Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
21 3S1 66
Docket: WA 9311-S
Paper No. 1
._
BASE-~T~YZED PRO OESS FOR
PREPARING ~Y~N-CONTAINING ORGANOPOLYSILOXANES
Field of Invention
The present invention relates to a process for preparing
organopolysiloxanes containing Si-bonded hydrogen using a basic
catalyst.
Background of Invention
The preparation of organopolysiloxanes containing Si-bonded
hydrogen via hydrolysis and condensation of hydrogen-containing
organosilanes or hydrolysates thereof has been carried out using
acid catalysts, since it was assumed that SiH-bonded hydrogen was
reacted to give hydrogen gas under the action of basic catalysts.
EP-A-251 435 Al describes a process for preparing hydrogen-
containing organopolysiloxane resins having tetrafunctional
siloxane units of alkyl silicate and organosilanes or an oligo-
meric organosiloxane compound in the presence of water and acid
catalysts. However, the resins have a broad molecular weight
distribution.
A process for the base-catalyzed preparation of polysiloxanes
not containing hydrogen is known from EP-A-004 2208, published Dec 23,1981.
SummarY of Invention
It is an object of the present invention to provide a process
by means of which organopolysiloxane oils, elastomers and resins
containing hydrogensilyl groups can be prepared in a simple manner
and reproducibly with a narrow molecular weight distribution.
The present invention relates to a process for preparing
organopolysiloxanes containing Si-bonded hydrogen, which comprises
~133166
- reacting a mixture of the components
(A) organosilicon compounds selected from
(A1) organosilanes of the general formula
RaHbSi(ORl)(4-a-b)~ (1)
where
R is optionally substituted C1- to C18-hydrocarbon
radicals,
Rl is optionally substituted C1- to C18-hydrocarbon
radicals or hydrogen atoms,
a is 0, 1, 2 or 3 and
b is 0, 1, 2 or 3, and
(A2) organosiloxanes comprising units of the general formula
RcHd(oRl)esio(4-c-d-e)/2l (2)
where
c and e are each 0, 1, 2 or 3,
d is 0, 1, 2 or 3 and
R and Rl are as defined above,
with the proviso that component A has at least 0.01 - 4 mole
of alkoxy groups per mole of silicon atoms and that at least
a part of the organosilicon compounds of the component A com-
prises Si-bonded hydrogen,
(B) at least 0.5 mole of water per mole of alkoxy groups in
component A, and
(C) optionally a water-miscible solvent, in the presence of
(D) ammonia, a primary or secondary C1-C4-alkylamine or a com-
pound which liberates ammonia or primary or secondary Cl-C4-
alkylamine on reaction with water.
The organopolysiloxanes containing Si-bonded hydrogen pre-
pared by the process of the invention have a more uniform molecu-
lar weight than organopolysiloxanes containing Si-bonded hydrogen
prepared by means of acid catalysts.
2133166
,
Examples of radicals R, wherein each R is independently,
alkyl radicals such as the methyl, ethyl, n-propyl, iso-propyl,
n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl,
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 iso-octyl radicals such as the 2,2,4-
trimethylpentyl radical; nonyl radicals such as the n-nonyl radi-
cal; 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, allyl,
n-5-hexenyl, 4-vinylcyclohexyl and the 3-norbornenyl radical;
cycloalkyl radicals such as cyclopentyl, cyclohexyl, 4-ethylcyclo-
hexyl, cycloheptyl radical, norbornyl radicals and methylcyclo-
hexyl radicals; aryl radicals such as the phenyl, bipheny,
naphthyl and anthryl and phenanthryl radical; alkaryl radicals
such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl
radicals; aralkyl radicals such as the benzyl radical, the ~, and
~-phenylethyl radical.
Examples of substituted hydrocarbon radicals as radical R are
halogenated hydrocarbon radicals such as the chloromethyl,
3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,-
4,3,3-heptafluoropentyl radical, and also the chlorophenyl,
dichlorophenyl and trifluorotolyl radical; mercaptoalkyl radicals
such as the 2-mercaptoethyl and 3-mercaptopropyl radical; cyano-
alkyl radicals such as the 2-cyanoethyl and 3-cyanopropyl radical;
aminoalkyl radicals such as the 3-aminopropyl, N-(2-aminoethyl)-3-
aminopropyl and N-(2-aminoethyl)-3-amino-(2-methyl)propyl radical;
aminoaryl radicals such as the aminophenyl radical; acyloxyalkyl
radicals such as the 3-acryloxypropyl and 3-methacryloxypropyl
radical; acetoxyalkyl radicals such as the 3-acetoxypropyl radi-
cal; diethylphosphonic ester radicals such as the diethylphos-
~133I66
phonic ester-ethyl radical; succinic anhydride alkyl radicals such
as the 3-succinic anhydride-propyl radical; hydroxyalkyl radicals
such as the 3-hydroxypropyl radical and radicals of the formulae
O~
CH2-CHCH20(CH2)3- and HOCH2CH(OH)CH2SCH2CH2-.
The radicals R are preferably the methyl, ethyl, n-propyl,
vinyl, n-5-hexenyl and phenyl radicals, in particular the methyl
and the vinyl radicals.
Examples of the radical Rl are the examples given for R. The
radical Rl are preferably alkyl groups having from 1 to 6 carbon
atoms which can be substituted by preferably Cl-C6-alkyloxy groups
or hydroxy groups.
The radicals Rl are preferably the methyl, ethyl, n-propyl,
iso-propyl and hexyl radicals, more preferably the methyl and
ethyl radicals.
Examples of the silanes Al of formula (1) used in the process
of the invention are tetramethoxysilane, tetraethoxysilane, tetra-
n-propoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane,
phenyltrimethoxysilane, vinyltriethoxysilane, dimethyldiethoxy-
silane, dimethyldimethoxysilane, trimethylethoxysilane, 3-chloro-
propyldimethylmethoxysilane, 3-chloropropyltrimethoxysilane,
3-acetoxypropyldimethylmethoxysilane, 3-mercaptopropyldimethyl-
methoxysilane, n-octyldimethylmethoxysilane, 3-methacryloxypropyl-
dimethylmethoxysilane, 2-cyclohexenylethyldimethylmethoxysilane,
3-aminopropyldimethylmethoxysilane and 3-cyanopropylmethyldimeth-
oxysilane, with preference being given to using tetraethoxysilane,
methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxy-
silane and vinyldimethylethoxysilane, and more preference being
given to using tetraethoxysilane, methyltriethoxysilane and
dimethyldiethoxysilane.
~1331fi6
- Examples of the hydrogen-containing silanes of formula (1)
used in the process of the invention are trihydrogenethoxysilane,
dihydrogenmethylethoxySilane, hydrogendimethylethoxysilane, hydro-
genmethyldiethoxysilane and hydrogenphenyldiethoxysilane.
The organosiloxanes (A2) used in the process of the invention
preferably have at most 15 units of formula (2). Examples of
organosiloxanes (A2) are linear organosiloxanes such as disilox-
anes, for example hexamethyldisiloxane, 1,3-diphenyltetramethyldi-
siloxane, l,3-bis(n-5-hexenyl)tetramethyldisiloxane, 1,3-divinyl-
tetramethyldisiloxane, preferably hexamethyldisiloxane and 1,3-di-
vinyltetramethyldisiloxane and cyclic organopolysiloxanes compris-
ing from 3 to 8, preferably 4 or 5, units of formula (2), such as
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and deca-
methylcyclopentasiloxane.
Examples of the hydrogen-containing organosiloxanes (A2) used
in the process of the invention are dihydrogentetramethyldisilox-
ane, tetrahydrogendimethyldisiloxane, dihydrogentetraphenyldisi-
loxane, trihydrogentrimethylcyclotrisiloxane, tetrahydrogentetra-
methylcyclotetrasiloxane and pentahydrogenpentamethylcyclopenta-
siloxane.
The component A can also comprise monomeric and polymeric
silicates. This is particularly the case for the preparation of
resins. Preferred silicates are methyl orthosilicate, ethyl
orthosilicate, methyl polysilicate and ethyl polysilicate, with
the silicates comprising alkoxy radicals.
The hydrogen content of the hydrogen-containing organopoly-
siloxane final products is preferably 0.0001% to 2% by weight, in
particular 0.01% to 0.6~ by weight.
The content of alkoxy groups of the component A is preferably
0.5 to 2 mole, in particular 0.65 to 1.5 mole, per mole of silicon
atoms.
21331fi6
-- As component B, use is made of preferably at least 0.5 mole,
in particular from 0.5 to 0.8 mole, of water per mole of alkoxy
groups of the component A. A higher proportion of water per mole
of alkoxy groups of the component A effects an increase in the
proportion of gels.
Component C, if used, consists preferably of organic solvents
which at 20~C are homogeneously miscible with water in the volume
ratio 1 : 1. Examples of solvents suitable as component C are
monohydric and polyhydric alcohols such as methanol, ethanol,
n-propanol, isopropanol and ethylene glycol; ethers such as
dioxane and tetrahydrofuran; amides such as dimethylformamide;
dimethyl sulfoxide and sulfolane or mixtures of these solvents.
Preference is given to solvents having a boiling point or
boiling range of up to 120~C at 0.1 MPa, in particular the above
monohydric alcohols.
Component C is preferably added in an amount such that,
depending on the system, the proportion of gel is equal to 0,
preferably from 20% to 300% by weight, in particular from 50% to
100% by weight, based on the proportion of silane in component A.
Those compounds of component D which liberate ammonia or
primary or secondary C1-C4-alkylamine on reaction with water, are
preferably of the formulae
R2nSiZ4-n
(R23Si)2NH (4),
(R22SiNH)X (5),
(R23Si)2NR3 (6)
and
(R22SiNR3)y (7)
where
R2 is a hydrogen atom or a C1-C4-alkyl radical,
R3 is a Cl-C4-alkyl radical,
Z is the group -NHR3 or NR32,
~133166
- n is 2 or 3,
x is an integer from 3 to 6 and
y is an integer from 1 to 12.
Particular preference is given to using compounds of formula
(4), in particular hexamethyldisilazane.
In the process of the invention, ammonia or primary or secon-
dary C1-C4-alkylamine act as catalyst and are preferably removed
after the reaction, in particular by treatment under reduced
pressure.
In the process of the invention, use is preferably made of
0.005 to 0.5 mole, in particular 0.05 to 0.3, mole of ammonia or
primary or secondary C1-C4-alkylamine or compounds which liberate
the above amounts of ammonia or primary Cl-C4-alkylamine on reac-
tion with water, per 1 mole of the component A.
The invention can be used to prepare hydrogen-containing
organopolysiloxane oils, elastomers and resins by varying the
selection of components A through D. Silanes of formula (1) in
which (4-a-b) = w and siloxanes of formula (2) in which (4-c-d) =
w are designated as M, D, T and Q units respectively when w = 1,
2, 3 and 4 respectively. The number of M, D, T or Q units used in
the process can vary from O up to 100 mole ~. The process of the
invention is particularly suitable for the preparation of hydro-
gen-cont~ining silicone resins, in particular of MQ resins in
which the M/Q ratio is preferably from 0.3 : 1 to 2 : 1, in par-
ticular from 0.5 : 1 to 1.25 : 1. For example, it is possible to
prepare transparent, monomodally distributed MQ resins which are
soluble in organic solvents and whose molecular weights can be set
to from 4,000 g/mole to 25,000 g/mole. Such MQ resins have a pro-
portion of gel of less than 2% by weight, based on the theoretical
yield.
~13316~
The process of the invention is preferably carried out at
from 0~C to 100~C, in particular at from 25~C to 75~C. All vola-
tile components such as water and solvent, such as ethanol, are
preferably removed after the reaction, preferably under reduced
pressure. In the process of the invention, the components A and D
are preferably initially charged and B and C are metered in.
Subse~uent to the reaction of the components A to D, the
hydrogen-containing organopolysiloxanes obtained, in particular
the resins, can be subjected to further condensation under the
action of acid or base to lower the content of _oR1 groups, in
particular the alkoxy group content. If this is carried out in
the absence of water, the hydrogen content can also be kept almost
unchanged using strong bases, such as alkali metal and alkaline
earth metal hydroxides as condensation catalysts in organic sol-
vents such as hydrocarbons.
The further condensation to lower the content of alkoxy
groups is also possible with hydrogen-containing organopolysilox-
anes which have been prepared in another way and not by the pro-
cess of the invention.
The hydrogen-containing organopolysiloxanes prepared by the
process of the invention can be used for all purposes for which
hydrogen-containing organopolysiloxanes can be used. For example,
the MQ resins are suitable as filler, as crosslinker in addition-
crosslinking systems and as adhesion promoter.
In the following examples, unless otherwise indicated,
(a) all amounts are by weight;
(b) all pressures are 0.10 MPa (abs.);
(c) all temperatures are 25~C.
~133166
- The following abbreviations were used:
AR = analytical reagent
dist. = distilled
Example 1
To the initially charged mixture, heated to 40~C under
protective gas, comprising 125.4 g of tetraethoxysilane (0.6
mole), 9.72 g of hexamethyldisilazane (0.06 mole) and 62.53 g
of hydrogendimethylethoxysilane (0.6 mole) were added drop-
wise 21.60 g of dist. water (1.2 mole) and 60.00 g of AR
ethanol (1.3 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at room
temperature and atmospheric pressure. The mixture was sub-
sequently adjusted to pH 7, freed by filtration of any
amounts of gel formed and then evaporated in a high vacuum at
100~C to constant weight.
This gave 44.48 g (55.9% yield) of a viscous, transparent
oil containing 0.53% by weight of Si-bonded hydrogen.
Example 2
To the initially charged mixture, heated to 40~C under
protective gas, comprising 20.90 g of tetraethoxysilane (0.1
mole), 1.62 g of hexamethyldisilazane (0.01 mole) and 6.72 g
of 1,1,3,3-tetramethyldisiloxane (0.05 mole) were added drop-
wise 3.60 g of dist. water (0.2 mole) and 12.00 g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3 hours at room temp-
erature and atmospheric pressure. The mixture was subse-
quently adjusted to pH 7, freed by filtration of any amounts
of gel formed and then evaporated in a high vacuum at 100~C
to constant weight.
~133166
~ This gave 7.90 g (55.48% yield) of a highly viscous,
transparent oil containing 0.56% by weight of Si-bonded
hydrogen.
Example 3
To the initially charged mixture, heated to 40~C under
protective gas, comprising 20.90 g of tetraethoxysilane (0.1
mole), 2.66 g of hexamethyldisilazane (0.0165 mole), 3.06 g
of 1,3-divinyltetramethyldisilazane (0.0165 mole) and 3.44 g
of hydrogendimethylethoxysilane (0.033 mole) were added drop-
wise 3.60 g of dist. water (0.2 mole) and 10.00 g of AR
ethanol (0.22 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at 60~C,
one hour at room temperature and atmospheric pressure. The
mixture was subsequently adjusted to pH 7, freed by filtra-
tion of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 11.13 g (84.9% yield) of a highly viscous,
transparent oil containing 0.11% by weight of Si-bonded
hydrogen and 5.34% by weight of vinyl groups.
Example 4
To the initially charged mixture, heated to 40~C under
protective gas, comprising 20.90 g of tetraethoxysilane (0.1
mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 5.55 g
of 3-chloropropyldimethylmethoxysilane (0.033 mole) and 2.24
g of 1,1,3,3-tetramethyldisiloxane (0.0167 mole) were added
dropwise 3.60 g of dist. water (0.2 mole) and 12.0 g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room
temperature and atmospheric pressure. The mixture was subse-
~uently adjusted to pH 7, freed by filtration of any amounts
- of gel formed and then evaporate~ ~n a high vacuum at 100~C
to constant weight.
This gave 9.53 g (62.5% yield) of a low-viscosity, trans-
parent oil containing 2.84% by weight of chloropropyl groups
and 0.038% by weight of Si-bonded hydrogen.
Example 5
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.41 g
of 3-acetoxypropyldimethylmethoxysilane (0.0167 mole) and
1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were
added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of
AR ethanol (0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 24 hours at room
temperature and atmospheric pressure. The mixture was subse-
quently adjusted to pH 7, freed by filtration of any amounts
of gel formed and then evaporated in a high vacuum at 100~C
to constant weight.
This gave 3.03 g (36.7% yield) of a low-viscosity, trans-
parent oil containing 2.36% by weight of acetoxypropyl groups
and 0.039% by weight of Si-bonded hydrogen.
Example 6
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 2.75 g
of 3-mercaptopropyldimethylmethoxysilane (0.0167 mole) and
1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were
added dropwise 1.80 g of dist. water (0.1 mole) and 6.0 g of
AR ethanol (0.13 mole), previously mixed in the feed vessel.
~1331 fib
The reaction mixture was stirred for 3.5 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 6.9 g (90.8% yield) of a transparent oil con-
taining 2.55% by weight of mercaptopropyl groups and 0.041%
by weight of Si-bonded hydrogen.
Example 7
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 4.48 g
of diethyl 2-(ethoxydimethylsilyl)ethylphosphonate (0.0167
mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835
mole) were added dropwise 1.80 g of dist. water (0.1 mole)
and 6.0 g of AR ethanol (0.13 mole), previously mixed in the
feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 6.90 g (76% yield) of a low-viscosity, transpar-
ent oil containing 2.99% by weight of diethyl ethanephospho-
nate groups and 0.041% by weight of Si-bonded hydrogen.
Example 8
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.38 g
of n-octyldimethylmethoxysilane (0.0167 mole) and 1.12 g of
-- 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added drop-
wise 1.80 g of dist. water (0.1 mole) and 6.0 g of AR ethanol
(0.13 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was subsequently adjusted to pH 7, freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 5.51 g (67% yield) of a viscous, transparent oil
containing 2.32% by weight of n-octyl groups and 0.043% by
weight of Si-bonded hydrogen.
Example 9
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.61 g
of 3-(methacryloxy)propyldimethylmethoxysilane (0.0167 mole)
and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole)
were added dropwise 1.80 g of dist. water (0.1 mole) and 6.0
g of AR ethanol (0.13 mole), prevlously mixed in the feed
vessel.
The reaction mixture was stirred for 5 hours at 60~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by
filtration of any amounts of gel formed and then evaporated
in a high vacuum at 100~C to constant weight.
This gave 7.52 g (88.9% yield) of a transparent oil con-
taining 3.56% by weight of 3-(methacryloxy)propyl groups and
0.037% by weight of Si-bonded hydrogen.
Example 10
To the initially charged mixture, heated to 40~C under
~1331 66
- protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.31 g
of 2-cyclohexenylethyldimethylmethoxysilane (0.0167 mole) and
1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were
added dropwise 1.80 g of dist. water (0.1 mole) and 7.0 g of
AR ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 3.56 g (43.7% yield) of a yellow, transparent
oil containing 3.1~ by weight of 2-cyclohexenyl groups and
0.03~ by weight of Si-bonded hydrogen.
Example 11
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.48 g
of 2-phenylpropyldimethylmethoxysilane (0.0167 mole) and 1.12
g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole) were added
dropwise 1.80 g of dist. water (0.1 mole) and 7.0 g of AR
ethanol (0.15 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 5.24 g (63.06% yield) of a viscous, transparent
oil containing 2.22% by weight of 2-phenylpropyl groups and
0.039% by weight of Si-bonded hydrogen.
~l33l66
-
Example 12
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 1.35 g of hexamethyldisilazane (0.00835 mole), 3.11 g
of 3,3,3-trifluoropropyldimethylmethoxysilane (0.0167 mole)
and 1.12 g of 1,1,3,3-tetramethyldisiloxane (0.00835 mole)
were added dropwise 1.80 g of dist. water (O.l mole) and 7.0
g of AR ethanol (0.15 mole), previously mixed in the feed
vessel.
The reaction mixture was stirred for 3.5 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 6.88 g (86.5% yield) of a viscous, transparent
oil containing 2.86% by weight of 3,3,3-trifluoropropyl
groups and 0.035% by weight of Si-bonded hydrogen.
Example 13
To the initially charged mixture, comprising 1.80 g of
dist. water (0.1 mole), 6.0 g of AR ethanol (0.13 mole) and
2.46 g of 3-aminopropyldimethylmethoxysilane (0.0167 mole)
was added 0.0167 mole of hydrogen chloride in the form of a
concentrated aqueous hydrochloric acid and the mixture was
adjusted to pH 7.0 using a pH meter. The neutralized initi-
ally charged mixture was heated to 40~C under protective gas,
and 10.45 g of tetraethoxysilane (0.05 mole), 1.35 g of hexa-
methyldisilazane (0.00835 mole) and 1.12 g of 1,1,3,3-tetra-
methyldisiloxane (0.00835 mole) were added dropwise.
~13316~
- The reaction mixture was stirred for 3.5 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by
filtration of any amounts of gel formed and then evaporated
in a high vacuum at 100~C to constant weight.
This gave 6.78 g (85.7% yield) of a yellow solid resin
containing 2.5% by weight of 3-aminopropyl hydrochloride
groups and 0.029% by weight of Si-bonded hydrogen.
Example 14
To the initially charged mixture, heated to 40~C under
protective gas, comprising 62.70 g of tetraethoxysilane (0.3
mole), 8.1 g of hexamethyldisilazane (0.05 mole), 27.49 g of
3-methyldiethoxysilylpropylsuccinic anhydride (0.1 mole) and
6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole) were
added dropwise 10.80 g of dist. water (0.6 mole) and 36.0 g
of AR ethanol (0.78 mole), previously mixed in the feed
vessel.
The reaction mixture was stirred for 24 hours at room
temperature and atmospheric pressure. The mixture was
adjusted to pH 7, subsequently freed by filtration of any
amounts of gel formed and then evaporated in a high vacuum at
100~C to constant weight.
This gave 44.72 g (88.6% yield) of a yellow solid resin
containing 3.2% by weight of propylsuccinic anhydride groups
and 0.02% by weight of Si-bonded hydrogen.
The resin was dissolved in a mixture of 50 ml of AR etha-
nol, 150 ml of dist. water and 2.0 g of potassium hydroxide
(0.036 mole). Using a pH meter and with the addition of a
further 1.0 g of potassium hydroxide (0.018 mole), the pH was
adjusted to 6.98. The solution was filtered and then evapo-
16
1 b' b'
_ rated in a high vacuum at 100~C to constant weight. The
product was subsequently dried over diphosphorus pentoxide in
a high vacuum at 80~C.
Example 15
To the initially charged mixture, heated to 40~C under
protective gas, comprising 20.9 g of tetraethoxysilane (0.1
mole), 2.70 g of hexamethyldisilazane (0.0167 mole), 5.77 g
of cyanopropylmethyldimethoxysilane (0.0333 mole) and 2.24 g
of 1,1,3,3-tetramethyldisiloxane (0.0167 mole) were added
dropwise 3.60 g of dist. water (o.2 mole) and 12.o g of AR
ethanol (0.26 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 3 hours at 75~C and
atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 8.91 g (61.8% yield) of a low-viscosity, trans-
parent oil containing 4.24~ by weight of cyanopropyl groups
and 0.044% by weight of Si-bonded hydrogen.
Example 16
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane
(0.05 mole), 1.35 g of hexamethyldisilazane (0.00835 mole),
4.21 g of 2,2-diethoxy-2,3,4,5-tetrahydro-1,2-benzoxasilepine
(0.0167 mole) and 1.12 g of 1,1,3,3-tetramethyldisiloxane
(0.00835 mole) were added dropwise 1.80 g of dist. water (0.1
mole) and 6.0 g of AR ethanol (0.13 mole), previously mixed
in the feed vessel.
The reaction mixture was stirred for 24 hours at room
temperature and atmospheric pressure. The mixture was
1 6 6
- adjusted to pH 7, subsequently freed by filtration of any
amounts of gel formed and then evaporated in a high vacuum at
100~C to constant weight.
This gave 8.11 g (74.5% yield) of a yellow, highly vis-
cous, transparent oil containing ~.19% by weight of ortho-
phenoxypropyl groups and 0.039% by weight of Si-bonded hydro-
gen.
Example 17
To the initially charged mixture, heated to 40~C under
protective gas, comprising 20.9 g of tetraethoxysilane
(0.1 mole), 2.70 g of hexamethyldisilazane (0.0167 mole),
6.71 g of dimethyldiethoxysilane (0.05 mole) and 7.42 g of
methyldiethoxysilane (0.05 mole) were added dropwise 3.60 g
of dist. water (0.2 mole) and 12.0 g of AR ethanol (0.26
mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 5 hours at 60OC and
atmospheric pressure and was then cooled to room temperature.
The mixture was adjusted to pH 7, subsequently freed by fil-
tration of any amounts of gel formed and then evaporated in a
high vacuum at 100~C to constant weight.
This gave 11.58 g (86.3% yield) of a low viscosity, trans-
parent oil containing 0.04% by weight of Si-bonded hydrogen
groups.
Example 18
To the initially charged mixture, heated to 40~C under
protective gas, comprising 17.84 g of methyltriethoxysilane
(0.1 mole), 4.035 g of hexamethyldisilazane (0.025 mole) and
5.21 g of hydrogendimethylethoxysilane (0.05 mole) were
added dropwise 3.60 g of dist. water (0.2 mole) and 10.00 g
of AR ethanol (0.22 mole), previously mixed in the feed
vessel.
18
1 6 6
- The reaction mixture was stirred for 24 hours at room
temperature and atmospheric pressure. The mixture was
adjusted to pH 7, subsequently freed by filtration of any
amounts of gel formed and then evaporated in a high vacuum at
100~C to constant weight.
This gave 8.03 g (56.8% yield) of a transparent oil con-
taining 0.089% by weight of Si-bonded hydrogen.
Example 19
For the initially charged mixture, 18.48 g of the hydrogen-
containing organopolysiloxane resin (ethoxy content: 17.5%
by weight) from Example 1 were dissolved in 200 ml of tolu-
ene; 500 ppm of potassium hydroxide (25% strength in AR
methanol) were introduced into the initially charged mixture,
the mixture was stirred for 3.5 hours at 80~C and atmospheric
pressure and then cooled to room temperature. The mixture
was adjusted to pH 7, subsequently freed by filtration of any
amounts of gel formed and then evaporated in a high vacuum at
100~C to constant weight.
This gave 16.91 g (91.5% yield) of the starting resin
having an ethoxy content of 13.99~ by weight. The content of
Si-bonded hydrogen did not change.
Example 20
For the initially charged mixture, 4.0 g of the hydrogen-
containing organopolysiloxane resin (ethoxy content: 17.5%
by weight) from Example 1 were dissolved in 40 ml of toluene;
500 ppm of aqueous, concentrated hydrochloric acid were
introduced into the initially charged mixture, the mixture
was stirred for 2.5 hours at 80~C and then cooled to room
temperature. The mixture was neutralized by the addition of
magnesium oxide, subsequently freed by filtration of any
19
~ ~ V ~
- amounts of gel formed and then evaporated in a high vacuum at
100~C to constant weight.
This gave 3.14 g (78.5% yield) of the starting resin
having an ethoxy content of 14.45% by weight. The content of
Si-bonded hydrogen did not change.
Example 21
To the initially charged mixture, heated to 40~C under pro-
tective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), 5.91 g of trimethylethoxysilane (0.033 mole) and 1.80
g of dist. water (0.1 mole) and 12.00 g of AR ethanol (0.26
mole), as previously mixed solution, were added dropwise 3.36
g of l,1,3,3-tetramethyldisiloxane (0.025 mole).
The mixture was stirred at this temperature for 5 minutes
and the solution was subsequently saturated with gaseous
ammonia. The reaction mixture was stirred for an additional
2 hours at room temperature and atmospheric pressure, subse-
quently freed by filtration of any amounts of gel formed and
then evaporated in a high vacuum at 100~C to constant weight.
This gave 2.39 g (22.2% yield) of a viscous, transparent
oil containing 0.1% by weight of Si-bonded hydrogen.
Example 22
To the initially charged mixture, heated to 40~C under
protective gas, comprising 10.45 g of tetraethoxysilane (0.05
mole), and 1.80 g of dist. water (0.1 mole) and 12.00 g of AR
ethanol (0.26 mole), previously mixed, were added dropwise
6.72 g of 1,1,3,3-tetramethyldisiloxane (0.05 mole).
The mixture was stirred at this temperature for 5 minutes
and the solution was subsequently saturated with gaseous
ammonia. The reaction mixture was stirred for an additional
2 hours at room temperature and atmospheric pressure, subse-
Xl~31 66
- quently freed by filtration of any amounts of gel formed and
then evaporated in a high vacuum at 100~C to constant weight.
This gave 3.0 g (30.7~ yield) of a low-viscosity, trans-
parent oil containing 0.4% by weight of Si-bonded hydrogen.
Example 23
To the initially charged mixture, heated to 40~C under
protective gas, comprising 20.90 g of tetraethoxysilane (0.1
mole), 2.66 g of hexamethyldisilazane (0.0165 mole), 4.30 g
of 1,3-divinyltetramethyldisilazane (0.033 mole) and 3.44 g
of hydrogendimethylethoxysilane (0.033 mole), were added
dropwise 3.60 g of dist. water (O.2 mole) and 10.00 g of AR
ethanol (0.22 mole), previously mixed in the feed vessel.
The reaction mixture was stirred for 2.5 hours at 60~C and
for one hour at room temperature at atmospheric pressure.
The mixture was subsequently freed by filtration of any
amounts of gel formed and then evaporated in a high vacuum at
100~C to constant weight.
This gave 9.55 g (67.7% yield) of a white solid resin con-
taining 5.56% by weight of vinyl groups and 0.099% by weight
of Si-bonded hydrogen.
l.o g of solid resin was subsequently dissolved in 9.0 g
of toluene and admixed with 100 ppm (based on pure platinum)
of a platinum catalyst comprising hexachloroplatinic acid and
divinyltetramethyldisiloxane.
This gave 10.0 g of a stable, transparent gel.
Example 24
5.0 g of hydrogen-containing organopolysiloxane resin from
Example 2 were mixed with 5.0 g of ~,w-divinylpolydimethyl-
siloxane having a viscosity of 500 mPa s, and admixed with
100 ppm (based on pure platinum) of a platinum catalyst
~f 331 66
- comprising hexachloroplatinic acid and divinyltetramethyldi-
siloxane.
This gave 10.0 g of a brittle, transparent product.
Example 25
To the initially charged mixture, heated to 40~C under
protective gas, comprising 41.8 g of tetraethoxysilane (0.2
mole), 3.24 g of hexamethyldisilazane (0.02 mole) and 13.44 g
of 1,1,3,3-tetramethyldisiloxane (0.1 mole), were added drop-
wise 7.20 g of dist. water (0.4 mole).
The reaction mixture was stirred for 3 hours at 75~C and
atmospheric pressure, and then cooled to room temperature.
The mixture was subsequently evaporated in a high vacuum at
100~C to constant weight.
This gave a white, insoluble powder containing 0.13% by
weight of Si-bonded hydrogen.
