Note: Descriptions are shown in the official language in which they were submitted.
1~09889
This invention relates to a new class of organosilicon
compounds. More particularly, this invention relates to novel
phenoxyalkyl-, thio- phenoxyalkyl- and pyridyloxyalkyl-silanes
and to a method for preparing these compounds.
According to the present invention, there is provided a
silane represented by the general formula
Rl
~OR Si (0R ) 3
wherein R is -CHO, -CN, -COR, -S02R, -SOR, or -SR
R is methylene or alkylene containing from 3 to 12 carbon atoms,
R3 is alkyl, cycloalkyl or aryl and R4 is selected from the group
consisting of alkyl, cycloalkyl, aryl, alkaryl and aralkyl wherein
any alkyl group present in R3 and R4 contains from 1 to 12 carbon
atoms.
The invention also provides a method for preparing a
silane represented by the general formula
Rl
-h
~ OR Si (OR ) 3
wherein R is -CHO, -CN, -COR, -SO2R, -SOR, SR, -NH2, -NR H,
or -N ( R4 ) 2~ R is methylene or alkylene containing from 3 to 12
carbon atoms, R3 is alkyl cycloalkyl or aryl and R4 is individually
selected from the group consisting of alkyl, cycloal~yl, aryl,
alkaryl and aralkyl wherein any alkyl group ~resent in R3 or R4
contains from 1 to 12 carbon atoms, said method consisting
essentially of reacting substantially equimolar amounts of an
Rl
,~
~10~3
with a haloalkylsilane of the general formula XR2Si(oR3)3 wherein
M represents an alkali metal and x is chlorine, bromine or iodine,
and wherein the reaction of said alkali metal compound and the
silane is conducted under substantially anhydrous conditions at
a temperature of from ambient to 200C in a liquid reaction
medium consisting essentially of a liquid hydrocarbon boiling
from 40 to 200C and a dipolar, aprotic liquid, maintaining the
resultant reaction medium at a temperature of from 40 to 200C
for a period of time sufficient to substantially completely con-
vert said alkali metal compound and said silane to the desiredphenoxyalkylsilane, and isolating said silane by filtering the
reaction medium and evaporating the solvent from the liquid phase.
- la -
~io9~9
Thc present compounds are functionally substituted
phcnoxyalkyl-, thiophenoxyalkyl- or pyridyloxyalkylsilanes
of the general formulae disclosed in the prec~ding section of
this specification. ~he substituent on the phenyl group,
represented by Rl in ~he aforementioned formula, can be
' ~rnn i c~fba~ Y 4
-MH2, dialkylamino, alkylamino, fcrm~ ~ar ~ }~ -COOR ),
O
cyano ~-CN), -~R~, a halogen ~chlorine, bromine or iodine),
-So2R4, -SoR4, nitro ~-N02), -SR4 or -oR4. Amino groups
are preferred because of the many useful applications of
this class of compounds. The substituent can be located
ortho, meta or para with respect to the oxygen atom. The
phenoxy, thiophenoxy or pyridyloxy group is joined to the
silicon atom by means of an alkylene group that can be
methylene or a higher alkylene group containing from 3 to 12
carbon atoms i~ either a linear or branched configuration.
Compounds wherein R2 is ethylene have been found to be so
unstable in the presence of even trace amounts of aqueous
acids or bases as to be useless for all practical purposes.
In addition to the aforementioned alkylene group the silicon
atom is also bonded to three alkoxide or aryloxide groups
represented by oR3 in the foregoing formula.
The presen~ compounds are conveniently prepared
by reacting an alkali metal salt, preferably the sodium salt,
of the desired phenol, thiophenol or hydroxypyridine with
a haloalkylsilane of the general formula XR2Si~oR3)3. This
reaction is highly exothermic and is preferably conducted
under an inert atmosphere and in the absence of even trace
amounts of water, since water is known to react readily
,~ _
~ 11~9889
with trialkoxy- and triaryloxysilanes to yield polymeric
products The reaction medium is a mixture of at least one
liquid hydrocarbon bciling from ~lO to about ~00C and a di-
polar, aprotic liquid such as dimethyl sulfoxide, N,N-dimethyl-
formamide, tetramethyl urea or hexamethylphosphoramide.
Preferably, the trialkoxyhaloalkylsilane is gradually added
to a reaction medium containing the alkali metal salt. ~en
the addition is complete and any exothermic reaction has
subsided, it is usually desirable to heat the reaction mixture
at from 70 to about 150C for several hours to ensure sub-
stantially complete conversion of the reactants to the desired
phenoxyalkyl-, thiophenoxyalkyl~ or pyridyloxyalkyl tri-
hydrocarbyloxysilane. The present compounds, many of which
are colorless, high-boiling, viscous oils, are soluble in
the reaction medium and readily isolatable by removal of
the aforementioned liquid hydrocarbon and dipolar solvent.
Some of the compounds may darken if exposed to light or air
for extended periods of time.
The trihydrocarbyloxyhaloalkylsilanes employed
as one of the reagents for preparing the present compounds
are either commercially available or can readily be obtained
by reacting the corresponding haloalkyltrihalosilane,
X'R2SiX2 wherein Xl and x2 are chlorine, bromine or iodine,
with an alcohol, R30H, that contains from l to 12 carbon
atoms. Alternatively, the hydroxyl group can be bonded
to a carbocyclic or heterocyclic ring structure such as a
cyclohexyl, pyridyl or phenyl group. The hydrocarbyloxy
~9 3
~y
9889
trihalosilane can be prepared by reacting a haloalkene such
as allyl chloride with a trihalosilane, HSiX2, at ambient
temperature in the presence of a platinum catalyst. Pro-
~ cedures for preparing the intermediate silanes are well
: 5 known in the art. A detailed discussion of reaction
conditions i~ therefore not required in this specification.
Illustrative of the phenols and thiophenols
that can be employed to prepare the present compounds are
aminophenols and aminothiophenols wherein the amino group
is located in the ortho, meta or para position relative
to the hydroxyl group, the isomeric hydroxybenzaldehydes
~,~ and the isomeric esters of hydroxybenzoic and mercapto-
' benzoic acids wherein the alcohol residue of the ester
contains from 1 to 12 carbon atoms. If the alcohol contains
a phenyl group, the number of carbon atoms is from 7 to 18.
~ Other substituents that can be present on the phenyl group
;~ ~ ~are disclQsed in the pres,ent s,pecification and claims.
The functionally substituted silanes of this
invention are useful as coupling agents for glass fiber-
reinforced composites, flocculating agents for water
,~ purification and as sizings for glass fibers or fabrics.
'~ The present compounds can be reacted with liquid hydroxy-
or a~koxy-terminated organopolysiloxanes together with
, optlonal fillers to form elastomeric products that are
useful as coating materials, sealants and molding compositions.
~ Compounds erein Kl of the ~regoing formula is amino or
~' ~ ~
11C~9~89
diallcylamino (-NH2 or -NR4) impart detergent resistance to
waxes and polishes.
The following examples disclose preferred
embodiments of the present compounds and should not be
interpreted as limiting the scope of the accompanying
claims. All parts and percentages are by weight unless
otherwise specified.
.
EXAMPLE 1
Preparation of 3(p-aminophenoxy)propyl Trimethoxysilane
A glass reactor was charged with 60 g (0.55 mole)
p-aminophenol, 43.28 g of a 50% aqueous solution of sodium
hydroxide (0.54 mole NaOH), 112 cc dimethylsulfoxide and
120 cc toluene. The resultant mixture was heated to the
boiling point for six hours under a nitrogen atmosphere to
remove all of the water present by azeotropic distillation.
The reaction mixture was then allowed to cool to about 75C,
at which time 109 g (0.55 mole) of 3-chloropropyl trimethoxy-
silane was added dropwise while the reaction mixture was
stirred. The temperature of the reaction mixture increased
~0 spontaneously to 85C during this addition. The temperature
of the reaction mixture was maintained at from 75 to 85C
by heating and control of the addition rate. Following
completion o~ the addition, the reaction mixture was heated
at 115C for 16 hours, following which the mixture was
allowed to cool, and was filtered to remove any solid material.
The solvents weré then removed under a pressure of about 15 mm
of mercury at a temperature of about 60C. The pressure
was then reduced to from 3 to 4 mm of mercury and the
mater~al bo ing from 170 to 180~C was recovsred. Thls
,.~ ' ll~g889
fraction, which weighed 70 g, was distilled using a
fractionating column and a 50 g portion boillng from 175
to 177C under a pressure of 3 mm of mercury,was collected.
The colorle~s liquid was found to contain 10.19% silicon
and 5.20% nitrogen. The calculated values for 3(p-amino-
phenoxy) propyl trimethoxy silane are 10.33% silicon and
5.17% nitrogen. The infrared and nuclear magnetic resonance
spectra o~ the product were in agreement with the proposed
structure.
.~
llOg889
EXAMPLE 2
Preparation of 3(m-aminophenoxy)propyl Trimethoxysilane
Using the general procedure described in the
precedin.g Example 1, ~ ~eactor was charged wit'~ 300 g (2.75 .,.Gle)
m-aminophenol~ 560 cc dimethylsulfoxide, 600 cc toluene
and 216 cc of a 50% aqueous solution of sodium hydroxide
(2.70 moles NaOH). The water present in the reactor was
removed by azeotropic distillation under a nitrogen atmosphere
at a temperature of 120C. The temperature of the reaction
mixture was then lowered to 90C and maintained at about
this value during the gradual addition of 545 g (2.75 mole)
of 3-chloropropyl trimethoxysilane. Following completion of
the addition, which required 2 hours, the reaction mixture
was heated at the boiling point for 16 hours. The product
was recovered and fractionally distilled as described in
the preceding example. The fraction boiling from 178 to
180C at a pressure of 3 mm of mercury was collected and
weighed 630 g (85% yield). The infrared and nuclear magnetic
resonance spectra of the recovered product confirm the
proposed structure
- OCH2CH2CH2Si(OCH3) 3
NH2
A vapor phase chromatogram of the product indicated a purity
of greater than 98%.
110~889
EXAMPLE 3
Preparation of 3(p-formylphenoxy)propyl Trimethoxysilane
Using the general procedure described in the
preceding Example l, a reactor was charged with 62.2 g
(0.55 mole) p-hydroxybenzaldehyde, 112 cc dimethylsulfoxide,
120 cc toluene and 43.2 g of a 50% aqueous sodium hydroxide
solution containing 0.54 mole NaOH. All of the water
present was removed by azeotropic distillation at a temperature
o~ about 110 to 115C. The reaction mixture was heated to,
the boiling point during the gradual addition o~ 109 g
(0.55 mole) of 3-chloropropyl trimethoxysilane. The product,
3(p-formylphenoxy)propyl trimethoxysilane, was isolated by
filtration and removal of the solvents from the recovered
liquid phase under reduced pressure followed,by fractional
distillation of the residue. The fraction boiling at 208C
at a pressure of 3 mm of mercury was collected (85% yield,
based on silane). The infrared and nuclear magnetic
resonance spectra of the recovered product confirm the
~ proposed structuPe
OCH - ~ - OCH 2 CH 2 CH 2 Si ( OCH 3 ) 3
The vapor phase chromatogram of the product indicated a purity
of greater than 98%.
~Y
~ 9889
EXAMPLE 4
Preparation of 3(m-diethylaminophenoxy)propyl Trimethoxysilane
Using the general procedure described in the
l nreceding ~xa~ple 1, a reac~,or was charged with 90.75 g
(0.55 mole) m-diethylaminopllenol, 112 cc dimethylsulfoxide,
120 cc toluene and 43.28 g of a 50% aqueous sodium hydroxide
solution. All of the water present in the reactor was
removed by azeotropic distillation. The reaction mixture
was allowed to cool to 80C, at which time 109 g (0.55 mole)
of chloropropyl trimethoxysilane were gradually added over
a period of 2 hours. The temperature of the reaction mixture
increased to 88C during the addition. Following completion
of the addition, external heating was applied to maintain
the temperature of the reaction mixture at 80C for 16 hours.
The reaction mixture was then allowed to cool and was filtered.
The liquid phase was recovered and evaporated under a
pressure of 5 mm of mercury to remove the toluene and di-
methylsulfoxide. The pressure inside the reactor was reduced
to 2 mm and the product, 3(m-diethylaminophenoxy)propyl
trimethoxysilane, collected at a temperature of 185-187C.
Analysis by vapor phase chromatography demonstrated that the
product was 97% pure.
~' ,l,~q-
'i~988~
EXAMPLE 5
Preparation of 3(3-pyridyloxy)propyl Trimethoxysilane
Using the general procedure described in Example 1,
a reactor was charged with 52.3 g (0.55 mole) 3-hydroxy-
pyridine, 112 cc dimethylsulfoxide, 120 cc toluene and 43.2 g
of a 50% aqueous sodium hydroxide solution. The water
present in the reactor was removed by azeotropic distillation
over a period of 64 hours. The temperature of the reaction
mixture was maintained at from 85 to 105C during this time
period. A 109 g portion of 3-chloropropyl trimethoxysilane
was gradually added while the temperature of the reaction
mixture was maintained at 95C. This temperature was
maintained for 7 hours, at which time a vaporphase chromato-
gram of the reaction mixture indicated that the reaction was
su~stantially complete. The reaction mixture was then
filtered and the diluents (toluene and dimethylsulfoxide)
evaporated under a pressure of 5 mm of mercury. The product,
3(3-pyridyloxy)propyl trimethoxysilane, was collected at
a temperature of 142C under a pressure of 1 mm of mercury.
A vapor phase chromatogram demonstrated that the product
was 97% pure.
