol, 2-decyl tetra-
decanol, 2-dodecyl hexadecanol, 2-tetradecyl octadecanol, 2-hexadecyl
eicosanol, Guerbet alcohol from erucyl alcohol, behenyl alcohol and ocenols.
Mixtures resulting from the guerbetization of technical fatty alcohols may
optionally be used.
Fatty compounds containing several hydroxyl groups, for example
ricinoleyl alcohol, 12-hydroxystearyl alcohol, dimer diol containing 18 to 52
carbon atoms and trimer triol (hydrogenation products of dimer and trimer
fatty acid esters).
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H 1759 PCT 12
In one preferred embodiment, the second class of oleochemical
additives may contain both at least one hydroxyl group and at least one ester
group. Examples of such oleochemical additives belonging to the second
class are castor oil, partly dehydrated castor oils, castor oils partly acylatedwith monobasic and polybasic carboxylic acids, polyesters of ricinoleic acid
and 12-hydroxystearic acid (Estolids); reaction products of epoxidized fatty
compounds with monobasic and polybasic carboxylic acids or monohydric
and polyhydric alcohols; transesterification products of fatty acid esters with
polyhydric alcohols (partial glycerides); transesterification products of castoroil with other triglycerides, such as rapeseed oil, sunflower oil under alkalinerandomization conditions; esters of fatty alcohols with hydroxycarboxylic
acids, for example tartaric acid, citric acid, glucose acid. These products may
also be obtained by a reaction similar to the alkyd resin synthesis of fatty
acids, monohydric and polyhydric alcohols and polybasic carboxylic acids to
forrn hydroxyl-terminated oligomers. Corresponding products may also be
prepared by transesterification of fatty acid esters of polyhydric alcohols and
subsequent esterification with polybasic carboxylic acids. Other typical
representatives are partial esters of fatty acids with polyhydric alcohols, for
example glycerol monooleate, trimethylol propane distearate, pentaglycerol
monolaurate, sorbitan monococoate. Hydroxyl-terminated esterification
products of hydroxyl-containing fatty compounds with polybasic carboxylic
acids.
Another subclass of the second class includes fatty compounds which
contain at least one amine group or a corresponding quaternary ammonium
salt in addition to at least one hydroxyl group and at least one ester group.
Examples of these fatty compounds are reaction products of epoxidized fatty
acid esters with monofunctional and polyfunctional amines without amidation
of the esterfunction. One example of such a reaction product is the reaction
product of epoxystearic acid methyl ester and 1 ,6-diaminohexane, amidation
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H 1759 PCT 13
of fatty acid esters, more especially triglycerides, with ammonia, monofunc-
tional and polyfunctional amines without removal of the glycerol, optionally
with partial amidation.
In another preferred subclass of the second class, the fatty compounds
contain not only at least one hydroxyl group, but also at least one ester group
and at least one amide group. Corresponding products are obtained by
amidation of fatty acid esters, more especially triglycerides, with ammonia,
monofunctional and polyfunctional amines without removal of the alcohol
component from the ester (glycerol). One example of such a product is the
reaction product of rapeseed oil with less than the equivalent quantity of
stearylamine.
In another preferred subclass of the second preferred embodiment of
fatty compounds, the fatty compounds may contain at least one ester group
and at least one anhydride group in addition to at least one hydroxyl group.
Examples of such fatty compounds are reaction products of a hydroxyl-
containing fatty acid ester, such as castor oil, with maleic anhydride in the
presence as catalysts of radical initiators such as, for example, ditert.butyl
peroxide, AIBN, tert.butyl hydroperoxide and dibenzoyl peroxide.
In another preferred subclass of the preferred second class, the
oleochemical additives may contain at least one ether group in addition to at
least one hydroxyl group. Corresponding compounds are obtained by
etherification (for example by dehydration using acidic catalysts) of fatty
compounds containing several hydroxyl group (for example ricinoleyl alcohol,
12-hydroxystearyl alcohol, dimer diol, trimer triol) to oligomeric hydroxyl-
terminated polyethers. The production of such fatty compounds is described
in DE 4316245 (A1).
Another preferred subclass of the second class of preferred fatty
compounds includes those fatty compounds which contain at least one amide
group in addition to at least one hydroxyl group. These fatty compounds are
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H 1759 PCT 14
reaction products of fatty compounds containing carboxyl and hydroxyl groups
with ammonia, monofunctional and polyfunctional amines. Examples include
ricinoleic amide, 1 2-hydroxystearic acid ethylenediamide, hydroxy-
methoxystearic acid octylamide, dihydroxystearic acid butylamide. The fatty
compounds in question are also reaction products of carboxyfunctional fatty
compounds with hydroxyamines, for example cocofatty acid monoethan-
olamide and stearic acid diethanolamide.
In a third preferred embodiment of the present invention, the fatty
compound contains at least one ester group. Corresponding fatty compounds
are, above all, synthetic fatty acid esters such as, for example, trimethylol
propane trioleate, rapeseed oil fatty acid methyl ester, glycerol tricaprylate
and oleic acid-2-ethylhexyl ester. Fatty compounds of the type in question
are also reaction products of fatty acid esters with dieneophiles, such as
acrylic acid, maleic acid, fumaric acid and acetylene dicarboxylic acid esters,
styrene, cyclopentadiene, etc. The reaction may be carried out thermally,
radically and photochemically.
Other fatty compounds covered by the third preferred embodiment of
the present invention are blown oils and fats, radical-polymerized fats, linseedoil-stand oil, completely dehydrated castor oil and stand oils produced
therefrom, thermally polymerized rapeseed oil and castor oil completely
acylated with monocarboxylic acids.
Finally, esters of fatty alcohols with monobasic and polybasic
carboxylic acids are also suitable. Carboxyl-containingfatty compounds may
also be used for esterification with the fatty alcohols. Examples include oleyl
oleate, distearyl adipate, oleyl acetate.
In the third preferred embodiment of the present invention, the fatty
compound contains at least one epoxide group and at least one ether group
in addition to at least one ester group. Fatty compounds of this type include
epoxidized fatty acid esters partly ring opened with monohydric or polyhydric
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H 1759 PCT 15
alcohols, for example the reaction product of epoxystearic acid methyl ester
with less than the equivalent quantity of octanol.
In another preferred subgroup of the third preferred embodiment, the
fatty compounds contain at least one amine group in addition to at least one
ester group. Fatty compounds of this type include esters of hydroxyl-
containing tertiary amines such as, for example, triethanolamine or 3-hydroxy-
N-methyl pyrrolidine with fatty compounds containing carboxyl groups. The
products may be quaternized and thus converted into amphiphilic compounds
by reaction with chloroacetic acid, methyl halides, dimethyl sulfate, etc.
Another subgroup of the preferred third class of fatty compounds
includes fatty compounds which contain at least one epoxide group in addition
to at least one ester group. Corresponding fatty compounds are partly and
completely epoxidized fatty acid esters such as, for example, epoxystearic
acid methyl ester, epoxystearic acid-2-ethylhexyl ester. Preferred glycerides
are the triglycerides, for example soybean oil epoxide, linseed oil epoxide,
rapeseed oil epoxide, epoxidized sunflower oil.
In another subclass of the third class, the fatty compounds according
to the invention contain at least one anhydride group in addition to at least
one ester group. Corresponding fatty compounds are reaction products of
fatty acid esters containing double bonds in their alcohol or acid component
with a dieneophile such as, for example, maleic anhydride.
In a fourth preferred embodiment, the fatty compounds according to
the invention contain at least one ether group, preferably an alkyl ether group
containing 8 to 26 and, more particularly 12 to 22 carbon atoms. Correspond-
ing ethers are obtained in known manner, for example by Williamson's ether
synthesis or by dehydration with acidic catalysts of saturated, unsaturated
and branched fatty alcohols. Examples of such fatty ethers are dioctyl ether,
didecyl ether, distearyl ether and dibehenyl ether.
In a fifth preferred embodiment, the oleochemical additives are at least
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H 1759 PCT 16
one fatty compound containing at ieast one amine group. These amines are
obtained by amidation of fatty acids, dehydration and reduction. Examples
of such fatty amines include stearylamine and laurylamine. The amines
mentioned may also be quaternized by reaction with chloroacetic acid, methyl
halides, dialkyl sulfate, etc. Examples include stearyl trimethyl ammonium
chloride, lauryl triethyl ammonium sulfate.
The fifth preferred embodiment, in one of its subclasses, encompasses
fatty compounds which contain at least one amide group in addition to at least
one amine group. Examples of such fatty compounds are reaction products
of epoxidized fatty acid esters with monofunctional and polyfunctional amines
in which the ester function is simultaneously amidated. Examples include
reaction products of epoxystearic acid methyl ester with stearylamine.
In a sixth preferred embodiment of the present invention, the fatty
compound according to the invention contains at least one amide group.
Corresponding fatty compounds are reaction products of carboxyl-containing
fatty compounds with ammonia, monofunctional and polyfunctional amines.
Examples include stearic acid amide, oleic acid amide, stearic acid ethylene-
diamide.
In a seventh preferred embodiment, the fatty compounds according
to the invention contain at least one epoxide group. Corresponding fatty
compounds are, for example, epoxidized products of C8 26 alkyl compounds
containing at least one double bond, for example 1-epoxyoctadecane.
In an eighth preferred embodiment, the oleochemical additive is a fatty
compound containing at least one anhydride group. Corresponding fatty
compounds are obtained in known manner by dehydration, for example using
acetanhydride, of fatty compounds containing one or more acid groups.
Examples of such fatty compounds are distearic anhydride, dioleic anhydride,
dimer fatty anhydride.
In a ninth preferred embodiment, the oleochemical additive according
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H 1759 PCT 17
to the invention is selected from at least one organophosphorus fatty
compound. Examples of such fatty compounds are, in particular, esters of
phosphoric acid and phosphorous acid with hydroxyl-containing fatty
compounds. Amides of phosphoric acid and phosphorous acid with fatty
compounds containing amine groups.
In a tenth preferred embodiment, the oleochemical additives contain
an organoboron fatty compound. Examples of such fatty compounds are
esters of boric acid with fatty compounds containing hydroxyl groups. The
organoboron fatty compounds may be obtained, for example, by reaction with
boric acid and sodium borate.
In an eleventh preferred embodiment, the oleochemical additive is a
fatty compound containing at least one organosulfur compound. Examples
of corresponding fatty compounds are esters of sulfuric acid (sulfates) and
sulfurous acid (sulfites) with fatty compounds containing hydroxyl groups.
Other examples are reaction products of fatty compounds containing
activated groups (double bonds, a-methylene groups) with chlorosulfonic
acid, sulfur trioxide or oleum to sultones and sulfonic acids. Reaction
products of unsaturated fatty acid esters with elemental sulfur and sulfur
dichloride. Examples include sulfated rapeseed oil, sulfonates of fatty acid
esters, fatty alcohol sulfates, the reaction product of linseed oil and sulfur
(brown and white factice), sulfated castor oil (turkey red oil).
In a twelfth preferred embodiment, the oleochemical additive is a fatty
compound containing at least one urethane group. Corresponding fatty
compounds are obtained by reacting fatty compounds containing hydroxyl
groups with monofunctional and polyfunctional isocyanates, optionally in the
presence of typical catalysts, to form monomeric, oligomeric and polymeric
products. Examples are reaction products of castor oil with diphenyl methane
diisocyanate, the reaction product of 1-octanol and methyl isocyanate.
In a thirteenth preferred embodiment of the present invention, the
, CA 02230024 1998-02-19
H 1759 PCT 18
oleochemical additive is a fatty compound containing at least one keto group.
Corresponding fatty compounds are obtained by rearrangement of
epoxidized fatty acid esters with Lewis acids or lithium salts or derivatives
thereof. Examples are ketostearic acid methyl ester and 9-ketostearic acid.
The corresponding esters may also be obtained by isomerization of castor
oil derivatives.
Fatty ketones may also be prepared from fatty acids by relevant
methods of preparative organic chemistry, for example by pyrolysis of fatty
acid magnesium salts at temperatures above 300~C with elimination of CO2
and water (DE-OS 2553900). Examples are distearyl ketone (stearone) and
dibehenyl ketone (behenone).
Monobasic carboxylic acids in the context of the invention are, for
example, the following compounds: formic, acetic, propionic, butyric, valeric,
caproic, oenanthic, caprylic, pelargonic, capric, undecanoic, lauric, trideca-
noic, myristic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic,
arachic, behenic, lignoceric, cerotic and melissic acid, benzoic acid,
substituted benzoic acid derivatives, 4-hydroxybenzoicacid, dichloropropionic
acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, hydroxyacetic acid,
salicylicacid, chlorovalericacid, 4-hydroxybutyricacid, mandelicacid, phenyl
acetic acid, gallic acid, cinnamic acid, resinic acids from pine resins and tallresins, for example abietic acid.
Polybasic carboxylic acids in the context of the present invention are,
for example, the following compounds: oxalic acid, malonic acid, succinic
acid, pimelic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, suberic
acid, sebacic acid, 1, 11 -undecanedioic acid , 1 , 1 2-dodecanedioic acid,
phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid,
hexahydrophthalic acid, tetrahydrophthalic acid, dimer fatty acid, trimer fatty
acid, tartronic acid, malic acid, acetylene dicarboxylic acid, tartaric acid, citric
acid.
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H 1759 PCT 19
In the context of the invention, monohydric alcohols are, for example,
the following compounds: methanol, ethanol, propanol, butanol, pentanol, 2-
ethyl hexanol, 2-octanol, monophenyl glycol, abietyl alcohol, polyethylene
glycol monoalkyl ether, cyclohexanol.
Polyhydric alcohols in the context of the present invention are, for
example, the following compounds: ethane-1,2-diol, propane-1,2-diol,
propane-1,3-diol, butane-1,4-diol, butane-2,3-diol, pentane-1,5-diol, hexane-
1 ,6-diol, octane-1 ,8-diol, diethylene glycol, neopentyl glycol, 1 ,4-bis-hydroxy-
methyl cyclohexane, 2-methylpropane-1,3-diol, hexane-1,2,6-triol, glycerol,
diglycerol, polyglycerol, trimethylol propane, trimethylol ethane, pentaerythri-tol, sorbitol, formitol, methyl glycoside, dimer diol, trimer triol, glucose, alkyl
polyglucosides, di- and polysaccharides. All the alcohols mentioned may also
be used in the form of EO or PO adducts. Polyethylene, polypropylene and
polybutylene glycols, cyclohexanediol, EO/PO block polymers (Pluronic9 and
Pluriol~ types).
In the context of the present invention, monofunctional amines are, for
example, the following compounds: methylamine, dimethylamine, ethylamine,
butylamine, stearylamine, oleylamine, aminobenzene or substituted
derivatives, aminocyclohexane and pyrrolidine.
Polyfunctional amines in the context of the invention are, for example,
the following compounds: ethylenediamine, tetramethylenediamine,
pentamethylenediamine, hexamethylenediamine, diethylenetriamine,
triethylenetetramine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-
diamino-2,2-dimethyl propane, 2,5-diamino-2,5-dimethyl hexane, 1,10-
diaminodecane, 1 ,4-diaminobutane, 12-diaminododecane, diamine of dimer
fatty acid, 1 ,8-diaminooctane, 1,8-diamino-p-menthane, 1 ,5-diaminopentane,
1,3-diamino-2-propanol, 1,3-diaminoadamantane, phenylenediamine,
diaminobenzene.
Hydroxyamines in the context of the present invention are, for
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H 1759 PCT 20
example, the following compounds: monoethanolamine, diethanolamine, 1,6-
hexanolamine, 2-aminocyclohexanol, 4-aminocyclohexanol, hydroxymethyl
pyrrolidine.
Monofunctional isocyanates in the context of the present invention are,
for example, the following compounds: phenyl isocyanate, alkyl isocyanate,
isocyanatoaceticacid ethyl ester, tolyl isocyanate and compounds containing
an isocyanate group obtainable by reaction of polyfunctional, more particularly
difunctional isocyanates and monofunctional alcohols or amines.
Polyfunctional isocyanates in the context of the present invention are,
for example, the following compounds which contain on average 2 to at most
4 NCO groups. Examples of suitable isocyanates are 1,5-naphthylene
diisocyanate, 4,4-diphenyl methane diisocyanate (MDI), hydrogenated MDI
(H12MDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate
(TMXDI), 4,4'-diphenyl dimethyl methane diisocyanate, di- and tetraalkyl
diphenyl methane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene
diisocyanate, 1,4-phenylene diisocyanate, the isomers of tolylene diisocya-
nate (TDI), optionally in admixture, 1-methyl-2,4-diisocyanatocyclohexane,
1,6'-diisocyanato-2,2,4-trimethyl hexane, 1,6-diisocyanato-2,4,4-trimethyl
hexane, 1'-isocyanatomethyl-3'-isocyanato-1,5,5'-trimethyl cyclohexane
(IPDI), chlorinated and brominated diisocyanates, phosphorus-containing
diisocyanates, 4,4'-diisocyanatophenylperfluoroethane, tetramethoxybutane-
1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI),
dicyclohexyl methane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene
diisocyanate, phthalic acid-bis-isocyanatoethyl ester; polyisocyanates
containing reactive halogen atoms, such as 1-chloromethylphenyl-2,4-
diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, 3,3-bis-chloro-4,4'-
diphenyl diisocyanate. Sulfur-containing polyisocyanates are obtained, for
example, by reaction of 2 moles of hexamethylene diisocyanate with 1 mole
of thiodiglycol or dihydroxydihexyl sulfide. Other important diisocyanates are
CA 02230024 1998-02-19
H 1759 PCT 21
trimethyl hexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-
diisocyanatododecane and dimer fatty acid diisocyanate. Also of interest are
partly masked polyisocyanates which enable self-crosslinking polyurethanes
to be formed, for example dimeric tolylene diisocyanate, or polyisocyanates
partly or completely reacted, for example, with phenols, tert.butanol,
phthalimide, caprolactam.
It is obvious that not only mixtures of oleochemical additives belonging
to each class, but also mixtures of any components belonging to the individual
classes with one another may be used.
The oleochemical additive mentioned above may be blended with
gypsum and, optionally, other ingredients in various ways. First, there is the
so-called one-component variant where the gypsum-based composition
contains gypsum, the oleochemical additive and the other auxiliaries and
additives. Accordingly, the user need only add water so that this variant is
particularly preferred. The oleochemical components may be mixed either
purely physically with the gypsum powder and the other auxiliaries and
additives. Alternatively, however, these components may also be applied to
the gypsum or adsorbed thereon or applied by coating, i.e. at temperatures
above room temperature (> 25~C).
Alternatively, there is of course also a two-component in situ variant
where the gypsum is mixed with water before the addition of water either after
or at the same time as the oleochemical components and the other auxiliaries
and additives.
In a third preferred embodiment of the invention, the salts of carboxyl-
containing fatty compounds, for example of the corresponding fatty acids with
amines, for example monoethanolamine, are added at room temperature and
may then be reacted to the corresponding amines, for example in the
production of gypsum plasterboards, with elimination of water.
Finally, the present invention also relates to the use of the oleo-
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H 1759 PCT 22
chemical additives mentioned above for the impregnation or coating of
prefabricated gypsum components or gypsum plasters. To this end, the oleo-
chemical components may be applied either directly or even in the form of a
solution in a solvent or in the form of a dispersion or emulsion in water. Any
of the usual methods of application, such as dip coating, spray coating, roll
coating, brush coating, etc., may be applied.
The present invention also relates to an oleochemical additive
containing
- at least one fatty compound containing at least one carboxyl group and at
least 8 carbon atoms with a molecular weight of 143 to 20,000 and/or a
salt thereof,
- at least one fatty compound containing at least one hydroxyl group and at
least 8 carbon atoms with a molecular weight of 130 to 20,000,
- at least one fatty compound containing at least one ester group, the acid
component and/or the alcohol component containing at least 8 carbon
atoms, with a molecular weight of 158 to 20,000,
- at least one fatty compound containing at least one ether group, at least
one of the two ether groups containing at least 8 carbon atoms, with a
molecular weight of 144 to 20,000,
- at least one fatty compound containing at least one amino group or at
least one quaternary ammonium salt, at least one of the three or four
groups arranged around the nitrogen atom containing at least 8 carbon
atoms, with a molecular weight of 129 to 20,000,
- at least one fatty compound containing at least one amide group, the acid
component of the amide containing at least 8 carbon atoms, with a
molecular weight of 157 to 20,000,
- at least one fatty compound containing at least one epoxide group and at
least 8 carbon atoms with a molecular weight of 128 to 20,000,
- at least one fatty compound containing at least one anhydride group and
CA 02230024 1998-02-19
H 1759 PCT 23
at least 8 carbon atoms with a molecular weight of 210 to 20,000,
- at least one organophosphorus fatty compound containing at least 8
carbon atoms with a molecular weight of 193 to 20,000,
- at least one organoboron fatty compound containing at least 8 carbon
atoms with a molecular weight of 174 to 20,000,
- at least one organosulfur fatty compound containing at least 8 carbon
atoms with a molecular weight of 164 to 20,000,
- at least one fatty compound containing at least one urethane group and
at least 8 carbon atoms with a molecular weight of 213 to 20,000 and/or
- at least one fatty compound containing at least one keto group and at least
8 carbon atoms with a molecular weight of 130 to 20,000,
- with the proviso that a fatty compound containing at least 10 carbon atoms
is not used on its own as the at least one fatty compound containing at
least one hydroxyl group,
for the subsequent treatment of gypsum components and gypsum plasters.
As already mentioned, the oleochemical additives containing carboxyl
groups, i.e. additives belonging to the first class, may be used both as such
and in the form of their salts. The counterion of the carboxyl group may be
selected both from inorganic ions, such as monovalent or polyvalent metal
ions, or ammonia and from the corresponding organic bases, such as
alkanolamines, amines, etc.
The salts are prepared in the same way as metal soaps from the acids
and the metal or amine compounds under mildly to strongly alkaline
conditions. In many cases, the oxides or hydroxides are also used in
equimolar quantities for salt formation. Salt formation may also be carried out
in situ during preparation of the gypsum/water mixture. In addition, salt
conversion, i.e. the conversion of sodium soaps or salts into calcium salts or
others, is also possible. Salt forming processes are described in the synoptic
article entitled "Metallic Soaps" in Ullmann, Encyclopedia of Technical
CA 02230024 1998-02-19
H 1759 PCT 24
Chemistry, Vol. A 16, pages 361 et seq.
In the case of oleochemical additives containing fatty compounds with
at least one amine group, corresponding salt formation can be carried out by
alkylation or protonation with acids. In the case of oleochemical additives
containing at least one carboxyl group in addition to at least one amine group,
inner salts may even be formed. Since both calcium sulfate hemihydrate and
calcium sulfate dihydrate have a certain solubility in water, free calcium ions
are present and are also capable of subsequently forming salts with the
carboxyl groups.
In addition, gypsums also contain other metal ions, for example
sodium, magnesium, potassium, strontium, lithium, rubidium, iron(ll), barium,
molybdenum(ll), zinc, aluminium and manganese(ll), which are also capable
of forming salts with carboxyfunctional fatty compounds during mixing of the
gypsum or even after curing, cf. for example the article in "Chemie in ~ sel er
Zeit", Vol. 19 (1985), pages 137 to 143. Saltformation can take place during
stirring of the gypsum by adding the substances capable of forming salts, for
example carboxyfunctional fatty compounds and bases (for example Ca(OH)2,
amines), either at the same time or after certain time intervals. In the case ofamine-containing fatty compounds, the corresponding acids have to be
added.
Other components of the gypsum-containing compositions according
to the invention are, for example, typical fillers, auxiliaries and additives which
vary according to the application envisaged. These additional components
are, above all, mineral and/or inorganic fillers, for example clays, sand, gravel,
cement, slags, glass, silica gels, sulfates (for example calcium sulfate
dihydrate), oxides (for example magnesium oxide, calcium oxide), glass and
mineral fibers, synthetic fibers, hollow microbeads, light organic fillers (for
example polystyrene foam), granules (refined) from recycling plants, paper
powder, wood chips and sawdust, cellulose fibers, etc. Other suitable
CA 02230024 1998-02-19
H 1759 PCT 25
additives are preservatives, rustproofing agents and dyes.
Drying agents of the type typically used in paints, varnishes and
printing inks may be added as another ingredient of the gypsum-based
composition according to the invention. According to 55901 (March 1988),
drying agents are understood to be metal salts of organic acids which are
soluble in organic solvents and binders and which are added to oxidatively
drying products to accelerate the drying process. Chemically, drying agents
belong to the metal soaps and may be present both in solid and in dissolved
form as so-called siccatives. However, they may also be applied in water-
emusifiable form in combination with emulsifiers. The acid component may
be, for example, an aliphatic carboxylic acid, such as octanoic acid, or a fattyacid, a naphthenic acid or even a resin acid. Corresponding salts of cobalt,
manganese or lead, but preferably cobalt or manganese, are used as primary
drying agents which directly accelerate oxidation of the fatty compounds.
Salts of zinc, iron, calcium, cerium, lead and barium may be used as
secondary drying agents which do not have any catalytic effect of their own,
but act synergistically in combination with the drying agents mentioned above.
Finally, salts of zirconium and aluminium may be used as coordinative drying
agents. Examples of commercially available drying agents are the products
Additol VXM 6206 and 4940, Solingen, Cobalt 10, linseed oil varnish, Nuodex
Cerium 6 and Zinc 8, Alusec 591 and Nourydrier 973. However, there is no
need for the salts mentioned above where the fatty compounds according to
the invention containing at least one carboxyl group are used. In that case,
inorganic salts, for example hydroxides, of the above-mentioned metals may
be used so that the drying agents are formed in situ. The drying agents are
normally used in quantities of 0.01 % by weight to 1 % by weight, based on the
oleochemical additive.
Other ingredients of the gypsum-based composition according to the
invention are substances with a setting effect which reduce the water demand
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H 1759 PCT 26
and which are normally referred to as plasticizers. Examples are alkylaryl
sulfonates, lignin sulfonic acid salts or melamine resins. A review of
plasticizers can be found, for example, in "Zement, Kalk, Gips", Vol. 21,
pages 415 to 419 (1968). The plasticizers are normally used in quantities of
0 to 10%, based on the composition according to the invention as a whole.
The water demand may also be increased by addition of substances
with a flocculating effect, for example the polyethylene oxides described, for
example, in GB-A-1,049,184. These auxiliaries may be added in quantities
of 0 to 10% by weight, based on the dry mixture.
A water/gypsum mix may be stabilized to prevent sedimentation or
separation by addition of thickening chemicals, for example cellulose and
starch ethers. These thickeners have hardly any effect on the water demand.
The thickeners are added to the dry mixture according to the invention in
quantities of 0 to 5% by weight, based on the dry mixture. Polymer disper-
sions may also be added to the gypsum during stirring, in particular to
improve elasticity and adhesion.
In addition, the compositions according to the invention may contain
auxiliaries acting as accelerators. The accelerators may be selected in
particular from various inorganic acids and salts thereof, more particularly
sulfuric acid and salts thereof. Calcium sulfate dihydrate occupies a special
position in this regard. In finely dispersed form, it has a strong accelerating
effect and, accordingly, has to be completely removed during the calcination
of raw gypsum. The accelerating effect of these substances is generally
based on an increase in the solubility and dissolving rate of the calcined
gypsum and on an increase in the nucleation rate.
Other auxiliaries in the gypsum-based composition according to the
invention are known retarders which slow down the stiffening and hardening
process. They include above all organic acids and salts thereof, organic
colloids which are also formed, for example, as degradation products in the
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H 1759 PCT 27
hydrolysis of high molecularweight natural substances, for example proteins,
and also salts of phosphoric acid or boric acid. Dextrins and hibiscus roots
are also suitable. The retarding mechanism is variable. Colloids of relatively
high molecularweight prolong the induction period because they are nucleus
poisons. Other retarders slow down the dissolving rate of the hemihydrate
and the growth of the dihydrate crystals. Retardation of anhydride ll is
generally of no practical interest because it already changes into dihydrate
sufficiently slowly and always has to be accelerated. The percentage content
of this component in the gypsum compositions according to the invention may
be from 0 to 5% by weight, based on the dry mixture.
As known to the expert, the quantity of water used depends upon the
type of gypsum starting material used, i.e. to obtain a free-flowing mix of
uniform consistency, a kiln ,~-gypsum requires more than one kettle gypsum
which in turn requires more than one multiphase gypsum which, for its part,
requires more than one autoclave gypsum. In addition, the quantity of water
also has a significant bearing both on the unit weight and on the strength of
the gypsum product formed. Without any special measures, a-gypsums
which can be processed with very small quantities of water give gypsum
products of high unit weight and high strength which are avoided in the
building industry on account of their unwanted brittleness. ~-Gypsums and
multiphase gypsums require more water than oc-gypsums for a free-flowing
consistency. Accordingly, they give gypsum products of average strength and
relatively high elasticity for lower unit weights which are used throughout the
building industry. To produce lightweight or porous gypsum, it is possible for
example to add hydrogen peroxide (evolution of oxygen) or dilute acids and
carbonates (evolution of CO2).
The present invention also relates to a gypsum-based composition of
the type mentioned above which, in addition to gypsum and the oleochemical
additive, also contains 0 to 80% of a filler, 0 to 2% of a wetting agent, 0 to 5%
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H 1759 PCT 28
of a plasticizer, 0 to 5% of an acceierator, 0 to 5% of a retarder, based in each
case on the mixture as a whole.
Another problem addressed by the present invention was to enable the
gypsum-based compositions according to the invention to be used for the
production of gypsum products.
The products in question are, on the one hand, so-called prefabricated
gypsum components used widely in the building industry in the form of
gypsum plaster boards, gypsum wall boards and gypsum ceiling boards. A
relevant overview can be found in Ullmann's Enzyklopadie der technischen
Chemie, Vol. 12, page 307 (1976). The gypsum-based compositions
according to the invention may also be used in the form of grouting com-
pounds and gypsum plasters, more particularly during further processing to
machine-applied gypsum plasters and ready-mixed gypsum plasters. Finally,
the gypsum-based compositions according to the invention may also be used
for floor screeds, for longwall packs in mining and, where they are based on
a-gypsum, as a hard mold material in the roof tile industry, in metal foundries
and in dental laboratories. A relevant overview can be found in Ullmann's
Enzyklopadie der technischen Chemie, Vol. 12, page 308 et seq. (1976).
The invention is illustrated by the following Examples.
The following oleochemical additives were investigated for setting time
and water absorption time as a constituent of gypsum-based compositions.
In the production examples described in the following, gel permeation
chromatography (GPC) was carried out with a PL gel preliminary column (30
x 8.7 mm), 2 x PL gel column 100 A (300 x 7.8 mm) and 2 x PL gel column
50 A (300 x 7.8 mm). Tetrahydrofuran was used as the mobile solvent at a
throughflow rate of 1 ml/min. at 40~C. Detection was based on the refractive
index; polyethylene glycols were used for calibration. The weight average
(Mw) and the number average (Mn) are both mentioned in the following
Examples whenever they were measured.
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H 1759 PCT 29
The preferred class to which the additives belong is shown in brackets
after the additive.
Polymerized rapeseed oil fatty [additive class 1]
2 Reaction product of soybean oil with maleic anhydride in a molar ratio
of 1:2 [additive class 3]
3 Epoxidized soybean oil (Edenol D 81, a product of Henkel KGaA)
[additive class 3]
4 Reaction product of soybean oil with maleic anhydride in a molar ratio
of 1:2.5 [additive class 3]
5 Reaction product of castor oil with maleic anhydride in a molar ratio of
1:2 [additive class 1]
6 Reaction product of castor oil with phthalic anhydride in a molar ratio
of 1:2 [additive class 1 ]
7 Magnesium salt of dimer fatty acid [additive class 1]
8 Reaction product of castor oil with acrylic acid [additive class 1]
9 Reaction product of castor oil with fumaric acid [additive class 1]
10 Reaction product of castor oil with phosphorus pentoxide [additive
class 9]
11 Reaction of the ring opening product of epoxidized soybean oil with
methanol with maleic anhydride in a molar ratio of 1:1 [additive class
1]
12 Reaction of the ring opening product of epoxidized soybean oil with
methanol with phthalic anhydride in a molar ratio of 1:1 [additive class
1]
13. Reaction product of epoxidized soybean oil with 4-hydroxybenzoic acid
and a distilled fatty acid containing 7% C,0, 48% C12~19 % C16~ 7% C18~
others 10%, a product of Henkel KGaA (Edenor K 8-18) [additive class
1]
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H 1759 PCT 30
14 Free acid of the reaction product of epoxystearic acid methyl ester with
glycol in a molar ratio of 1:2 [additive class 1] -
15 Free acid of the reaction product of epoxystearic acid methyl ester with
an ethylene oxide/propylene oxide block copolymer of BASF AG (20%
EO, MW = 2,500 g/mole (Pluronic PE 6200) [additive class 1]
16 Reaction product of castor oil with citric acid [additive class 1]
17 Free acid of the reaction product of epoxystearic acid methyl ester with
glycol in a molar ratio of 2:1 [additive class 1]
18 Dimer fatty acid of Empol 1022, a product of Henkel KGaA with a
saponification value of 193 based on technical oleic acid and linoleic
acid [additive class 1]
Production of additive 1
872 g of new rapeseed oil (saponification value 193) were heated to
160~C in a 2-liter four-necked flask equipped with a reflux condenser,
dropping funnel and water separator. 146.2 g of ditert.butyl peroxide were
then added over a period of 3 h at that temperature and the tert.butanol
formed was removed through the water separator. In the meantime, the
reaction mixture became increasingly more viscous and, finally, could no
longer be stirred. After cooling, a yellow gel-like substance with an iodine
value of 57 was obtained in a yield of 843 g. According to GPC, the Mw value
was 5300 and the Mnvalue 2542.
206 g of polymeric rapeseed oil were refluxed for 10 hours with 77 g
of 50% NaOH,300 ml of water and 600 ml of ethanol in a 2-literthree-necked
flask. The brownish clear reaction mixture was concentrated to dryness in a
rotary evaporator. The solid obtained was taken up in 1 liter of water and
adjusted to pH 1 with 10% hydrochloric acid. The aqueous phase was
extracted with 800 ml of tetrahydrofuran. The organic phase was washed
with water until neutral and dried over Na2SO4. Concentration of the solution
CA 02230024 1998-02-19
H 1759 PCT 31
produced 150 g of the polymerized rapeseed oil fatty acid (1) in the form of
a brown viscous liquid with an acid value of 202 and an iodine value of 94.
According to GPC, the Mw value was 904 and the Mn value 698.
Production of additive 5
1860 9 (2 moles) of castor oil are heated under nitrogen for 2 h at
120~C with 392 9 (4 moles) of maleic anhydride. After cooling,2200 9 of the
product were obtained in the form of a yellow low-viscosity liquid with an acid
value of 102, an iodine value of 69 and a saponification value of 344.
Viscosity: 8600 mPas (Hoppler, 20~C).
Production of additive 6
1860 9 (2 moles) of castor oil are heated under nitrogen for 2 h at
120~C with 592 9 (4 moles) of maleic anhydride. After cooling,2400 9 of the
product are obtained in the form of a yellow-brown, high-viscosity liquid with
an acid value of 93, an iodine value of 64, a hydroxyl value of 32 and a
saponification value of 318. Viscosity: 35400 mPas (Hoppler, 20~C).
Production of additive 7
Additive 7 is obtained by reacting 100 9 of the dimer fatty acid 18
Empol 1022, a product of Henkel KGaA (saponification value 193) based on
technical oleic acid and linoleic acid, with 10 9 of magnesium hydroxide.
Production of additive 8
640 9 of castor oil (saponification value 177, 0.7 mole) were heated
under nitrogen to 150~C in a 2-liter three-necked flask equipped with a reflux
condenser and dropping funnel. A mixture of 52.5 9 of ditert.butyl peroxide
and 310 9 of castor oil were slowly added dropwise over a period of 4 h at
that temperature. After the temperature had been lowered to 100~C,
CA 02230024 1998-02-19
H 1759 PCT 32
tert.butanol and unreacted acrylic acid were distilled off in vacuo. After
treatment with the filter aid Tonsil Optimum FF and filtration, 900 g of the
product were obtained in the form of a clear reddish-yellow liquid with an acid
value of 31, an iodine value of 78 and a hydroxyl value of 159.
Production of additive 9
Similarlyto the production of additive 8 using 1200 g of castor oil (1.26
moles),90 g of fumaric acid (0.8 mole) and 2.6 g of ditert.butyl peroxide,1200
g of product were obtained in the form of a yellow, slightly cloudy viscous
liquid with an acid value of 55, an iodine value of 72, a saponification value
of 229 and a hydroxyl value of 146.
Production of additive 10
Additive 10 is produced by reacting 475 g of castor oil with 70 g of
phosphorus pentoxide. The product was characterized by an acid value of
161 and a hydroxyl value of 66.
Production of additive 11
Additive 11 is produced similarly to additive 10 from 762 g (2.5 moles)
of the ring-opening product of epoxidized soybean oil with methanol (OH
value 184) and 98 g (2.5 moles) of maleic anhydride. 850 g of a dark brown
high-viscosity liquid with an acid value of 81 and a saponification value of 325are obtained as the product.
Production of additive 12
Additive 12 is produced similarly to additive 11 from 671 g (2,2 moles)
of the ring-opening product of epoxidized soybean oil with methanol (OH
value 184) and 358 g (2.4 moles) of phthalic anhydride. 1050 g of a dark
brown solid with an acid value of 58 and a saponification value of 369 are
CA 02230024 l998-02-l9
H 1759 PCT~ 33
obtained as the product.
Production of additive 13
A mixture of 155 g (1.1 mole) of 4-hydroxybenzoic acid and 228 g of
a distilled fatty acid containing 7% C10, 48% C12~ 19% C14, 9 % C1~. 7% C18.
others 10%, a commercial product of Henkel KGaA (Edenor K 8/18), is
heated under nitrogen to 160~C and 662 g (2.8 moles) of epoxidized soybean
oil (Edenol D 81) are then added over a period of 3 h. After cooling,1030 g
of the reaction product are obtained in the form of a lard-like substance with
an acid value of 40, a saponification value of 211 and a hydroxyl value of
140.1.
Production of additive 14
A mixture of 53 kg (156 moles) of epoxystearic acid methyl ester
(Edenor MeTiO5 Epoxid, 4,71% epoxide), 19.3 kg (312 moles) of ethylene
glycol and 17.2 g of concentrated sulfuric acid is heated under nitrogen for
about 1 h at 100~C. The reaction mixture is then neutralized at that
temperature with 10 g of 30% sodium methylate solution and partly distilled
in vacuo (2 torr) by increasing the temperature to 200~C. After cooling to
room temperature, a solution of 13.5 kg of 50% NaOH (169 moles) in 20 kg
of water is added, followed by stirring for 1 h at 80-100~C. After addition of
250 ml of 13% sodium hypochlorite solution, the reaction mixture is neutral-
ized at 70~C with 23.6 kg of 35% sulfuric acid. After removal of the aqueous
phase, the residue is washed repeatedly with water and dried in vacuo. 46
kg of the product are obtained in the form of a light brown viscous liquid with
an acid value of 157, an iodine value of 10, a saponification value of 162 and
a hydroxyl value 253.
Production of additive 15
CA 02230024 1998-02-19
H 1759 PCT 34
-
Additive 15 is produced similarlyto additive 14 from 398 g (1.2 moles)
of epoxystearic acid methyl ester (Edenor MeTiO5 Epoxid, 4.71% epoxide)
and 1025 g (0.4 mole) of glycol. Around 1200 g of the product are obtained
in the form of a dark yellow, solid/liquid substance with an acid value of 53,
a saponification value of 58 and a hydroxyl value of 52.
Production of additive 16
1032 g (1 mole) of castor oil are heated under nitrogen for 2 h at
180~C in a water separatorwith 187 g (1 mole) of anhydrous citric acid. After
cooling, 1135 g of the product are obtained in the form of a yellow viscous
liquid with an acid value of 70, an iodine value of 73, a saponification value
of 292 and a hydroxyl value of 134.
Production of additive 17
Additive 17 is produced similarlyto additive 14 from 60 kg (177 moles)
of epoxystearic acid methyl ester (Edenor MeTiO5 Epoxid, 4.71% epoxide)
and 5.5 kg (88.5 moles) of glycol. Around 60 kg of the product are obtained
in the form of a yellow viscous liquid with an acid value of 177, a saponifica-
tion value of 180 and a hydroxyl value 140.
The measurements of the setting rate and the water absorption
capacity were carried out as follows:
The oleochemical additive was added to 70 ml of water. 140 g of
gypsum (CaSO4 - H2O) (Alfor, a product of Borgardts-Sachsenstein; density
2.63, apparent density 900 g/l) were then added with vigorous stirring. When
the mixture was homogeneous, a test specimen was cast in an 85 mm
diameter aluminium dish and its setting rate was measured. After storage for
48 hours, water absorption was measured by pouring 10 ml of water into a
depression in the test specimen and measuring the time (in minutes) required
CA 02230024 1998-02-19
H 1759 PCT 35
for complete pemmeation. The percentage of additives shown is based on the
water/gypsum mixture as a whole (210 g). So far as this test is concerned,
it is important to remember that, where the permeation time is several hours,
as is possible in the case of additive 1, a large part of the water also
evaporates.
The results are set out in the following Table. All the oleochemical
additives act as setting retarders and, in some cases, as hydrophobicizing
agents.
CA 02230024 1998-02-19
H 1759 PCT 36
Additives Concentration Setting Time Water Absorption Time
% byweight mins. mins.
0 14 2.08
0.25 26 2.63
0.5 24 2.93
0.75 28 3.05
29 3.42
2.5 30 13.85
496.00
86.00
2 0.1 21 3.15
2 0.25 25 3.15
2 0.5 27 3.30
2 0.75 32 4.20
2 1.32 27 5.45
2 4.76 45 18.45
2 9.1 ~300 26.15
3 4.76 38 5.30
4 4.76 >240
5.00 960
6 5.00 22 1.98
7 5.00 24 15.33
8 5.00 65 1.73
9 5 70 1.80
106 1.97
11 5 960
12 5 20 1.90
13 5 26 5.03
14 5 960
960
16 5 133 2.50
17 5 36 9.00
18 5 25 14.00
