Note: Descriptions are shown in the official language in which they were submitted.
2~71~5~
The present invention relates to improved yypsum-based
materials containing polyether polyol additive~ and to a
process for their preparation. The improved materials are
suitable, ~or example, for medical purposes (for example
for casts and dental compositions), for the ~uilding
sector ~for example as seam-sealing compositions, plaster
~ materials and for ~he production of fiLnished parts), for
; the production of decorative mouldecl articles and for
making ceramic moulds.
Anhydrous gypsum is used as water-hardening active
inyredient for a wide range of applications, for example
as material for plastering, for casts for immobilisation
~; of parts of the body, as construction material in
building-interior extension work and as modelling com-
positions. ~fter soaking in water, anhydrous gypsum
hardens with setting. However, the hardened gypsum also
has serious disadvantages. It is, for example, not water-
resistant and is so hard and brittle that it often breaks
on exposure to mechanical stress
There have already been attempts to improve the proper-
ties of set gypsumO Thus, German Offenlegungsschrift
3,320,217 states that gypsum can be mixed with aqueous
polyurethane and/or polyurea dispersion , if appropriate
with the addition of alcohols, without premature coagula~
tion of the dispersion and after sPtting has improved
water and breaking resistance. The disadvantage of gypsum
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2~7~51
modified in this manner is its poor reproducibility, .in
particular as a result of nonouniform air inclu~ions and
the non-uniform flow behaviour.
Propo~als to make gypsum moxe water-re~istant for ap-
plications in the building ~ector by soaking in salt
solutions, bitumen or plastic emul3ions have not been
successful ~see "Blick dur~h die Wirtschaft" from
19.9.1982, No. 175, p. 7).
Matesials based on gypsum and organic additives have now
: lO been found which are characterised in that they contain
: polyethers.
Materials according to the invention are distinguished
by improved mechanical propertie~, improved
processability and reduced water~absorption capacity.
Materials according to the invention can contain, for
ex~mple, 0.02 to 5% by weight of polyether in the har-
: dened state. This amount is preferably 0.03 to 2% by
weiqht, particularly preferably Q.05 to 1% by weight.
Based on the not yet hardened gypsum, for example on the20 anhydrous gyp~um or a~hydrite used, materials according
to the invention can be prepared, for example, with the
addition of 18 to 400% by weight of water. Thi~ amount is
preferably 30 to 100~ by weight, particularly preferably
35 to 70% by weight.
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2~710~
The polyethers can be, for example, adducts of ethylone
oxide and/or propylene oxide with starter molecules
containing reactive hydrogen atoms. If ethylene oxide and
propylene oxide were used for adduct formation with the
starter molecules, this can have taken place
simultaneously ~which produces a random distribution of
ethylene oxide and propylene oxide units) or in succes-
sion in any desired order (which produces a block-like
distribution of ethylene oxide and propylene oxide
units). Mixtures of polyethers of different composition
can also be used, for example mixtures of monofunctional
polyethers with polyfunctional polye~her~, mixtures of
random polyethers and block copolyethers or mixtures of
polyethers of the formulae (I) to ( IV) . The polyethers
to be us~d according to the invention can contain
hydroxyl group~ and terminal groups formed by reaction
of the hydroxyl yroups, for example ester, ether,
urethane or caxbonate groups. Analogously, amino poly-
ethers can contain amide or imide groups.
Preferred polyethers have the formulae (I) and/or (II)
St~--(CH2-CH-O)a (CH2-CH2-O)~--(CH2-fH-O)C H' (1),
CH3 CH3 n
St ~ (CH2-fH-O)~--(CH2-CH2-O)e--Hl (Il),
CH3 n
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in which
St repre~ents the radical of a starter molecule, for
example the radical of propylene glycol,
trimethylolpropane, glycerol, ~orbitol,
ethylenediamine, ~tearylamine, ammonia or hydroxyl-
containing polysiloxane,
n represents the number of reactive hydrogen atoms
~ originally present in the starter moleculel
: a represents an integer or a fractional number from
17 to ~3, preferably 19 to 21,
~'
b represent~ an integer or a fractional number from 3
to 6, preferably 3 to 4,
c represents an integer or a fractional number from 1
to 6, preferably 1 to 3,
d represents an integer or a fractional number from
17 to 23, preferably 19 to 22, and
e represents an integer or a fractional number from 3
; to 15, preferably 4 to 7 3
If one or more of numbers a to e represent a fractional
number, these are average number~ characterising mixtures
of different molecules o the formulae (I) andtor (II).
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Further preferred polyethers are products obtained by
reacting vegetable or animal fat~ and oils ~= tri-
glyaerides of fatty acid ) with ethylene oxide and/or
propylene oxide in the pre~ence of basic catalysts.
S Examples of fats and oils which can b~ used for this are
coconut butter, palm kernel oil, tallow fat, lard, rape
oil, soya bean oil, sunflower oil and thistle oil.
Examples of basic catalysts which can be used for thi~
are alkaline metal hydroxides and alcoholates, in par-
ticular oil-soluble alcoholates, such as potassium
propylene glycolate.
If the fats and oils are reacted with ethylene oxicle and
propylene oxide, products can form which a~e analogous to
the formulae (I) or (II), in which ca~e n is then,
however, an integer or a fractional number from 0.5 to 3
and St then represents the radical of a glycerol molecule
additionally containing 2.5 to 0 fatty acid raclicals.
If the fats and oils are r!eacted only with ethylene oxide
or only with propylene oxide, products of the formulae
(III) or (IV) can form.
St ~ (~H2- ~H2- O)fH ¦ (Ill)
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St ~ ~CH2 CH - O) H1
1 g (IV)
CH3 n
in which
St~ represents the radical of a glycerol molecule ~till
containing 2.5 to 0 fatty acid radicals,
~; n' represents an integer or a fractional number from
0O5 to 3 and
f and g are each an integer or a fractional number from
2 to 30, preferably 3 to 15.
If n', f and g and the number mentioned under St' are
fractional numbers, these are average values characteris-
ing the mixture of different moleculPs of the formulae
(III) or (IV~.
The polyethers derived from vegetable and animal fats and
oils can have, for example, molecular weights in the
ran~e from l,000 to 3,000, preferably in the range from
l,300 to 2,500.
Polyether~ to be used for the present invention are often
compounds known per ~e which are commercially available
or, if desired, can be prepared in a manner known per se
~ s ee, for example, German Offenlegungsschrift 2,756,770,
German Offenlegungsschrift 3,330,197, US Patent
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Specification 4,481,367, US Patent Specification2,979,528, US Patent Specification 2,674,619, US Patent
Specification 3,472,781, US Patlent Specification
4,452,712, US Patent Specification 2,677,700, European
Offenlegungsschrift 54,953, European Patent Specification
47,371, European Offenlegungsschrift 116,564, European
Offenlegungsschrift 109,515, GDR Patent Specification
237,178, German Offenlegungsschrift 2,220t338, Macro-
molecules 20, page~ 3089-3091 (19B7) and Technical Data
on Pluronic~ Polyol~, a newsletter fxom ~ASF-Wyandotte
Corp.)O The preparation of polyethers derived from
vegetable and animal fats and oils is described above and
in the examples.
The polyethers to he used according to the invention can
be added to the mixing water, for example, during the
production of gypsum materials. If they are present as
water-soluble and/or water-dispersible solids, they can
be added, for example, to the mixing water and/or to the
gypsum powder. However, they can al80 be used, for
example, in the form of mas~er ~atch granules together
with gypsum or other powders which may be inert.
A particular embodiment of the materials according to the
invention is characterised in that they additionally
contain polyurethanes and/or polyurethane-urea~.
Materials according to the invention of thi~ embodiment
can contain, for example, a total of 0o02 to 50% by
weiyht o~ polyurethanes, polyurethane-ureas and poly-
ether~ in the hardened state . This amount i3 preferably
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0O05 to 10~ by weight, particularly preerably 0.2 to 3
by weight.
Polyurethanes and/or polyurethane~ureas are in general
used in the form of an aqueous dispersion or ~olution.
The Yolids content of such dispersions can be, for
example, 0.5 to 50% by weight. Preferably, it is 1 to 10%
by weight. The overall amounts of water which can be used
for producing the materials according to the invention of
this type are as stated above. It mus~ only be erlsured
that the water in this case is introduced entirely or in
part in the form of the polyurethane and/or polyurethane-
urea dispersion.
Polyurethanes and/or polyurethane-ureas suitable for thi~
embodiment of the present invention in general contain
hydrophilic groups. These can be, for example, a) ionic
groups, b) groups which can be converted into ionic
groups by a neutralisation reaction and/or c) ethylene
oxide units incorporated in the polyether chains present
in the polyurethane or polyurethane-urea.
In principle, any cu~tomary aqueous poly-
urethane(urea)dispersions which, possibly by virtue of
containing alcohols, and, if desired, further organic
solvents, are substantially insensitive to coagulation,
are suitable. A number of processe~ for the preparation
of suitable polyurethane(urea)dispersions in water are
known. A comprehensive list is given, for example, by D.
Dieterich and H. Reiff in ~'Die Angewandte Makromolekulare
;
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Chemie", 26, pages 85-106 (1972), ~. nieterich et al. in
"Angewandte Chemie", 82, pageE 53-S3 (1970), D. Dieterich
et al. in J. Oil Col. Chem. Assoc. 53, pages 363-379
(1970), D. Dieterich in "Die Angewandte Makromolskulare
Chemie'l, 98, pages 133-158 (1981) and in "Chemie und
Technologie makromolekularer Stoffe" [Chemistry and
Technology of Macromolecular Compound~] (29th Publication
of Fachhochschule Aachen on the occasion of the 9th
Colloquium on 8 May 1981 at PH Aachen, Department of
Chemical Engineering). Unless expressly stated otharwise,
in the following the term l'polyurethane" is also under-
stood to mean urea-containing pol~mers, i.e. poly-
urethane-ureas.
A preferred process for preparing suitable aqueous
polyurethane dispersions consists in reacting an NCO
prepolymer dissolved, for example, in an organic solvent
with a chain-lengthening agent. Either the prepolymer or
the chain-lengthening agent contains ionic groups or
groups capable of ion formation. In the course of the
polyaddition reaction or afte~wards, these groups capable
of ion formation can then be converted into ionic groups.
The aqueous dispersion can be formed at the same tLme or
afterwards, for example by addition of water and removal
of the organic 301vent by distillation.
Further d~tails regarding the polyurethane dispersions to
be used and their preparation can ~e taken, for example,
from German Offenlegungsschrift 3,320,217.
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The hydrophilic or potentially hydrophilic group~ are in
general pre~ent in the polyurethanes to be used in such
amounts th~t dispersibility of the polyurethanes in water
i5 en3ured. The hydrophilic group conte.nt of the poly-
urethanes can be, for example, 30 ~o 130 milliequivalentsp~r 100 g of polyure~hane solid, if only ionic group
and/or groups which can be convert~d into ionic group6
are used. If only ethylene oxide units are used as
hydrophilic groups, their conten~ in l:he polyether chains
can be, for example, 2 to 20% by ueight. If both types of
hydrophilic groups are present, 0.1 to 40 milli-
equivalents of ionic groups and/or groups which can be
converted into ionic groups per lQ0 g of polyurethane
solid and simultaneously 0.5 to 10~ by weight of
lS polyethylene oxide units within the polyether chains are
preferably present in the polyurethanes.
Instead of polyurethanes and/or polyurethane~uxeas or in
a mixture with polyurethanes and/or polyurethane~ureas,
other polymers can also be present in the materials
according to the invention. Thus other polymers can also
be in~roduced, for example, in the foxm of products known
per se, such as polybutadiene, polybutadiene/s~yrene,
polyvinyl ~cetate, polystyrene/(meth~ac~ylate and/or
polybutadiene/styrene/acrylonitrile dispersions. In
principle, aqueous dispersions of any monomers which are
copolymerisable with one another are suitable, of which
butadiene, styrene, acrylonitrile, various alkyl acry-
lates, various methacrylates, maleic acid derivatives,
olefins and other vinyl and diene monomers may be
Le A 28 354 - 10 -
2~7~ 0~
mentioned as mon~mers. O~ particular interest are vinyl
acetate ethyl~ne copolymers and rubber lattices.
Polysiloxane dispersions con~aining, if desired, reactive
groups and other reactive systems, such as polyisocyanate
prepolymsrs/ unsaturated polyester resins and epoxy
resins and emulsions of monomers which, after mixing wi~h
gyp~um and water, can be made to react are also suitable.
Yox the preparation of these dispers:ions, the following
examples of olefinically unsaturated monomers may be
mentioned:
a) ~ olefinically unsaturated monocarboxylic acids
having 3 to 5 C atoms and esters or nitriles and
amides thereof, such as acrylic, methacrylic and
crotonic acid, acrylamides and methacrylamides,
ac~ylonitrile and methacrylonitrile, esters of
acrylic and methacrylic acid, in particular those
with saturated monohydric aliphatic or
cycloaliphatic alcohols having 1 to 20 carbon atom~,
such as esters of the acids mentioned with m~thyl
alcohol, ethyl alcohol, propyl alcohol, isopropyl
alcohol, n-butyl alcohol, isobutyl alcohol, hexyl
alcohol, 2-ethylhexyl alcohol, octyl alcohol,
~tearyl alcohol, cyclohexanol, methylcyclohexanol,
further with benzyl alcohol, phenol, cresol, fur-
furyl alcohol, monoesters of ~,~-monoolefinically
un~aturated monocaxboxylic acids having 3 to 4 C
atom~ with dihydric saturated aliphatic alcohols
having 2 to 4 C atoms, such as, for example,
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2-hydro~ypropyl acrylate, 4-hydroxybutyl ~crylate,
glycidyl esters of acrylic and methac~yli~ acid,
~uch as glycidyl (meth)acrylater aminoalkyl esters
and aminoalkylamide~ of acrylic and methacrylic
S acid, such as 2-aminoethyl (meth)acrylate
hydrochloride, N,~-dimethylaminoethyl
(meth)acrylate, N,N-dLmethylaminopropylacrylamide.
Monomers having two or more double bonds in ~he
molecule can also be used. Examples of sui.table
monomers of this type are ethylene glycol diacrylate
or ethylene glycol dimethacrylate.
b~ Olefinically un~aturated dicarboxylic acids
having 3 to 5 C atoms and their derivatives, such as
fumaric acid, maleic acid, itaconic acid, mono- and
diesters of the abovementioned dicarboxylic acids
having 1 to 18 C atoms in the alcohol radical, such
as dimethyl maleate, diethyl maleate, dibutyl
maleate, monohexyl malea~e, monocyclohexyl maleate.
c) Mono- and diesters of vinyl alcohol with carboxylic
aci~s or with hydrohalic acid~, vinyl ethers, vinyl
ketones, vinylamides, such as vinyl acetate, vinyl
propionate, vinyl laurate, vinyl stearate, vinyl
ben~oate, chlorovinyl acetate, divinyl a~ipate,
vinyl chloride, vinylidene chloride, vinyl ethyl
ether, vinyl butyl ether, vinyl ethyl ether or vinyl
i~obutyl ether, vinyl ethyl ketone, vinylformclmide,
N-vinylacetamide.
'
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d) Vinyl compoundR of aromatic and heterocyclics, such
as styrene, ~-methylstyrene, vinyltoluene, p-chloro-
styrene, divinylbenzene, 2-vinylpyrrolidone, 2-
vinylpyridine.
e) N-MPthylol ethers of acrylami~e and methacrylamide
of the gener~l formula
CH2-C-C0-N-CH20R2
R R
in which
R represents hydrogen or methyl,
Rl represents hydrogen, alkyl, aralkyl or aryl,
R2 repre~ents alkyl or cycloalkyl, such as, for ex-
ample, methyl, ethyl, n~propyl, isopropyl, n-
butyl, isobutyl, cyclohexyl
(see DE-B-1,035,363), furth~rmore the non-esterified
N-methylol compounds of acrylamide and methacryl~
: 15 amide.
f) Mannich bases of acrylamide and methacrylamide of
the qeneral formula
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20rlJ
CH2 C - CO- N - CH2- N '
I I ~R
in which R and Rl have the ~ame meaning as above and
R3 and Rq repres*nt alkyl, cycloalkyl or together a
heterocyclic radical, ~uch a~ the morpholine radi-
cal. Suitable compounds of thi~ type are mentioned
in DE-B-1,102,404.
g) Acrylic acid and methacrylic acid derivatives having
a terminal halogenomethylcarbonyl group o the
general formula
O O
Il 11
CH2 =C-C-A-C-C~I2-~
R
in which
R represents hydrogen or methyl,
represents -NH-CHz-NH-, -NH-CO-NH-,
-O-CH2-lH-O-~O-~H or
CH3
-O-CH2-C~-O- and
~H3
X repre~.ents chlorine or bromine ~see
BE-A 696,010)~
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h) Allyl compounds, such as ~rially:L cyanurate, trial-
lyl phosphate, allyl alcohol, allylamine.
i) Monoolefinically unsaturated aliphatic hydrocarbons
having 2 to 6 C atoms, such as ethylene, propylene,
butylene, isobutylene.
j) Conjugated diolefins having 4 to 6 C atom~, such as
butadiene, isoprene, 2,3-dimethylbutadiene, chloro-
butadiene.
k) Furthermore norbornene and hydroxymethylnorbornene.
Preferably, the following are uned:
Acrylic and methacrylic esters having 1 to 12 C atoms in
the alcohol radical, acrylic acid, methacrylic acid and
the C2-C4-hydroxyalkyl esters of these acids, styrene,
acrylonitrile and methacrylonitrile, vinyl acatate~ vinyl
propionate, vinyl chloride, vinylidene chloride, ethylene
or propylene in combination with one or more of the
monomers listed.
These monomers are in general (co)polymerised at tempera
ture~ from 10 to 150C.
Suita~le initiators are in general 0.05 to 5% by weight,
relative to the monomer~, of initiators decomposing into
free radicals~ Examples of such initiators are organic
peroxides, such a~, for example, lauroyl peroxide,
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2~710~
cyclohexanone hydroperoxide, tert.~butyl peroctoate,
tert.-butyl perpivalate, tert.-butyl perbenzoate, di
chlorobenzoyl peroxide, benzoyl peroxide, di-tert.-butyl
peroxide, tert.-butyl hydroperoxide, cumine hydro-
peroxide, peroxycarbonates, such a diisopxopyl peroxydi-
carbonate, dicyclohexyl peroxydicarbonate, diisooctyl
peroxydicarbonate, sulphonyl peroxide-s, such as acetyl-
cyclohexylsulphonyl peracetate, sulphonyl hydrazides, azo
compounds, such a9 azodiisobutyronitrile and water-
soluble azo compounds, such as described, for example, inGerman Auslegeschrift 2,841,045.
Inorganic peroxides, such as hydrogen peroxide, pota~ m
peroxodisulphate and ammonium peroxodisulphate are also
suitable.
The initiators decomposing into free radicals can be used
alone or elRe in combination with reducing agents or
heavy metal compounds. Examples of such compounds are
sodium pyrosulphite ox potassium pyrosulphite, formic
acid, ascorbic acid, thiourea, hydrazine and amine
derivatives, Rongalite. The heavy me~al compounds can be
present either in oil-soluble or in water-soluble form.
Examples of water-soluble heavy metal compounds are
silver nitrate, halides or sulphates of di- or trivalent
iron, cobalt, nickel, salts of titanium or vanadium in
low oxidation states. Examples of oil-soluble heavy metal
; compounds are cobalt naphthenate or the acetylacetone
complexes of vanadium, cobalt, titanium, nickel or iron.
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The polymerisation is in general carried out at a pH of
2 to 10, preferably 4 to 9, whil~ a pH of below 7 is
preferred when cationic oligourethanes ar~ u~ed and a pH
of above 6 for anionic oligourethanes. The pH is ad~usted
within the ranges mentioned often by ~he addition of
aqueous ammonia if acid groups are pre~ent in the reac-
tion mixture.
The molecular weights of the polymers can be regulated by
using conventional regulators, for example n-dodecyl-
thiol, t-dodecylthiol, diisopropyl dixanthate, thioglycol
and thioglycerol. They are in general added in amoun~s of
- 0.1 to 2~ by weight, relative to the monomer mixture.
The emulsion polymerisation in aqueous medium can be
carried out by known polymerisation processes either
batchwise or ccntinuously or by the feed process.
The continuous and the fead process are particularly
preferred. In ~he latter, water is initially introduced
under a nitrvgen atmosphere together with a portion or
the entire emulsifier system and, if desired, a portion
of the monomer mixture, the mixture is heated to the
polymerisation temperature, and the monomer mixture and
the initiator and, if de~ired, emulsifier are added
dropwise over a period of 0.5 to 10 hours, preferably 1
to 6 hours.
After a certain period, the mixture is reactivated, and
the reaction is completed until a conversion of about
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9g.0~ to 99.9% by weight has been reached. Re~idualmonomers and any organic solvent still pre~ent can be
removed after the emul3ion pol~merisation, if desired
to~ether with the water present or a portion thereof, by
distillation in vacuo. Then, if des:Lred, further water
can be added, ultimately resulting in 10 to 60% strength
by weight, preferably 20 to 50% ~3trength by weight
dispersions, as the process product.
Depending on the reaction conditions, the average par-
ticle diameters measured by laser scattered light cor~
relation spectroscopy are between 20 and lO00 nm,
preferably between 50 and 500 nm. Dispersions having
particle sizes of below 50 nm appear transparent/ while
those having larger particle~ appear increasingly cloudy.
The dispersions can be blended with dispersions of the
same charge, such as, for example, with polyvinyl
acetate, polyet~ylene, polystyrene, polybutadiene~
polyvinyl chloride and polyac~ylate dispersions.
Finally, fillers, plasticisers, pi~ments, hydrofluoric
acid and silicic acid sols, aluminium and clay disper-
sions can also be incorpora~ed.
Polymers other than polyurethanes a~d/or poly-
urethane-ureas can al~o be used, for example in the form
of aqueous dispersions having a solids content of 1 to
50% by w~ight and in such amounts that, relative to the
hardened material, 0.02 to 50% by weight of
Le A 28 354 - 18 -
2~051
polyurethanes, polyurethane-ureas, polyethers and/or
other polymers are present.
Materials according to the invention can be prepared, for
example, by first mixing water and polyether or an
5 aqueous polymer di~persion, polyether and, if desired,
water in the desired amount~, then adding the de~ired
amount of gyp5um to this mixture with stirring, and
allowing the mixture then present to har en, i desired
with shaping. Examples of suitable temperatures for the
preparation of the mixture of the components are 10 to
40C, for the hardening 10 to 70C. If desired, mixi.ng of
polyether and gypsum can be ~ollowed by deaeration under
vacuum, if appropriate using a polymer dispersion or
water, in order to remove air inclusions. Gypsum can be
used, for example, in the form of anhydrous gypsum or
anhydrite.
Materials according to the invention prepared in this
manner and possibly present in a certain shape can be,
for example, filed, worked with a knife, ground, sawed,
bored, coated and metallised. They are nonflammable. Upon
treatment with water, these materials absorb water which
they release again virtually completely upon drying in
air. Upon storage in water, in particular polymer-
containing materi~ls according to the invention
substantially retain their strength, whereas a moulded
article stored in water and produced only from gypsum
disintegrates upon exposure to the slightest mechanical
stress.
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Material~ according to the in~ention are suitable, for
example, for the production of slabs for use in the
building ~ector. If desired, for example, fillers and/or
dyestuffs can be added to the materials. Examples of
S suitable fillers are: in each case, up to 10% by weight,
but no~ more than a total of up to 50% by weight (rel-
ative to the entire mixture) of Kieselgur, ground pumice,
carbon black, prepared chalk, ground slate, glass wool,
aluminium powder, silicate materials ~e.g. clay),
alumino~ilicate&, kaolins, finely d:ivided mica, glassfibres, cotton fibres, polyamide fibxes, polyacrylo-
nitrile fibres, cellulose fibres, polyester fibres, wood
flour, cotton linters, polymethylene-ureas, titanium
dioxide, hydrated alumina, ~inely divided lead, lead
oxides, iron oxides, azulmic acid, starch and~or paper,
in particular defibred waste paper. Examples of suitable
dyestuffs are: azo, anthraquinone, pigment and phthalo-
cyanine dyestuffs and optical brighteners and fluorescent
and/or luminescent dyestuffs.
The slabs made from the materials according to the
invention can be, for example, bonded or covered wi~h
tiles~ veneers and/or plastics when used in the building
sector. Moreover, they have excellent heat-insulating
propertiPs.
Materials according to the invention can also be used in
the building sector for improving plasters, mortars,
insulating materials or other construction materials.
L~ A 28 354 - 20
2~71051
Polymer-containing materials according to the invention
are especially also suitable for casts in medical
application~. For this purpose, for example, commercially
available gypsum bandages can be impregnated with an
aqueous polymer dispPrsion and a polyether polyol and the
cast can then be manufactured by cust:omary techniques.
Furthermore, materials according to the invention are
suitable for improving gypsum moulds, or example with
respect to their mechanical stability.
It i~ highly surprising that material~ according to the
invention in general constitute a homogeneous material
and have reproducibly improved mechanical properties (for
example bending resistance and co~pressi~e strength). The
use of hydrated yypsum as iller for polymexs, which is
known per se, does not result in analogous improvements
in properties. If aqueous polymer dispersions and
hydrated gypsum are used for ~he production of materials
for the purpose of co~parison~ and the water is allowed
to evaporate, an inhomogeneous ma~erial with respect to
the breaking resistance compared with the unfilled
polymer is obtained.
The same negative result is obtained if a polymer sheet
of excellent mechanical properties is dissolved in a
mixture of toluene and i opropanol, anhydrous gypsum is
added to this solution, and the amount of water in
ethanol neces ary for setting the gypsum is added. In
this case, the mixture is first homogeneous, but after
Le A 28 354
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evaporation of the solvent a brittle, inhomogeneou~
polymer/gypsum material without any mechanical s~rength
i~ obtained.
The ~act that the setting time~ of polymerJgyp~um mate-
rials can be regula~ed accordin~ to the invention by
additions of alcohol is also highly surprising. Thus,
upon mixing 10~ g of snhydrou6 gypsum with 100 g of a 50%
strength by weight polyurethane-urea dispersion in 20 ml
of ethanol, a homogeneous mixture is obtained which after
being poured onto a plastic slab sets within 15 minutes.
After 2 days, the material reaches its final properties
with respect to breaking and water resistance. In con-
trast, if 100 g of anhydrous gypsum are mixed with 100 g
of the same 50% strength by weight polyurethane disper-
sion without the addition of ethanol, the material setssimilarly to pure gypsum after as little as 3 minutes.
After 2 days, the material thus obtained has reached its
final properties, which differ only a little from that of
a slab whose setting has been delayed by means of
ethanol.
The examples which follow illustrate the present inven-
tion in more detail.
Polyether (PE) useds
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PE 1
Polyether of the formula (I~ ~tartecl with trLmethylol-
propane haYing an a of 19, b of 3, c of 104, an OH number
of 40 and a molecular weight of 4000
S PE ~
Polyether of he formula (II) started with propylene
glycol having a d of 20~ e of 4, an OH number of 41 and
a molecular weight of 2750.
PE 3
Polyether of the ~ormula tII) started with propylene
glycol having a d of 20, e of 5, an OH number of 40 and
a molecular weight of 2800.
PE 4
Polyether of the formula (I) started ~ith glycerol having
an a of 19, b of 3, c of 1.4/ an OH number of 41~6 and a
molecular w~ight of 4500.
PE 5
Polyether of the formula ( I 3 star~ed with trimethylol-
propane having an a of 18, b of 3, c of 2.~, an OH number
of 42.5 and a molecular weight of 4000.
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PE 6
Polyether of the formula (I) started with trimethylol-
propane having an a of 17.5, b of 4.4, c of 1.3, an OH
number of 41.5 and a molecular weight of 4000.
PE 7
Polyether of the formula (I) star~ed with propylene
glycol having an a of 18.5, b of 2.9, c of 1.3, an OH
number of 44.2 and a molecular weight of 2500.
PE 8
In an autoclaYe equipped for ethoxylations, 9 g of sodium
hydroxide powder were added to 850 g of rape oil, and the
mixture was dried ~y heating to 130C in vacuo. 594 g of
ethylene oxide were then metered in with thorough stirr-
ing. The first portions of ethyle~e oxide were added
slowly, and the rest, after the reaction had started,
swiftly. The reaction took a total of 5 hours. The
produc~ thus obtained was washed once at 85C with on~
litre of a 1% strength sodium sulphate solution and twice
with 500 ml each time of water, ~he oil was then
separated off and dried in ~acuo. The product thus
isolated contained 41~ by weight of ethylene glycol ether
groups, relative to the rape oil.
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PE 9
700 g of CQCOnut butter were initially introduced into a
stirred autoclave and melted by heating to 100C. By
applying a vacuum at the ~me time, the coconut butter
and the apparatus were completely dried. S0 g of potas-
sium propylene glycolate solution were ~hen added. The
latter had heen obtained by dissolvi.ng 7 g of potassium
h~droxide in 60 g of propylene glycol. and dis~illing off
water and excess pxopylene glycol at a slight vacuum.
After heating of the batch t~ 125C under nitrogen, 870 g
of propylene oxide were run in with thorough stirringl
while maintaining a pressure of less than 3 PA. .~t the
end of the reaction, it was allowed to continue at 125C
for another hour, until the pre~sure had dropped.
The oil obtained was washed, dried and isol~ted as
described in detail under PE 8. ~he propylene glycol
ether content of the product was 124% by weight, relative
to the coconut butter used.
Example 1
1O3 g of polyether PE 1 were added to 500 g of deionised
water, and the mixture was stirred at 420 rpm for
15 minutes. 800 g of commercially available anhydxous
: moulding plaster were added, the reaction mixture was
stirred for another 30 seconds and then cast in~o moulds.
Aftex a residence time of 1 hour, the moulded articleR
(dimensions: 160 x 40 x 40 mm) were removed from the
moulds, then stored at room temperature for ~ hours, a~
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40C for 48 hours and after cooling to room temparature
for ~nother 18 day~, After thi~, the moulded article~ had
the following properties:
Bending ~trength in accord~nce wi~h ~IN 1164: 7.1 N/mm2
Compressive strength in accordance with DIN 1164:
94.8 N~mm2
Water absorption after 20 minutes: 34.0 g ~specimen
placed upright in water).
Th~se methods of measurement were used in all examples.
Comparative Example 1
A moulded article produced under otherwise identical
conditions but without addition of ~he polyether had the
following properties:
Bending strength: 5.8 N/mm2
Compressive strength: 85.9 N/mm2
Water absorption after 20 minutes: 45.3 g.
Examples 2 to 4
The procedure of ~xample 1 was repeated, except ~hat
different ~mounts of polyether PE 1 ~ere used. rhe
moulded articles obtained had the ollowing proper~ies:
Le A 28 354 - 26
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Ex- Poly~ther Bending Compressive Water
ample strength strength absorption
No. (g) (N/mm ) (N/mm ) ~g~
2 0.~5 6.2 ~6.7 36.4
3 2.6 6.7 91.6 33.2
4 5.~ 6.6 88.3 32.2
Examples 5 to_8
The procedure of Examples 1 to 4 was repeated, except
that polyether P~ 2 was used, giving moulded articles
having the properties listed below:
Ex- Polyether Bending Compressive Water
ample s~ren~th s~rength absorption
No. (g) (N/mm2) (N/mm ) (g)
0.65 7.1 86.5 36.2
6 1.3 7.4 89.3 33.6
7 2.6 7.4 88.5 33.5
8 5.2 6.5 87.3 32.8
ExamPles 9 to 13
The procedure of Examples 1 to 4 was repeated, except
th~t commercially available stucco was used instead of
the moulding plaster. The moulded articles obtained had
the following properties:
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Ex- Polyether Bending Compressive Water
~mple stren ~ h streng~h ab~orption
No. (g) ~N/mm ) (N/mm ) (g)
9(PE 1)0~8 6.7 92.7 74.3
lO(PE l)l.~ 6.7 92.1 25.3
11(PE ~)0.5 fi.9S 84.2 29.1
12(PE 2)1.0 7.05 92.7 26.2
13(PE 2)2.0 6.15 90.1 26.0
ComParative Example 2
The procedure of Examples 9 to 13 was repeated, except
that no polyether was added, giving moulded articles
having the properties listed below:
Bending strength: 6.0 N/mm2
Compressive strength. 77 N/mm2
Water absorption after 20 minutes: 40.2 g
Example 14
The procedure of Example 1 was repeated, except that 40 g
of a 50~ strength by weight aqueous polyurethane disper-
sion was added to the mi~ture before adding ~he mouldingplaster, and the mixtur~ was stirred for another 2 min-
utes, giving moulded articles having the following
properties:
Bending strength: 8.8 N/mm2
~5 Compressive strengths 112.4 ~/mm2
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Water ab~orption after 20 minutes: 24.9 g.
Examples 15 to 29a
The procedure a~ described in Example 14 was repeated,
except that the polyurethane dispersion was u ed in
varying amounts and various polyethers were used in
varying 2~nounts.
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Ex- Poly- Poly- Poly- Bendin~ Compres- Water
ample urethane ether ether ~rens~th s ive absorp-
~ % by ( 9~ by strength tion
weight weight
5solid/ (type) 601id/ (N/mm2) (N/man2) ~g)
solid) ~ solid) )
__ ______~_____~_~_______________ ____________ .
1 PE 1 0 .15 7 . 9 112 O 4 24 . 4
16 1 PE 1 0 . 08 g . 9 111. 6 25 . 3
17 5 PE 2 0 .15 8 . 8 104 . 8 18 . 8
18 5 PE 2 0.80 9.0112.3 17.~
l9 5 PE 1 0 .15 11. 3 115 . 5 20 . 8
PE l 0.80 9.7104.8 19.4
21 1 PE 1 0.15 8.0108.7 25.8
22 2.5 PE 1 0.15 8.3lO9.0 21.4
23 5 PE 1 0.08 8.~l98.3 21.4
24 5 PE 4 û.û8 9.593.0 23.3
PE 5 0.08 9.5100.4 21.4
26 5 PE 6 0.08 8.4103.4 22.0
27 5 PE 3 0 . 08 8 . 0 102 . 2 23 . 0
28 5 PE 7 0 . 08 8 . 3 103 . l 22 . 0
29 0 .15 - - 5 . 985 . 8 42 . 2~for
29a 1 - - 5 . 970 .1 32 .4~,c~
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solid/solid here and in the tables below denotes
polyuxethane or polymer or polyether in Pach case
calculated as anhydrous substance, relative to
~psum.
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Exam~les 30 to_34 ~7~
The procedure as described in Example 14 was repcated,
except ~h~t polyethers PE 8 and PE 9 and commercially
availahle stucco were u~ed instead of moulding plaster.
Ex- Poly- ~oly- Poly- BendingCompres- Water
ample urethane ether ether strenqth sive absorp-
(~ by (% by strength tionweight w~ight
solid~ (type) solid/ (N/mm2) (N/mm2) ~g)
solld~ solid)
.
1.5 PE 90.02 7.6111.0 18.0
31 PE 90.02 8.197.0 2~.3
32 1.5 PE 80.02 7.91111.0 18.2
33 - PE 80.02 6.689.0 32.4
34~ 6.378.2 39.1
for comparison
Examples 35-40
The procedure as described in Example 14 was repeatedl
except that other polymer dispersions were used instead
of the polyurethane dispersion and commercially available
stucco was used instead of moulding plaster.
Polymer t~pe 1 was a dispersion containing polybuta-
diene~styrene.
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Polymer type 2 was a dispersion containing
poly6tyreneJbutyl methacrylate.
x~ Poly- Poly~ Poly- BendingComp.res Water
ample mer ether ether streng~h ~ive absorp-
(% by (% b~ strength tion
weight weigh~
solid/ (type) solid/ (N/mm2) (N/mm2) (g)
solid) solid)
_
1/2 . 5 P~ 1 0 . 15 7 . S 104 . ~ ~ 1 . 3
36 1/2 . 5 PE 2 0 .15 7 . 6 101. 7 23 . 6
37 1/~ . 5 PE 9 0 o 15 7 . 7 102 .1 22 . 3
38 2/2 . 5 PE 1 0 .15 7 . 9 106 . 3 22 . 5
39 ~/2 . 5 PE 9 0 .15 7 . 8 105 . 0 23 .1
) ~ 6 . 3 ~8 . 2 3g . 1
for comparison
Examples 41 to 4 5
The procedure as described in Example 14 was repeated,
except that polyethers PE 8 and PE 9 were used and a
polyurethane dispersion obtained in the following manner
was used in Examples 41 and 43.
0.25 mol of butoxyethoxybutanol (OH number 40), 0.25 mol
of propylene oxide polyether (MW 1000), O.40 mol of
monosulphonsted 1,4-butanediol, 1.2 mol of isophorone
diisocyanate and 0.20 mol of hydroxyethylethylenedi~mine
were reacted with one another to give a polyurethane
dispersion ~ontaining 68~ by weight of water.
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Ex~ Poly- Poly- Poly- ~ending Compres~ Water
ample urethane ether et;he:r s ~xength sive absorp-
( % by ( % by s~rength tion
weight weight
5solid/ (type) solid/(N/lluna) (N/mm2) (g~
solid) ~olid)
41 0.56PE 9 0.02 7.6 112.3 1~.3
42 - PE 9 0.02 8.0 98.0 2g.5
43 0 . 58 PE 8 0 . 02 7 . 75 111. 2 19 . 2
44 - PE 8 0.02 6.5 88.0 31.1
45 ~ - - - 6 . 378 39
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for comparison
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