Note: Descriptions are shown in the official language in which they were submitted.
133311~
-1- Docket No. Wa-8560
Paper No. 1
A PROCESS FOR PREPARING
ORGANOPOLYSILOXANES CONTAINING
SiC-BONDED ORGANIC RADICALS
HAVING A BASIC NITROGEN
The present invention relates to a process for pre-
paring organopolysiloxanes and more particularly to a process
for preparing organopolysiloxanes containing SiC-bonded organic
radicals having a basic nitrogen atom.
Background of the Invention
Organopolysiloxanes containing SiC-bonded organic
radicals which have a basic nitrogen atom and processes for
preparing the same are described in U. S. Patent No. 2,947,771
to Bailey. The organopolysiloxanes described by Bailey contain
units of the formula R3SiO~, R2SiO and YSi(CH3)0, in which R
represents the same or different monovalent hydrocarbon radicals
or fluorinated monovalent hydrocarbon radicals and Y represents
a monovalent SiC-bonded organic radical having a basic nitrogen.
It is an object of the present invention to provide
a process for preparing organopolysiloxanes containing SiC-
bonded organic -radicals having a basic nitrogen from readily
available organosilicon compounds. Another object of the
present invention is to provide a process for preparing organo-
polysiloxanes of the type described above, in which at least
some of the units of the formula YSi(CH3)0 are replaced by
units of the formula YSiO3/2, where Y represents a monovalent
SiC-bonded organic radical having a basic nitrogen. Still
another object of the present invention is to provide organo-
polysiloxanes which are substantially free of groups that are
capable of condensation, such as silanol groups or atoms which
are capable of condensation, such as Si-bonded hydrogen atoms.
133311~
--2--
A further object of the present invention is to
provide organopolysiloxanes that are storage stable and are
obtained in high yields.
Summary of the Invention
The foregoing objects and others which are apparent
from the following description are accomplished in accordance
with this invention, generally speaking, by providing a process
for preparing organopolysiloxanes containing SiC-bonded organic
radicals having a basic nitrogen which comprises reacting in a
first step, a silane of the formula
YSi~CH3)x(oR )3-x
in which Rl represents the same or different alkyl radicals
having from 1 to 4 carbon atoms in each radical, Y represents
a monovalent SiC-bonded organic radical having a basic nitrogen,
and x is 0 or 1, or partial hydrolysates of such a silane, or
a mixture containing the silane and partial hydrolysates
thereof with an organo(poly)siloxane of the formula
R3SiO(SiR2O)nSiR3
in which R represents the same or different, monovalent hydro-
carbon radicals or monovalent fluorinated hydrocarbon radicals,
and n represents 0 or an integer having the value of from 1 to
100, in an amount of from 0.1 to 10 parts by weight per part
by weight of the silane having the above formula or partial
hydrolysates thereof, in the presence of a basic catalyst and
in the absence of water, and in a second step, reacting the
organopolysiloxane obtained from the first step, with water in
order to hydroly~e groups of the formula
-ORl,
in which Rl is the same as above, to form an alkanol and
silanol groups which are simultaneously and/or subsequently
condensed with one another, and the resultant product formed
in the condensation is separated from the alkanol and water,
and in a third and optional step, reacting the product obtained
from the second step with a cyclic organopolysiloxane of the
formula
(R2sio)m
133~115
--3--
in which R is the same as above, and m is an integer having a
value of from 3 to 12, or a linear organo(poly)siloxane of
the formula
R3Sio(SiR2O)pSiR3
in which R is the same as above, and p is 0 or an integer
having a value of at least 1, or a mixture containing the
linear organo(poly)siloxane and the cyclic organopolysiloxane,
in the presence of a basic catalyst.
- Description of the Invention
The monovalent hydrocarbon radicals and the monovalent
fluorinated hydrocarbon radicals represented by R preferably
contain from 1 to 18 carbon atoms in each radical. Examples
of hydrocarbon radicals represented by R are the methyl,
ethyl, n-propyl, isopropyl, butyl, octyl, tetradecyl and
octadecyl radicals; radicals which contain carbon and hydrogen
atoms and have aliphatic multiple bonds, such as the vinyl,
allyl and hexenyl radicals; cycloaliphatic hydrocarbon radicals,
such as the cyclopentyl, cyclohexyl and methylcyclohexyl
radicals; aromatic hydrocarbon radicals, such as the phenyl
and xenyl radicals; alkaryl radicals, such as the tolyl radicals;
and aralkyl radicals, such as the benzyl radical. An example
of a fluorinated hydrocarbon radical is the 3,3,3-trifluoro-
propyl radical.
Examples of alkyl radicals represented by R are
the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and
the tert-butyl radicals, in which the methyl and the ethyl
radicals are the preferred radicals.
The monovalent SiC-bonded organic radicals having a
basic nitrogen, i.e., the radicals represented by Y, are
preferably those of the formula
R2NR3--
in which R2 represents hydrogen or the same or different
alkyl, cycloalkyl or aminoalkyl radicals, and R3 represents a
divalent hydrocarbon radical which is free of aliphatic mul-
tiple bonds and which contains one carbon atom or 3 or 4carbon atoms in each radical, such as the radical of the
formula
( 2)3 -
` _4_ 1333115
The specific examples of alkyl radicals represented
by R also apply to the alkyl radicals represented by R2.
Examples of aminoalkyl radicals represented by R2
are those of the formulas
H2N(CH2)3-
H2N(CH2)2NH(CH2)3
H2N(CH2)2-
(H3C) 2N(CH2)2
H 2N(CH2)4-
H(NHCH 2CH2) 3- and
4 gNHcH2cH2NH(cH2) _
An example of a cycloalkyl radical represented by R2
is the cyclohexyl radical.
The monovalent, SiC-bonded radicals having a basic
nitrogen, i.e., the radicals represented by Y may also be, for
example, radicals of the formula
2 ~ / 2 ~
O NR3- or \2 ,,,, NR3-
CH2CH2 CH2CH2
in which R3 is the same as above.
Specific examples of silanes of the formula
YSi(CH3)x(oR )3-x
which can be employed in the first step of the process of this
invention are those of the formula
2N(CH2) 3Si(CH3)(0C2H5)2
H2N(CH2)2NH(CH2)3Si(CH3) (0CH3)2
/CH2CH2
CH~ /cHNH(cH2)3si(cH3)(ocH3)2
CH2CH2
~ CH2CH~
o N(CH2)3Si(CH3)(CH3)2
CH2CH2
5~ 1~3Il ~
/ 2 ~
CH~ N(CH2)3Si(cH3)(ocH3)2
CH2CH2
H2N(CH2)3Si(OcH3)3
H2N(CH2)3si(oc2 5)3
H2N(CH2)2NH(CH2)3Si(OCH3)3
/ 2 ~
CH~ CHNH(CH2)3si(OCH3)3
CH2CH2
CH2CH2
\ / N(CH2)3Si(OCH3)3 , and
CH2CH2
/ 2 ~
CH ~ N(CH2)3Si(oCH3)3
CH2CH2
A specific example of a partial hydrolysate of such
a silane is a disiloxane of the formula
2 2)2 H(CH2)3Si(CH3)(OC2H5)] O
In the first step of the process of this invention,
it is possible to use one type of silane of the formula
YSi(CH3)x(oR )3-x
or a partial hydrolysate thereof. However, it is also possible
to use a mixture of at least two different types of such
silanes or partial hydrolysates thereof in the 1st step of
the process of this invention.
In the organo(poly)siloxanes of the formula
R3Sio(SiR2o)nSiR3
at least two of the radicals represented by R in the siloxane
units of the formula
R3SiO%
are preferably methyl radicals. Moreover, it is preferred
13331t~
that at least 50 percent of the radicals represented by R in
the units of the formula
- SiR2o
be methyl radicals because of their availability.
It is possible to employ only one type of organo-
(poly)siloxane of the formula
R3SiO(SiR2o)nSiR3
in the first step of the process of this invention, or it is
possible to use a mixture of at least two different types of
such organopolysiloxanes in the first step of the process of
this invention.
Any basic catalysts which promote the equilibration
of mixtures of organosilicon compounds containing SiC-bonded
organic radicals having a basic nitrogen and organo(poly)si-
loxanes free of such radicals can be employed in the firststep of the process and also in the optional third step of the
process of this invention. Examples of suitable catalysts
which may be employed are alkali metal hydrides, alkali metal
hydroxides, alkali metal silanolates, alkali metal siloxanolates,
quaternary ammonium hydroxides, quaternary ammonium silanolates,
quaternary ammonium siloxanolates, quaternary phosphonium
hydroxides, quaternary phosphonium silanolates, quaternary
phosphonium siloxanolates, alkali metal alkyls, alkali metal
alkenyls, alkali metal aryls, base activated montmorillonites
and basic ion exchange resins. Specific examples of basic
catalysts are sodium hydroxide, potassium hydroxide, caesium
hydroxide, potassium methylsilanolate, tetra-n-butylphosphonium
hydroxide, products obtained from the reaction of tetramethyl-
ammonium hydroxide and octamethylcyclotetrasiloxane, tetra-
methylammonium hydroxide, benzyltrimethylammonium hydroxide,naphthalene-potassium, n-butyllithium and amylsodium.
In the first step of the process of this invention,
and also in the optional third step of the process of this
invention, the basic catalysts can be employed in the same
amounts in which they have been employed heretofore for equili-
brating mixtures of organosilicon compounds containing SiC-
bonded organic radicals having a basic nitrogen and organo-
(poly)siloxanes free such radicals. In the case of base
7 133311~i
activated montmorillonites, basic ion exchange resins and
other basic catalysts which are comparable to these solid,
basic catalysts, the amount of catalyst preferably ranges from
about 0.1 to 10 percent by weight, based on the total weight
of the organosilicon compounds to be reacted with one another
in the first step of the process of this invention. In the
case of the other basic catalysts and basic catalysts which
are comparable to these catalysts, the amount ranges prefer-
ably from about 1 to about 1,000 ppm by weight, based on the
total weight of the organosilicon compounds to be reacted with
one another in the first step of the process of this invention.
The first step of the process of this invention is
preferably carried out at from 15 to about 200C, depending
on the temperature stability of the basic catalyst used and at
atmospheric pressure, i.e., at 1020 hPa (abs.) or about 1020
hPa (abs.). However, higher or lower pressures can also be
used, if desired.
If desired, the first step and the optional third
step of the process of this invention can be carried out under
a protective gas, such as a nitrogen or argon atmosphere.
In the first step of the process of this invention,
it is preferred that the contents of the reaction vessel be
agitated, for example, by stirring.
The reaction carried out in the first step of the
process of this invention is complete when the contents of the
reaction vessel are clear, at least after the removal of the
catalyst contained therein. Generally, a reaction time of
from about 0.1 to 10 hours is sufficient for this reaction.
The organopolysiloxane obtained in the first step of
the process of this invention can be stored before carrying
out the second step of the process of this invention or the
organopolysiloxane obtained from the first step can be pro-
cessed further in the second step of the process of this
invention, more or less immediately after its preparation
without removing or deactivating the basic catalyst present in
the organopolysiloxane from the first step of the process of
this invention.
In the second step of the process of this invention,
water is preferably used in an amount of from about 18 g to
133311~
--8--
- 180 g per gram-equivalent of the group of the formula
-ORl
present in the first step of the process of this invention.
The hydrolysis of the groups of the formula
-SiOR1
and the condensation of the silanol groups formed as a result
of the hydrolysis in the second step of the process of this
invention are preferably carried out at from about 40 to
about 200C, and preferably at atmospheric pressure, i.e., at
1020 hPa (abs.) or about 1020 hPa (abs.). If desired, however,
higher or lower pressures can be used during the hydrolysis
and lower pressures can be used during the condensation of the
silanol groups.
The hydrolysis of the groups of the formula
-SiOR1
and the condensation of the silanol groups in the second step
of the process of this invention are promoted by the catalyst
still present from the first step and/or by adding additional
catalyst.
The water and alkanol can be removed from the product
obtained in the second step of the process of this invention
by, for example, distillation.
The contents of the reaction vessel can be agitated,
for example by stirring, at least during the hydrolysis of the
groups of the formula
-SiORl
and/or condensation of the silanol groups in the second step
of the process of this invention.
In order to obtain a highly storage-stable organo-
polysiloxane containing SiC-bonded organic radicals having a
basic nitrogen, the catalyst can be removed from the organo-
polysiloxane or deactivated after carrying out the second step
of the process of this invention. In the case of catalysts
such as, for example, quaternary ammonium hydroxides, quater-
nary ammonium silanolates and quaternary ammonium siloxanolates,heating the product to a temperature above the decomposition
temperature of the catalysts, usually above 150C, is suffi-
cient for deactivation.
13331I5
At least 50 percent of the radicals represented by R
in the units of the formula
s iR2o
and at least two of the radicals R in the units of the formula
R3SiO
are preferably methyl radicals. Likewise, the R radicals in
the cyclic organopolysiloxanes having the formula
(R2SiO)m
and organopolysiloxanes of the formula
R3SiO(SiR2O)pSiR3
which are employed in the optional third step of the process
of this invention are preferably methyl radicals.
The average value of m is preferably 4 or approxi-
mately 4.
There is no upper limit for p since the third and
optional step of the process of this invention can be carried
out, if necessary, in a solvent which is inert towards the
reactants and the catalyst.
It is possible to use only one type of cyclic dior-
ganopolysiloxane or linear organopolysiloxane in the third and
optional step of the process of this invention. However, it
is also possible to employ a mixture of at least two different
organopolysiloxanes in this step.
The amount of reactants employed in the third and
optional step of the process of this invention are determined
merely by the desired proportion of SiC-bonded organic radicals
having a basic nitrogen in the organopolysiloxanes produced in
the third and optional step of the process according to this
invention and by the average chain length desired.
The third and optional step of the process of this
invention is preferably carried out at 15 to 200C, depending
on the temperature stability of the basic catalyst used, and
at atmospheric pressure, i.e., at 1020 hPa (abs.) or about
1020 hPa (abs.). However, higher or lower pressures can also
be used, if desired.
The contents of the reaction vessel can also be
agitated, for example, stirred in the third and optional step
-lo- 133311~
~ of the process of this invention.
Although the third step of the process of this
invention is optional, when the third step is carried out, it
is complete when the contents of the reaction vessel are
clear, at least after the catalyst contained therein has been
removed. Generally, from about 0.1 to 10 hours are sufficient
for completing the third step of the process.
After carrying out the third step of the process of
this invention, the catalyst is preferably either removed from
the organopolysiloxane or deactivated.
The various steps of the process of this invention
can be carried out successively in one and the same reaction
vessel or in separate reaction vessels. The process, accor-
ding to this invention, can be carried out batchwise, semi-
continuously or continuously.
The organopolysiloxanes or the salts of such organo-
polysiloxanes prepared in accordance with this invention with
organic or inorganic acids in the second or third step can be
used for all purposes for which such organopolysiloxanes con-
taining SiC-bonded organic radicals having a basic nitrogen,
or salts thereof, can be employed.
They may be employed, for example, as release agents
or lubricants, for example, in tire manufacturing or as adhe-
sion-repellent finishes for glass and ceramic surfaces, as
components of textile treating agents, as lubricating oils,
defoamers, foam stabilizers, emulsifiers, antistatic agents
and as additives for thermoplastics and elastomers.
In the following examples, all parts and percentages
are by weight, unless otherwise specified.
Example 1
First step: A mixture containing 82.5 parts of N-(2-amino-
ethyl)-3-aminopropylmethyldimethoxysilane, i.e., a silane of
the formula
H2N(CH2)2NH(CH2)3Si(CH3)(oCH3)2
59.2 parts of a dimethylpolysiloxane which is endblocked by
trimethylsiloxy groups and has an average of 10 siloxane units
per molecule, and 0.1 part of a 40 percent solution of benzyl-
-11- 1333115
trimethylammonium hydroxide in methanol is stirred at 80C for
1 hour under dry nitrogen.
Second step: In the reaction vessel used for carrying out the
first step, the contents thereof are mixed with 50 parts of
water and stirred at 80C for 2 hours, in which a portion of
the methanol formed as a result of the hydrolysis of the
methoxy groups bonded to the silicon atoms, is removed by
distillation. The remaining methanol and water are then
removed by distillation at 13 hPa (abs.). The quaternary
ammonium hydroxide is deactivated by heating for 60 minutes at
150C at 13 hPa (abs.), and the other components which boil
below 150C at 13 hPa (abs.) are simultaneously separated from
the organopolysiloxane. About 113 parts of a clear, colorless
oil are obtained. The resultant organopolysiloxane has an
amine value (number of ml of lN HCL which are necessary to
neutralize 1 g of the oil) of 6.6, a viscosity of 205 mm2.s 1
at 25C, and contains less than 0.1 percent of methoxy groups
as determined by H nuclear magnetic resonance (NMR) spectrum.
Third step: A mixture containing 4 parts of the organopoly-
siloxane obtained in the second step, 500 parts of a mixture
of cyclic dimethylpolysiloxanes having from 3 to 10 siloxane
units in each molecule and having octamethylcyclotetrasiloxane
as the major component, 20 parts of the dimethylpolysiloxane
which is endblocked by trimethylsiloxy groups and which has an
average of 10 siloxane units in each molecule, and 0.2 parts
of a 40 percent solution of benzyltrimethylammonium hydroxide
in methanol is stirred at 80C for 2 hours under dry nitrogen.
The quaternary ammonium hydroxide is then deactivated by
warming for 60 minutes at 150C and at 13 hPa (abs.), and the
other components which boil below 150C at 13 hPa (abs.) are
simultaneously separated from the organopolysiloxane. About
430 parts of a clear, colorless oil are obtained. The organo-
polysiloxane has an amine value of 0.06 and a viscosity of
1140 mm2.s 1 at 25C.
Example 2
The procedure described in Example 1 is repeated,
except that in the third step, 128 parts of the organopoly-
siloxane obtained in the first step are used instead of 4
133~
-12-
parts of the organopolysiloxane, 1600 parts of the mixture of
cyclic dimethylpolysiloxanes are used instead of 500 parts of
the mixture, 27 parts of the dimethylpolysiloxane which is
endblocked by trimethylsiloxy groups and which has an average
of 10 siloxane units in each molecule are used instead of 20
parts of the endblocked dimethylpolysiloxane, and 0.7 parts of
the 40 percent solution of benzyltrimethylammonium hydroxide
are used instead of 0.2 parts of the solution.
About 1400 parts of a clear, colorless oil having an
amine value of 0.6 and a viscosity of 960 mm2.s 1 at 25C are
obtained.
Example 3
First step: A mixture containing 222 parts of N-(2-amino-
ethyl)-3-aminopropyltrimethoxysilane, i.e., a silane of the
formula
H2N(CH2)2NH(CH2)3Si(oCH3)3
296 parts of a dimethylpolysiloxane which is endblocked by
trimethylsiloxy groups and which has an average of 10 siloxane
units in each molecule, and 0.25 parts of a 40 percent solution
of benzyltrimethylammonium hydroxide in methanol is stirred at
80C for 1 hour under dry nitrogen.
Second step: In the reaction vessel used for carrying out the
first step, the contents of the reaction vessel are mixed with
125 parts of water and stirred at 80C for 2 hours, in which a
portion of the methanol formed as a result of the hydrolysis
of the methoxy groups bonded to the silicon atoms, is removed
by distillation. The remaining methanol and the water are
then removed by distillation at 13 hPa (abs.). About 390
parts of a clear, colorless oil are obtained as a residue
after the distillation. This organopolysiloxane has an amine
value of 4.6, a viscosity of 614 mm2.s 1 and contains less
than 0.1 percent of methoxy groups as determined by the 1HN~R
spectrum.
Third step: A mixture containing 120 parts of the organopoly-
siloxane obtained in the second step, 1220 parts of a mixture
of cyclic dimethylpolysiloxanes containing 3 to 10 siloxane
units in each molecule and having octamethylcyclotetrasiloxane
as the major component, 30 parts of the dimethylpolysiloxane
1333115
-13-
which is endblocked by trimethylsiloxy groups and which has an
average of 10 siloxane units in each molecule, and 0.5 parts
of a 40 percent solution of benzyltrimethylammonium hydroxide
in methanol is stirred at 80C for 2 hours under dry nitrogen.
The quaternary ammonium hydroxide is then deactivated by
warming for 60 minutes at 150C at 13 hPa (abs.), and the
components which boil below 150C at 13 hPa (abs.) are simul-
taneously separated from the organopolysiloxane. About 1150
parts of a clear, colorless oil are obtained. The organo-
polysiloxane has an amine value of 0.59 and a viscosity of
1174 mm2 s-l
