Note: Descriptions are shown in the official language in which they were submitted.
CA 02221949 1997-11-21
WO 96/37556 - 1 - PCT/EP96/02227
Aqueous dispersions of organopolysiloxanes
The invention relates to aqueous dispersions of
organopolysiloxanes which following removal of water can
be converted into elastomers, to processes for their
preparation and to their use as sealing and coating
materials.
Environmental protection measures are increas-
ingly dictating the avoidance of organic solvents in
chemical formulations. As a consequence, aqueous systems
are finding application more and more.
Aqueous dispersions of organopolysiloxanes per se
are widely known. The basic structure of such disper-
sions, which vulcanize even at room temperature to form
elastomers, is composed of a linear polymer, a crosslink-
ing component and a crosslinking catalyst. In general,
the initial charge to the reaction vessel is an aqueous
emulsion of polydiorganosiloxanes whose end groups
contain condensable groups. These high molecular weight
polysiloxanes are either emulsified directly or, usually,
are prepared in emulsion by customary techniques by
polymerization, condensation and equilibration from
linear or cyclic, low molecular weight polysiloxanes. The
polymer emulsion is then generally mixed with a cross-
linking component and condensation catalyst, in each case
in bulk or as an emulsion, and with further constituents,
such as fillers, adhesion promoters, etc., the catalyst
comprising almost exclusively (organo) metallic compounds.
The (organo) metallic catalysts employed virtually
without exception as catalysts have the disadvantage that
on the one hand they impair both the storage stability of
the unvulcanized compositions and the stability of the
vulcanized elastomers, and on the other hand they are
regarded as toxicologically objectionable. In many of the
prior developments, the highly complex, time-consuming
and therefore costly preparation of the aqueous emulsions
constitutes a disadvantage. These problems result prin-
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cipally from the emulsion polymerization, emulsion
condensation or equilibration of the polydiorganosilox-
anes to be employed, which takes up reaction time and
must be carried out prior to the preparation of the end
product by mixing in the other constituents. A further
disadvantage of the majority of aqueous emulsions known
to date is their low solids content. It is a high solids
content, however, which is the precondition for low or
insignificant shrinkage during vulcanization, which is
desirable for most areas of application.
For example, US-A 6,054,523 (Wacker-Chemie GmbH)
describes aqueous dispersions of organopolysiloxanes,
comprising condensable organopolysiloxane, silicone
resin, polyvinyl alcohol, (organo)metallic catalyst and
amino-functional substances, which dispersions can be
used to obtain transparent vulcanizates.
Additionally, US-A 5,045,231 (Wacker-Chemie
GmbH) claims aqueous dispersions of organopolysiloxanes,
comprising condensable organopolysiloxanes,
(organo) metallic catalysts, organopolysiloxane resins
and diorganosilanolates, it being possible for the
solids content of the dispersions to be up to 90%.
In DE-B 1037707 (Dow Corning; published on
August 28, 1958) a process for the preparation of emul-
sions of high molecular weight organopolysiloxanes is
disclosed which starts from an emulsion of low molecular
weight siloxanes. The desired molecular size is achieved
with the aid of strongly acidic or alkaline catalysts.
These emulsions do not lead to elastomers.
According to US-A 5,004,771 (Rhone Poulenc;
published on April 2, 1990) or in the corresponding
EP-A 365 439, the acidic condensation of a terminally OH-
blocked polydiorganosiloxane is carried out in aqueous
emulsion. After neutralizing the polymer emulsion, the
further constituents, such as methylsiliconate solution
CA 02221949 2003-05-05
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and nonsiliceous fillers, but not compounds containing
basic nitrogen, are added. The emulsions described, which
have a solids content of less than 90%, do not give rise
to elastomers.
US-A 4,894,412 (Shin-Etsu Chemical Co. Ltd.;
published on January 16, 1990) describes a process for
the preparation of textile coatings. The low-solids
polysiloxane emulsion concerned comprises organosilicon
component, amino-functional siloxane and organosilanes.
The process described comprises an emulsion
polymerization and subsequent neutralization. The disper-
sion obtained is applied in a thin coat to textiles and
vulcanized with heating, for example at 105 C for
3 hours.
Furthermore, CA 2,136,491 (Wacker-Chemie GmbH)
describes aqueous dispersions comprising condensable
organopolysiloxane, low molecular weight silicon resin
and a compound containing basic nitrogen, which
dispersions are free from organic transition metal
compounds.
The invention provides an aqueous RTV
dispersion of organopolysiloxanes, which is free from
organic transition metal compounds and organic
compounds of metals of main groups III, IV and V of the
periodic table, comprising:
(A) one or more organopolysiloxanes containing
condensable groups, of the formula
HO- [SiR1aO] n-H ( I ) ,
in which
each R1 is an identical or different SiC-bonded
hydrocarbon radical having 1 to 18 carbon atoms
which is optionally substituted with halogen
atoms, ether groups, ester groups, epoxy groups,
mercapto groups, cyano groups or (poly) glycol
radicals, said (poly)glycol radicals being
comprised of oxyethylene units, oxypropylene
units, or mixtures thereof, and
n is an integer of at least 30;
(B) from 0.01 to 20 parts by weight, based on 100
CA 02221949 2003-05-05
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parts by weight of organopolysiloxane (A)
containing condensable groups, of organosilicon
compounds of the formula
{ [(RO)3Si-R3-]e R21_e}Si(OR)a_, (II),
in which
each R is identical or different and is a hydrogen
atom or alkyl radical having 1 to 6 carbon atoms,
each R2 is identical or different and is an SiC-
bonded hydrocarbon radical having 1 to 18 carbon
atoms which is optionally substituted with halogen
atoms, ether groups, ester groups, epoxy groups,
mercapto groups, cyano groups or (poly)glycol
radicals, said (poly)glycol radicals defined
above,
each R3 is identical or different and is a
divalent hydrocarbon radical,
a is 0 or 1 and
e is 0 or 1,
and/or partial hydrolyzates thereof having not
more than 8 Si atoms;
(C) organosilicon compound containing basic nitrogen
comprising units of the formula
R4bYcSi (OR5) d04-b-c-d (IV)
2
in which
each R4 is identical or different and is a
monovalent, SiC-bonded organic radical which is
free from basic nitrogen,
each R5 is identical or different and is a
hydrogen atom, alkyl radical, alkali metal cation,
ammonium or phosphonium group,
each Y is identical or different and is a
monovalent, SiC-bonded radical containing basic
nitrogen,
b is 0, 1, 2 or 3,
c is 0, 1, 2, 3 or 4 and
d is 0 , 1, 2, or 3,
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with the proviso that the sum of b, c and d is
less than or equal to 4, at lest one radical Y is
present per molecule, and component (C) is
employed in a quantity such that the content of
basic nitrogen is from 0.01 to 5 parts by weight
based on 100 parts by weight of organopolysiloxane
(A) containing condensable groups; and
(D) one or more surfactants selected from the group
consisting of anionic emulsifiers, nonionic
emulsifiers, and mixtures thereof, said
surfactants present in quantities of from 0.5 to
parts by weight based on 100 parts by weight of
organopolysiloxane (A) containing condensable
groups.
Examples of hydrocarbon radicals R' are alkyl
radicals, such as the methyl, ethyl, n-propyl, isopropyl,
1-n-butyl, 2-n-butyl, isobutyl, tert-butyl, n-pentyl,
r/f
~
ir
CA 02221949 1997-11-21
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isopentyl, neopentyl and tert-pentyl radical; hexyl
radicals, such as the n-hexyl radical; heptyl radicals,
such as the n-heptyl radical; octyl radicals, such as the
n-octyl radical and isooctyl radicals such as the 2,2,4-
trimethylpentyl radical; nonyl radicals, such as the
n-nonyl radical; decyl radicals, such as the n-decyl
radical; dodecyl radicals, such as the n-dodecyl radical;
octadecyl radicals, such as the n-octadecyl radical;
alkenyl radicals, such as the vinyl and the allyl radi-
cal; cycloalkyl radicals, such as cyclopentyl, cyclohexyl
and cycloheptyl radicals and methylcyclohexyl radicals;
aryl radicals, such as the phenyl, naphthyl, anthryl and
phenanthryl radical; alkaryl radicals, such as o-, m- and
p-tolyl radicals, xylyl radicals and ethylphenyl radi-
cals; and aralkyl radicals, such as the benzyl radical,
the a- and the A-phenylethyl radical.
Examples of substituted hydrocarbon radicals Ri
are halogenated radicals such as the 3-chloropropyl
radical, the 3,3,3-trifluoropropyl radical, chlorophenyl
radicals, hexafluoropropyl radicals, such as the 1-tri-
fluoromethyl-2,2,2-trifluoroethyl radical; the 2- (perflu-
orohexyl)ethyl radical, the 1,1,2,2-tetrafluoroethyloxy-
propyl radical, the 1-trifluoromethyl-2,2,2-trifluoro-
ethyloxypropyl radical, the perfluoroisopropyloxyethyl
radical, the perfluoroisopropyloxypropyl radical; ether-
functional radicals, such as the 3-methoxypropyl radical
and the 3-ethoxypropyl radical; cyano-functional. radi-
cals, such as the 2-cyanoethyl radical; ester-functional
radicals, such as the methacryloxypropyl radical; epoxy-
functional radicals, such as the glycidyloxypropyl
radical, and sulfur-functional radicals, such as the
3-mercaptopropyl radical.
Preferred radicals R1 are hydrocarbon radicals
having 1 to 10 carbon atoms with particularly preferably
at least 80%, in particular at least 90%, of the radicals
Rl being methyl radicals.
The average value for the number n in formula (I)
is preferably chosen such that the organopolysiloxane of
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CA 02221949 1997-11-21
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the formula (I) has a viscosity of more than 1000 mm2/s,
particularly preferably more than 10,000 mm2/s, in
particular about 80,000 mm2/s, measured in each case at
a temperature of 25 C.
Although not indicated in formula (I), up to
mol percent of the diorganosiloxane units may be
replaced by other siloxanes, although these other units
are usually present only as impurities which are more or
less difficult to avoid, such as R13SiO1/2, R1SiO3/2 and
10 Si04/2 units, in which Rl is as defined above.
The polydiorganosiloxanes of formula (I) can be
prepared by methods which are known in the technical
field, for example by polymerization or condensation of
low molecular weight cyclic or linear organopolysiloxanes
which are terminally hydroxyl- and/or alkoxy-blocked.
The organopolysiloxane (A) containing condensable
groups which is employed in accordance with the invention
may comprise one single type or else a mixture of at
least two types of such organopolysiloxanes containing
condensable groups.
The organosilicon compound of the formula (II)
may be a silane of the formula
R2aSa. (OR) 4-a (II' ) ,
and a compound of the formula
(RO) 3Si-R3-Si (OR) 3 (II" ) ,
where R, R2, R3 and a are as defined above.
Examples of the radical R2 are those given for
R1, where hydrocarbon radicals having 1 to 18 carbon
atoms are preferred and particular preference is given to
methyl, ethyl, vinyl and phenyl radicals, especially
methyl radicals.
Preferred radicals R are hydrogen atom and alkyl
groups having 1 to 4 carbon atoms, with methyl and ethyl
radicals being particularly preferred.
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Radical R3 preferably comprises divalent hydro-
carbon radicals having 1 to 6 carbon atoms, for example
the methylene, ethylene, propylene and butylene radicals,
with ethylene and propylene radicals being particularly
preferred.
Examples of the organosilicon compound (B)
employed in accordance with the invention are methyltri-
methoxysilane, methyltriethoxysilane, vinyltrimethoxy-
silane, vinyltriethoxysilane, phenyltrimethoxysilane,
phenyltriethoxysilane, tetraethoxysilane, tetrapropoxy-
silane, methacryloxypropyltrimethoxysilane and
(C2H5O)3Si-CHZCH2-Si(OC2H5)3 and the partial hydrolyzates
thereof having not more than 8 silicon atoms, for
instance hexaethoxydisiloxane, with preference being
1B given to methyltrimethoxysilane, methyltriethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane and tetra-
ethoxysilane and the partial hydrolyzates therof having
not more than 6 silicon atoms.
Component (B) particularly preferably comprises
pure silanes of the formula (II') and mixtures of silanes
of the formula (II') and partial hydrolyzates thereof
having not more than 6 silicon atoms, with a proportional
partial hydrolyzate of not more than 90 percent by
weight, particularly preferably of not more than 50
percent by weight, based in each case on the weight of
the silane/partial hydrolyzate mixture.
For the preparation of the aqueous dispersions of
organopolysiloxanes, according to the invention, organo-
silicon compound (B) is employed in quantities of prefer-
ably from 0.01 to 50 parts by weight, particularly
preferably from 0.1 to 20 parts by weight, in particular
from 0.1 to 5 parts by weight, based in each case on
100 parts by weight of organopolysiloxane (A) containing
condensable groups.
The organosilicon compound (B) employed in
accordance with the invention may comprise one single
type or else a mixture of at least two types of such
organosilicon compounds.
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The compounds (C) containing basic nitrogen which
are employed in accordance with the invention are prefer-
ably those comprising units of the formula
R4bYcSi (OR5) d04-b-c-d (IV) ,
2
in which
each R4 can be identical or different and is a
monovalent, SiC-bonded organic radical which is free
from basic nitrogen,
each R5 can be identical or different and is a hydrogen
atom, alkyl radical, alkali metal cation, ammonium
or phosphonium group,
each Y can be identical or different and is a monovalent,
SiC-bonded radical containing basic nitrogen,
b is 0, 1, 2 or 3,
c is 0, 1, 2, 3 or 4 and
d is 0, 1, 2, or 3,
with the proviso that the sum of b, c and d is less than
or equal to 4 and that at least one radical Y is present
per molecule.
Radical R4 preferably comprises hydrocarbon
radicals having 1 to 18 carbon atoms, with particular
preference being given to the methyl, ethyl and propyl
radicals, especially the methyl radical.
Examples of the radical R4 are the examples of
hydrocarbon radicals given for Rl.
Radical RS preferably comprises hydrogen atom,
methyl radical, ethyl radical and alkali metal cation,
with particular preference being given to hydrogen atom,
methyl radical, ethyl radical, sodium cation and potas-
sium cation.
Examples of radical R5 are the hydrocarbon
radicals given for radical R, the cations of the alkali
metals, such as those of lithium, sodium, potassium,
rubidium and cesium, and also radicals of the formula
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CA 02221949 1997-11-21
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* NR64 (V)
or
+ PR6 4 ( VI )
in which each R6 can be identical or different and is a
hydrocarbon radical having 1 to 6 carbon atoms.
The radicals Y are preferably radicals of the
formula
R7 2Nga- (VII),
in which each R7 can be identical or different and is
hydrogen, alkyl, cycloalkyl or aminoalkyl radical and R8
is a divalent hydrocarbon radical.
The examples of alkyl and cycloalkyl radicals
R1 apply in their full scope to alkyl or cycloalkyl
radicals R7, respectively, as well.
In the radicals of the formula (VII) there is
preferably at least one hydrogen atom attached to each
nitrogen atom.
Radical R8 preferably comprises divalent hydro-
carbon radicals having 1 to 10 carbon atoms, particularly
preferably 1 to 4 carbon atoms, especially the n-propyl-
ene radical.
Examples of radical R8 are the methylene,
ethylene, propylene, butylene, cyclohexylene, octadecyl-
ene, phenylene and butenylene radicals.
Examples of radicals Y are
H2N(CH2)3-1
H2N ( CH2 ) 2NH ( CH2 ) 2-,
H2N ( CH2 ) 2NH ( CH2 ) 3-,
H2N ( CH2 ) 2 - ,
H3CNH(CH2)3-,
C2H5NH(CH2)3-.
H3CNH(CH2)2 -,
CZH5NE(CH2)2
REPLACEMENT SHEET (RULE 26)
CA 02221949 1997-11-21
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H2N(CH2)4-1
H2N(CH2)5-,
H ( NHCH2 CH2 ) 3 - ,
C4H9NH ( CH2 ) 2NH ( CH2 ) Z-,
cyclo-C6H11NH (CH2) 3-,
cyclo-C6H11NH (CHZ ) 2-1
(CH3)2N(CH2)3-,
(CH3)2N(CH2)2-1
(C2H5)2N(CH2)3- and
(C2H5)2N(CH2)2-.
Y is preferably H2N(CH2) 3-1 H2N(CH2) 2NH (CH2) 3-,
H3CNH(CH2)3-, CZH5NH(CH2)3- and cyC1o-C6H11NH(CH2)3-, With
particular preference being given to H2N(CH2)2NH(CH2)3-
and cyclo-C6H11NH(CH2)3-.
Where the organosilicon compounds comprising
units of formula (IV) are silanes, b is preferably 0, 1
or 2, particularly preferably 0 or 1, c is preferably 1
or 2, particularly preferably 1, and d is preferably 1,
2 or 3, particularly preferably 2 or 3, with the proviso
that the sum of b, c and d is equal to 4.
Examples of the silanes of the formula (IV)
according to the invention are
H2N(CH2)3-Si(OCH3)3
H2N(CHZ) 3-Si (OC2H5) 3
H2N(CHZ) 3-Si (OCH3) 2CH3
H2N(CH2) 3-Si (OC2H5) 2 CH3
H2N(CH2)3-Si(OH)3_x(OM)
H2N(CH2)3-Si.(OH)2_y(OM)yCH3
H2N ( CHZ ) 2NH ( CH2 ) 3- S i( OCH3 ) 3
HZN(CH2) 2NH (CH2) 3-Si (OC2H5) 3
HZN ( CH2 ) 2NH ( CH2 ) 3- S i( OCH3 ) 2CH3
H2N(CH2)2NH(CH2)3-S(OC2H5)2CH3
H2N(CH2)2NH(CH2)3-Si(OH)3_x(OM)x
H2N (CH2) 2NH (CH2) 3-Si (OH) 2_Y (OM) yCH3
cyclo-C6H11NH(CH2) 3-Si (OCH3) 3
cyclo-C6H11NH (CH2) 3-Si (OC2H5) 3
cyclo-C6H11NH(CH2)3-Si(OCH3)2CH3
cyclo-C6H11NH (CH2) 3-Si (OC2H5) 2CH3
REPLACEMENT SHEET (RULE 26)
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cyclo-C6H11NH(CH2) 3-Si (OH) 3-x(OM) x and
cyc l o- C 6H11NH ( CH2 ) 3- S i( OH ) 2_ Y( OM ) yCH3 ,
where
H2N ( CH2 ) 2NH ( CH2 ) 3- S i( OCH3 ) 3
H2N (CH2) ZNH (CH2) 3-Si (OC2H5) 3
H2N(CH2)2NH(CH2)3-S(OCH3)2CH3
H2N(CH2) 2NH (CH2) 3-Si (OC2H5) 2CH3
H2N(CH2)2N8(CH2)3-Si(OH)3_x(ONa)x
H2N ( CH2 ) 2NH ( CH2 ) 3- S ( OH) 2_Y ( ONa ) YCH3
cyc10-C6H11NS(CH2) 3-Si (OCH3) 3
cyclo-C6H11NH(CH2) 3-Si (OC2H5) 3
cyclo-C6H11NH (CH2 ) 3 -Si (OCH3 ) 2CH3
cyc10-C6H11NH(CH2)3-Si(OC2H5)2CH3
cyclo-C6H11NH (CH2) 3-Si (OH) 3_x (ONa) x and
cyclo-C6H11NH(CH2)3-Si(OH)2_y(ONa)yCH3 are preferred and
H2N(CH2)2NH(CH2)3-Si(OCH3)3
H2N(CH2)2NH(CH2)3-Si(OCH3)2CH3
cyclo-C6H11NH(CH2) 3-S1 (OCH3) 3
cyc 10 - C 6H11NH (CH2) 3-Sf. (OCH3) 2CH3
H2N(CH2) ZNH(CHZ) 3-Si (OH) 3-x (ONa)x and
H2N (CH2) 2NH (CHZ) 3-Si (OH) 2_Y (ONa) yCH3 are particularly
preferred, where x is 0, 1, 2 or 3, y is 0, 1 or 2 and M
is the cation of sodium or potassium.
Silanes of the formula (IV) are commercially
available products and can be prepared by the methods
customary in silicon chemistry.
Where the organosilicon compound comprising units
of the formula (IV) is an organopolysiloxane, the average
value of b is preferably between 0.5 and 2.5, particu-
larly preferably between 0.8 and 2.0, the average value
of c is preferably between 0.01 and 1.5, particularly
preferably between 0.01 and 1.0, and the average value of
d is preferably between 0 and 2.0, particularly prefer-
ably between 0 and 0.2, with the proviso that the sum of
b, c and d is less than or equal to 3.
The organopolysiloxanes employed in accordance
with the invention, comprising units of the formula (IV),
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have a viscosity at 25 C of preferably from 5 to
105 mm2/s, particularly preferably from 10 to 104 aM2/s.
Examples of the organopolysiloxanes employed
according to the invention which comprise units of the
formula (IV) are
H2N(CH2)2NH(CH2)3
(CH3)3SiO [(CH3)2SiO]k [CH3SiO]m Si(CH3)3 (IVa),
H2N(CH2)2NH(IH2)3
CH30 [(CHg)2SiO]k [CH3SiO]m CH3 (IVa`),
H2N(CH2)2NH(IH2)3
CH3CH2O [(CH3)2SiO]k [CH3SiO]m CH2CH3 (IVa " ),
cyclo-C6H11NH(CH2)3
(CH3)3SiO [(CH3)2SiO]k [CHgSiO]m Si(CH3)3 (IVb),
Cyclo-C6H11NH(iH2)3
CH3O [(CH3)2SiO]k [CH3SiO]m CH3 (IVb`)
and
cyclo-C6H11NH(CH2)3
t ..
CH3CH2O [(CH3)2SiO]k [CH3SiO]m CH2CH3 (IVb " ),
the ratio of k to m being in each case between 2:3 and
9:1 and the sum of k and m being between 10 and 1000,
and also
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H2N(CH2)2NH(~H2)3
[(CH3)2SiO]o [Si03/2]p 1(CH3)3Si01/21r (IVc),
H2N(CH2)2NH(iH2)3
[CH30]0 [Si03/2]p [(CH3)3SiO1/2]r (IVc`),
H2N(CH2)2NH(CH2)3
1CH3CIi2010 [Si03/2]p [(CH3)3Si01/21r (IVc ")
and
cyclo-C6H11NH(CH2)3
1
[(CH3)2SiO7o [Si03/23p [(CH3)3SiO2/2lr (IVd),
with the sum of o+p+r being between 10 and 1000, the
ratio of o:(o+p+r) being between 0 and 0.9, in particular
between 0.2 and 0.7, the ratio of p: (o+p+r) being between
0.05 and 0.6, in particular between 0.1 and 0.5, and the
ratio of r:(o+p+r) being between 0.05 and 0.75, in
particular between 0.2 and 0.6,
and also
H2N(CH2)2NH(IH2)3
CH30-[CH3SiO]n-CH3 (IVe),
n being between 5 and 100.
Organopolysiloxanes comprising units of the formula (IV)
are commercially available products and can be prepared
by methods which are customary in silicon chemistry.
As component (C) it is preferred to employ
potassium N-(2-aminoethyl)-3-aminopropylmethylsilanolate,
sodium N-(2-aminoethyl)-3-aminopropylmethylsilanolate,
a,w -dimethoxypoly(N-(2-aminoethyl)-3-aminopropylmethyl-
siloxane) and N-(2-aminoethyl)-3-aminopropylmethyldimeth-
REPLACEMENT SHEET (RULE 26)
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oxysilane.
The compound (C) containing basic nitrogen which
is employed in accordance with the invention may comprise
one single type or else a mixture of at least two types
of such compounds.
For the preparation of the aqueous dispersions of
organopolysiloxanes according to the invention, component
(C) is employed in a quantity such that the content of
basic nitrogen is preferably from 0.01 to 5 parts by
weight, particularly preferably from 0.01 to 1 part by
weight, in particular from 0.04 to 0.5 part by weight,
based in each case on 100 parts by weight of organopoly-
siloxane (A) containing condensable groups.
The aqueous organopolysiloxane dispersions
according to the invention are generally stabilized by
means of emulsifiers (D). Cationic, nonionic, ampholytic
and nonionic emulsifiers can be used. The person skilled
in the art is sufficiently aware of these emulsifiers and
the quantity in which they are added. It is possible to
use one type of emulsifier, for example an anionic type,
or else mixtures of at least two types of emulsifiers,
for example a mixture of at least one anionic with at
least one nonionic emulsifier.
The emulsifiers (D) can be added as such to the
mixture to be dispersed or to the mixture which is to be
stabilized as a dispersion, but can also be formed by
chemical reaction(s) in the mixture to be dispersed or
the mixture to be stabilized as a dispersion from a
precursor, for example the corresponding acid, base or a
salt of the actual emulsifier.
The anionic emulsifiers are preferably the salts
of the surface-active sulfonic acids used in the course
of the emulsion polymerization for forming the organo-
polysiloxane (A) containing condensable groups, these
sulfonic acids being in accordance with US-A 3,294,725
(D.E. Findley, Dow Corning Corporation; published on
December 27, 1966), which indicates the surface-active
sulfonic acids and salts thereof. The alkali metal salts
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or ammonium salts of the sulfonic acids are preferred,
especially the potassium salts.
Examples of the sulfonic acids are aliphatically
substituted benzenesulfonic acids, aliphatically substi-
tuted naphthalenesulfonic acids, aliphatic sulfonic
acids, silylalkylsulfonic acids and aliphatically substi-
tuted diphenyl ether sulfonic acids.
Other anionic emulsifiers which can be used are
alkali metal sulforicinoleates, sulfonated glycerol
esters of fatty acids, salts of sulfonated monovalent
alcohol esters, amides of aminosulfonic acids, for
example the sodium salt of oleylmethyl tauride, alkali
metal salts of sulfonated aromatic hydrocarbons, such as
sodium a-napthalenemonosulfonate, condensation products
of naphthalenesulfonic acids with formaldehyde, and
sulfates, such as ammonium lauryl sulfate, triethanol-
amine lauryl sulfate and sodium lauryl ether sulfate.
Nonionic emulsifiers are preferably used in
addition to anionic emulsifier. Examples of such nonionic
emulsifiers are saponines, addition products of fatty
acids with ethylene oxide, such as dodecanoic esters with
tetraethylene oxide, addition products of ethylene oxide
with sorbitan trioleate, addition products of phenolic
compounds having side chains with ethylene oxide, such as
addition products of ethylene oxide with isododecylphe-
nol, and imine derivatives, such as polymerized ethylene-
imine, and addition products of alcohols with ethylene
oxide, such as polyethylene glycol(10) isotridecyl ether.
Examples of cationic emulsifiers are salts of
fatty amines, quaternary aamionium compounds, and
quaternary compounds of pyridine, morpholine and imid-
azoline.
Examples of ampholytic emulsifiers are long-chain
substituted amino acids, such as N-alkyldi(aminoethyl)-
glycine, N-alkyl 2-aminopropionate, and betaines, such as
(3-acylaminopropyl)dimethylglycine and alkylimidazolium
betaines.
In addition it is also possible to employ water-
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soluble polymers which are described in the literature as
being suitable for the stabilization of dispersions, for
instance polyvinyl alcohols, polyvinylpyrrolidones,
- polyvinyl sulfates, polyacrylates, polyacrylamides and
malonic acid-styrene copolymers or else polysaccharides,
all of which can be used as emulsifiers for preparing the
dispersions according to the invention.
Where emulsifier (D) is employed, it preferably
comprises anionic emulsifiers, nonionic emulsifiers and
mixtures thereof, particularly preferably alkali metal
salts of organic sulfonic acids, organopolyglycol ethers,
and polyvinyl alcohols.
Emulsifier (D) is preferably employed in prepar-
ing the aqueous organopolysiloxane dispersions according
to the invention.
The quantity of emulsifier which is advantageous
for stabilizing the aqueous organopolysiloxane disper-
sions of the invention is heavily dependent on the
composition of the respective dispersion. In general,
from 0.5 to 10 parts by weight of emulsifier(s) are
sufficient per 100 parts by weight of organopolysiloxane
(A) containing condensable groups.
The aqueous organopolysiloxane dispersions
according to the invention can also contain fillers (E).
Examples of fillers (E) are nonreinforcing
fillers, i.e. fillers having a BET surface area of up to
50 m2/g, such as quartz, diatomaceous earth, calcium
silicate, zirconium silicate, zeolites, metal oxide
powders, such as aluminum oxide, titanium oxides, iron
oxides or zinc oxides and their mixed oxides, barium
sulfate, calcium carbonate, gypsum, silicon nitride,
silicon carbide, boron nitride, powdered glass and
powdered plastics; reinforcing fillers, i.e. fillers
having a BET surface area of more than 50 m2/g, such as
pyrogenically prepared silica, precipitated silica,
carbon black, such as furnace black and acetylene black,
and silicon-aluminum mixed oxides of large BET surface
area; fibrous fillers, such as asbestos, and plastic
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fibers. The fillers specified can have been rendered
hydrophobic, for example by treatment with organosilanes
or organosiloxanes or by etherification of hydroxyl
groups to alkoxy groups.
If fillers (E) are employed, the quantities
involved are preferably from 0.1 to 200 parts by weight,
particularly preferably from 0.5 to 100 parts by weight,
based in each case on 100 parts by weight of organopoly-
siloxane (A) containing condensable groups. The quantity
of filler (E) employed can be varied within wide ranges
and depends in particular on the specific intended
application of the dispersions according to the inven-
tion.
Furthermore, the aqueous organopolysiloxane
dispersions of the invention can comprise additives (F),
which are selected preferably from the group consisting
of adhesion promoters, plasticizers, foam suppressants,
thixotropic agents and dispersants, pigments, soluble
dyes, fungicides, aroma substances and organic solvents
which are inert with respect to the dispersions.
Examples of adhesion promoters, which are added
in order to improve the adhesion of the elastomeric
products, obtained from the novel aqueous dispersions
after removal of their solvent content, to the substrate
to which the novel dispersions have been applied, are
amino-functional silanes, such as N-(2-aminoethyl)-3-
aminopropyltrialkoxysilanes, in which the alkoxy radical
is a methoxy, ethoxy, n-propoxy or isopropoxy radical.
Examples of plasticizers are dimethylpolysilox-
anes which are terminally blocked by trimethylsiloxy
groups, are liquid at room temperature and have a visco-
sity of at least 10 mm2/s.
Examples of organic solvents which are inert with
respect to the dispersions are hydrocarbons, such as
petroleum ethers of various boiling ranges, n-pentane,
n-hexane, hexane isomer mixture, toluene and xylene.
Examples of thixotropic agents are carboxymethyl-
cellulose and polyvinyl alcohol.
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Examples of dispersants are polyacrylic acid
salts and polyphosphates.
The thixotropic agents and dispersants mentioned
also have emulsifying properties in some cases, so that
they can be used as emulsifiers.
From each of the groups of substances mentioned
above as possible component for the aqueous dispersions
according to the invention it is possible in each case
for one component used to be a substance from this group
or else a mixture of at least two different such sub-
stances.
The aqueous organopolysiloxane dispersions
according to the invention preferably have pH values of
from 5 to 13, particularly preferably from 6 to 11.
In the aqueous organopolysiloxane dispersions
according to the invention, solids contents of up to
96 percent by weight may be achieved. Lower solids
contents are of course possible. Even in the case of
aqueous silicone dispersions according to the invention
which do not contain fillers, a solids content of more
than 90 percent by weight can be achieved. The solids
content in this context is the proportion by weight of
all of the constituents of the dispersion, with the
exception of water and, if used, organic solvent, in the
overall weight of the dispersion.
The aqueous organopolysiloxane dispersions
according to the invention may be of coherent consistency
or flowable, depending on the application.
Preferred organosiloxane dispersions according to
the invention are those prepared exclusively using
components (A), (B), (C), (D), water and, if desired, (E)
and ( F ) .
Particularly preferred organosiloxane disper-
sions according to the invention are those prepared
exclusively using components (A), (B), (C), (D) and
water, if desired, (E).
It is possible in principle to prepare the
aqueous dispersions of the invention by any desired
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methods known to date.
From the composition according to the invention
the aqueous dispersions of organopolysiloxanes there
results, as a substantially simplified and therefore
economic mode of preparation, a process (process 1) which
comprises mixing together all of the constituents in the
dispersion, except for filler (E), and dispersing them
together. Thereafter, if desired, the filler (E) can be
incorporated immediately into the dispersion.
According to another procedure (process 2), all
of the constituents of the dispersion, except for compon-
ent (C) and filler (E), are mixed with one another and
dispersed together. Thereafter, component (C) and, if
desired, filler (E) are incorporated into the dispersion.
The dispersions according to the invention are
preferably prepared by process 2.
The emulsification or dispersion operation can be
carried out in customary mixing equipment which is
suitable for the preparation of emulsions or dispersions,
for example high-speed stator-rotor stirrers according to
Prof. P. Willems, known under the trade name "IIltra-
Turrax". In this context reference is made also to
Ullmanns Encyklopadie der Technischen Chemie [IIllmann's
Encyclopedia of Industrial Chemistry], Urban &
Schwarzenberg, Munich, Berlin, 3rd edition, Volume 1,
page 720 ff.
The dispersion according to the invention.can of
course also be prepared in another way. However, it has
been found that the procedure is critical and that not
all types of preparation produce dispersions which lead
to elastomers after removal of water.
The processes of the invention have the advantage
that they are very simple to carry out and that it is
possible to prepare aqueous dispersions having very high
solids contents. A high solids content is the precondi-
tion for a low or insignificant degree of shrinkage on
vulcanization, which is desirable for the majority of
areas of application.
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The processes of the invention also have the
advantage that the individual constituents of the aqueous
dispersion of organopolysiloxanes can be employed without
pretreatment operations; in particular, there is no need
for the operation, described frequently in the prior art,
of condensing or polymerizing the polyorganosiloxane
component prior to emulsification.
The processes of the invention therefore have the
advantage that the aqueous dispersions can be prepared in
a single operation, without waiting times for maturation
during the preparation, which would complicate and slow
down the preparation process.
The process according to the invention can be
carried out discontinuously or else continuously.
The aqueous dispersions according to the inven-
tion have the advantage that they are free from organic
transition metal compounds and organic compounds of the
metals of main groups III, IV and V, with the result,
inter alia, that the dispersions are of high stability on
storage.
The aqueous dispersions according to the inven-
tion are preferably stable on storage at room temperature
in the absence of air, under the pressure of the sur-
rounding atmosphere, for a period of at least three
years; in other words, when the unvulcanized dispersions
are stored under the specified conditions for a rela-
tively long period of at least three years, the pro-
perties both of the unvulcanized dispersions and of the
elastomers which result therefrom after removal of the
water are not altered or are altered only to an insig-
nificant extent. In particular, the consistency of the
aqueous dispersions, and the mechanical properties and
adhesion properties of the elastomers obtained from the
dispersions, are retained after prolonged storage of the
unvulcanized dispersions in the absence of air and at
room temperature.
The aqueous dispersions according to the inven-
tion and the elastomers which result therefrom have the
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advantage of being odorless and toxicologically unobjec-
tionable.
The aqueous dispersions according to the inven-
tion have the advantage that the elastomers which result
after removal of the water possess an absolutely dry and
tack-free surface. Tacky vulcanizate surfaces, as fre-
quently result from aqueous dispersions based on organo-
polysiloxane resins and based on acrylate, in fact show
a tendency toward increased soiling, owing to the attach-
ment of dirt particles such as, for instance, dust.
The aqueous organopolysiloxane dispersions
according to the invention cure within a short time even
at room temperature after evaporation of the solvent
fraction, i.e. the water and, if used, organic solvent,
to form elastomers.
The aqueous dispersions according to the inven-
tion, especially those prepared using polyvinyl alcohols,
have the advantage that they cure in thin films to form
transparent elastomers.
The aqueous organopolysiloxane dispersions
according to the invention can be employed for all
purposes for which aqueous organopolysiloxane dispersions
have also been used hitherto. They can be employed, for
example, as sealing compounds, paints, coating systems
and as electrically insulating or conducting, hydrophobic
coating systems which repel tacky substances, or as bases
for or additives to such systems.
The aqueous dispersions according to the inven-
tion have the additional advantage that they form firmly
adhering coatings on numerous substrates, examples being
paper, textiles, mineral construction materials, plas-
tics, wood and many other substrates. Coating in this
context can be carried out, for example, by brushing,
rolling, dipping or spraying.
A preferred area of application is the use as
sealing compounds and coating materials. Examples which
may be mentioned include joint-sealing compositions for
fagades and buildings, and window glazing, and their use
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as sealants in the sanitary sector. Examples of coatings
include masonry coatings and impregnations, elastic
masonry paints, and coatings on textiles and fabrics.
In the examples described below all parts and
percentages are by weight unless specified otherwise.
Furthermore, all viscosity data relate to a temperature
of 25 C. Unless specified otherwise, the examples below
are carried out at the pressure of the surrounding
atmosphere, i.e. at about 1000 hPa, and at room tempera-
ture, i.e. at about 22 C, or at the temperature which
results when the reactants are combined at room tempera-
ture without additional heating or cooling.
The amine number corresponds numerically to the
value which indicates the consumption in ml of 1 N HCl
for the neutralization of 1 g of amino-functional organo-
silicon compounds.
The elastomer properties are determined in each
case in accordance with the following standardized tests:
Tear strength: DIN 53504-85S1
Elongation at break: DIN 53504-85S1
Modulus: DIN 53504-85S1
Shore A hardness: DIN 53505-87
Tear propagation strength: ASTM D624B-73
The following abbreviations are used:
Me: methyl radical
Et: ethyl radical
Pr: propyl radical
Bu: butyl radical
Vi: vinyl radical
Ac: acetyl radical
Ph: phenyl radical
Example 1
500 g of a, w-dihydroxypolydimethylsiloxane having
a viscosity of 80,000 mm2/s, 5 g of ViSi(OMe)3 and 5 g of
a,w -dimethoxypoly(N-2-aminoethyl)-3-aminopropylmethylsil-
oxane) having a viscosity of 4000 mm2/s and an amine
number of 12 are mixed together with 30 g of a 75%
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strength aqueous sodium dodecylbenzenesulfonate solution
(commercially available under the name "Marion A 375
from Huls AG) and 75 g of water, and the mixture is
converted into a dispersion with the aid of an Ultra-
Turrax mixer. The addition of 345 g of precipitated chalk
gives a creamy soft, smooth, permanently homogeneous mass
of firm consistency with a solids content of 91% and a pH
of 10, which is dispensed under airtight conditions into
cartridges. The properties of the dispersion thus stored
are unchanged over a period of over 1 year.
Films 2 = thick are produced from the resulting
dispersion of organopolysiloxanes by applying the aqueous
dispersion to a polytetrafluoroethylene (PTFE) surface
and allowing the water to evaporate at room temperature.
The dry elastic films which form are investigated two
weeks after application for their elastomer properties.
Data on the elastomer properties can be found in Table 1.
Ecample 2
The procedure described in Example 1 is repeated
with the modification that, instead of the 5 g of
ViSi(OMe)31 the organosilicon compounds specified in
Table 2 are employed, in each case in different batches:
Table 2
Example Organosilicon compound employed
2a) 5 g of ViSi(OEt)3
2b) 5 g of MeSi(OMe)3
2c) 5 g of PhSi (OMe) 3
2d) 5 g of a partial hydrolyzate mixture of
Si(OEt)4 comprising 10 mol% monomer,
34 mol% (EtO)3SiO1/2 units, 38 mol%
(EtO)2SiO units and 18 mol% EtOSiO3/2
units
2e) 5 g of H2C=CMe-COO-(CH2)3Si(OMe)3
After adding 345 g of precipitated chalk to each
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of the above batches a) to e), in each case a creamy
soft, smooth, permanently homogeneous composition is
obtained which is of firm consistency and has a solids
content of about 91% and a pH of about 10, and is dis-
pensed under airtight conditions into cartridges. The
properties of one of the dispersions stored in this way
are unchanged over a period of more than 1 year.
Films 2 mm thick are produced from each of the
resulting dispersions of organopolysiloxanes by applying
the aqueous dispersion to a polytetrafluoroethylene
(PTFE) surface and allowing the water to evaporate at
room temperature. The dry elastic films which form are
investigated two weeks after application for their
elastomer properties. Data on the elastomer properties
can be found in Table 1.
Example 3
The procedure described in Example 1 is repeated
with the modification that, instead of the 30 g of a 75%
strength aqueous sodium dodecylbenzenesulfonate solution,
the compounds or mixtures specified in Table 3 are
employed, in each case in different batches:
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Table 3
Example compounds or mixtures employed
3a) 30 g of a 1:1 mixture of a 75% strength
aqueous sodium dodecylbenzenesulfonate
solution and an 80% strength aqueous solu-
tion of polyethylene glycol(10) isotridecyl
ether (commercially available under the
name "ArlyponT" IT 10" from Grunau)
3b) 30 g of an 80% strength aqueous solution of
polyethylene glycol(10) isotridecyl ether
3c) 30 g of a 3:1 by weight mixture of nonyl-
phenol polyethylene glycol(15) ether
(commercially available under the name
"ArkopalTm N-150" from Hoechst AG) and nonyl-
phenol polyethylene glycol(5) ether
(commercially available under the name
"ArkopalT14 N-050" from Hoechst AG)
After adding 345 g of precipitated chalk to each
of the above batches a) to c), in each case a creamy
soft, smooth, permanently homogeneous composition is
obtained which is of firm consistency and has a solids
content of about 91% and a pH of about 10, and is dis-
pensed under airtight conditions into cartridges. The
properties of one of the dispersions stored in this way
are unchanged over a period of more than 1 year.
Films 2 mm thick are produced from the resulting
dispersion of organopolysiloxanes by applying the aqueous
dispersion to a polytetrafluoroethylene (PTFE) surface
and allowing the water to evaporate at room temperature.
The dry elastic films which form are investigated two
weeks after application for their elastomer properties.
Data on the elastomer properties can be found in Table 1.
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Example 4
200 g of a,w-dihydroxypolydimethylsiloxane having
a viscosity of 80,000 aua2/s, 5 g of ViSi(OMe)3 and 10 g
of 3-(2-aminoethylamino)propyl-functional polydimethyl-
siloxane having a viscosity of 1000 nm2/s and an amine
number of 0.3 (commercially available under the name
"Finish WR 1300" from Wacker-Chemie GmbH) are mixed
together with 2 g of a,w-dimethoxypoly(N-(2-aminoethyl)-
3-aminopropylmethylsiloxane) having a viscosity of
4000 mm2/s and an amine number of 12, 20 g of water and
50 g of a 10% strength aqueous solution of polyvinyl
alcohol having a molecular weight of 85,000 g/mol and a
hydrolysis number of 240 (commercially available under
the trade name "PolyviolTm" W 30/240 from Wacker-Chemie
GmbH) and the mixture is ccnverted ~.nt.o a dispersion with
the aid of an Ultra-TurraxTm mixer. This gives a white,
creamy soft, smooth, permanently homogeneous mass of firm
consistency with a solids content of 84% and a pH of 7.5,
which is dispensed under airtight conditions into cart-
ridges. The properties of the dispersion thus stored are
unchanged over a period of over 1 year. The vulcanized
product is transparent.
Films 2 mm thick are produced from the resulting
dispersion of organopolysiloxanes by applying the aqueous
dispersion to a polytetrafluoroethylene (PTFE) surface
and allowing the water to evaporate at room temperature.
The dry elastic films which form are investigated two
weeks after application for their elastomer properties.
Data on the elastomer properties can be found in Table 1.
Example 5
The procedure described in Example 1 is repeated
with the modification that, instead of the 5 g of a,w-
dimethoxypoly(N-(2-aminoethyl)-3-aminopropylmethyZsilox-
ane), the organosilicon compounds containing basic
nitrogen specified in Table 4 are employed, in each case
in different batches:
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Table 4
Example Organosilicon compound containing basic
nitrogen employed
5a) 5 g of a 50% strength aqueous solution of
potassium N-(2-aminoethyl)-3-aminopropyl-
methylsilanolate (prepared in accordance
with the initially cited German Application
P 43 40 400.6)
5b) 5 g of N-(2-aminoethyl)-3-aminopropyl-
methyldimethoxysilane (coamercially avail-
able under the name "Silan GF 95" from
Wacker-Chemie GmbH)
5c) 5 g of N-(2-aminoethyl)-3-aminopropyltri-
methoxysilane (commercially available under
the name "Silan GF 91" from Wacker-Chemie
GmbH)
5d)
g of a trimethylsiloxy-terminated sili-
cone oil consisting of dimethylsiloxy and
aminopropylmethylsiloxy units, having a
viscosity of 30 mm2/s and an amine number
of 2.5
After adding 345 g of precipitated chalk to each
of the above batches a) to d), in each case a creamy
white, smooth, permanently homogenous composition is
10 obtained which is of firm consistency and has a solids
content of about 91% and a pH of about 10, which is dis-
pensed under airtight conditions into cartridges. The
properties of each of the dispersions stored in this way
are unchanged over a period of more than 1 year.
15 Films 2 atm thick are produced from each of the
resulting dispersions of organopolysiloxanes by applying
the aqueous dispersion to a polytetrafluoroethylene
(PTFE) surface and allowing the water to evaporate at
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room temperature. The dry elastic films which form are
investigated two weeks after application for their
elastomer properties. Data on the elastomer properties
can be found in Table 1.
Comparison $xample 1
The procedure described in Example 1 is repeated
with the modification that, instead of 5 g of a,w-dimeth-
oxypoly(N-(2-aminoethyl)-3-aminopropylmethylsiloxane),
the basic compounds indicated in Table 5 are employed, in
each case in different batches:
Table 5
Comparison Example basic compound employed
CEla) 5 g of 2-amino-2-methylpropanol
CEIb) 5 g of 2-aminoethanol
CElc) 5 g of ethylenediamine
CEld) 5 g of hexylamine
CEle) 5 g of 50% strength aqueous KOH
CElf) 5 g of guanidine carbonate
The addition of 345 g of precipitated chalk to
each of the above batches CEla) to CElf) produces in each
case a creamy soft, homogeneous mass of firm consistency
with a solids content of 91% and a pH of about 10, which
is dispensed under airtight conditions into cartridges.
The dispersions from Comparison Examples..CEla,
CEld, CEle and CElf go stiff in the cartridge within
three days, i.e. the dispersion becomes inhomogeneous and
breaks down, and unwanted elastic components are formed
in the cartridge itself. The dispersions are unusable. It
is therefore no longer possible to produce films of these
compositions for mechanical testing.
Films 2 am thick are produced from each of the
dispersions of organopolysiloxanes of batches CElb and
CElc by applying the aqueous dispersion to a
polytetrafluoroethylene (PTFE) surface and allowing the
water to evaporate at room temperature. Even after a
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period of more than one month, no elastic films suitable
for measurement are formed.
Example 6
The procedure described in Example 1 is repeated
with the modification that 800 g instead of 345 g of
precipitated chalk are employed. The creamy, homogeneous
mass of firm consistency which is obtained has a pH of 10
and a solids content of 95.6%.
A film 2 mm thick is produced from the resulting
dispersion of organopolysiloxanes, by applying the
aqueous dispersion to a polytetrafluoroethylene (PTFE)
surface and allowing the water to evaporate at room
temperature. The dry elastic film which forms is investi-
gated two weeks after application for its elastomer
properties. Data on the elastomer properties can be found
in Table 1.
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Table 1
Test Tear Elonga- Modu- Shore A Tear pro-
strength tion at lusl) hardness pagation
(N/mm2) break ( ~ ) (N/mm2) strength
N/mm)
1 0.4 930 0.1 11 3.4
2a) 0.4 1240 0.1 9 3.5
2b) 0.2 320 0.1 5 1.2
2c) 0.5 1570 0.1 6 2.7
2d) 0.5 990 0.1 6 3.8
2e) 0.4 1090 0.1 6 3.6
3a) 0.5 710 0.2 14 4.0
3b) 0.7 530 0.2 17 4.3
3c) 0.6 470 0.2 12 3.5
4 0.5 320 0.3 15 3.9
5a) 0.5 1290 0.1 12 2.7
5b) 0.5 930 0.2 12 3.3
5c) 0.4 790 0.1 8 3.0
5d) 0.3 810 0.1- 7 2.9
CEla) goes stiff in the cartridge
CElb) no vulcanization
CElc) no vulcanization
CEld) goes stiff in the cartridge
CEle) goes stiff in the cartridge
CElf) goes stiff in the cartridge
6 0.6 370 0.4 23 5.3
1) Tensile strength at 100% elongation
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