U.S. patent application number 11/503213 was filed with the patent office on 2008-01-17 for selective hydrosilylation method and product.
Invention is credited to David D. Farris, Mark D. Leatherman, Chauncey J. Rinard.
Application Number | 20080015325 11/503213 |
Document ID | / |
Family ID | 38373971 |
Filed Date | 2008-01-17 |
United States Patent
Application |
20080015325 |
Kind Code |
A1 |
Farris; David D. ; et
al. |
January 17, 2008 |
SELECTIVE HYDROSILYLATION METHOD AND PRODUCT
Abstract
An asymmetric siloxane is made by reacting a silicone having the
formula M.sup.HD.sub.xM'.sup.H where M.sup.H is
R.sup.1R.sup.2HSiO.sub.1/2, M.sup.'H is R.sup.4R.sup.5HSiO.sub.1/2
and x is an integer 0.ltoreq.x.ltoreq.10 under selective
hydrosilylation conditions in the presence of a precious metal
hydrosilylation catalyst, with a first olefinic compound and in a
second step, a monohydridosiloxane produced in the first step is
reacted under hydrosilylating conditions with another olefinic
compound different from the first olefinic compound.
Inventors: |
Farris; David D.; (Marietta,
OH) ; Rinard; Chauncey J.; (Newport, OH) ;
Leatherman; Mark D.; (Elmsford, NY) |
Correspondence
Address: |
PHILIP D FREEDMAN PC;PHILIP D FREEDMAN
317 S. FAYETTE STREET
ALEXANDRIA
VA
22314-5902
US
|
Family ID: |
38373971 |
Appl. No.: |
11/503213 |
Filed: |
August 14, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11457446 |
Jul 13, 2006 |
7259220 |
|
|
11503213 |
|
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Current U.S.
Class: |
528/15 ; 528/31;
528/33; 528/34 |
Current CPC
Class: |
C08G 77/38 20130101;
C08G 77/46 20130101; Y10S 424/10 20130101 |
Class at
Publication: |
528/15 ; 528/31;
528/33; 528/34 |
International
Class: |
C08G 77/08 20060101
C08G077/08; C08G 77/06 20060101 C08G077/06; C08L 83/04 20060101
C08L083/04 |
Claims
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48. A method to make an asymmetrically substituted organosiloxane
containing at least one polyalkylene oxide group comprising, (a) in
a first step, reacting a dihydridosiloxane having the chemical
Formula (1), M.sup.HD.sub.xM'.sup.H (1) in the presence of a
precious metal catalysts independently selected from the group
consisting of rhodium, ruthenium, palladium, osmium, iridium and
platinum under selective hydrosilylation conditions with an
unsaturated hydrocarbon containing from about 2 to about 100 carbon
atoms, and one or more terminal carbon to carbon double bonds or
with an unsaturated heterocarbon containing from about 3 to about
100 carbon atoms, one or more terminal carbon to carbon double
bonds and at least one oxygen or at least one silicon atom that has
replaced a carbon atom to form a monohydridosiloxane wherein: each
occurrence of M.sup.H is independently selected from the species
R.sup.1R.sup.2HSiO.sub.1/2; each occurrence of M'.sup.H is
independently selected from the species R.sup.4R.sup.5HSiO.sub.1/2;
each occurrence of D is independently selected from the species
(R).sub.2SiO; each occurrence of the subscript x is independently
an integer from about 0 to about 10; each occurrence of R, R.sup.1,
R.sup.2, R.sup.4 and R.sup.5 is independently selected from the
group consisting of a hydrocarbon of from 1 to about 50 carbon
atoms and a heterocarbon of from about 1 to 100 carbon atoms
containing at least one oxygen or at least one silicon atom that
has replaced a carbon atom; and (b) in a second step,
hydrosilylating the monohydridosiloxane with a different
unsaturated hydrocarbon containing from about 2 to about 100 carbon
atoms and one or more terminal carbon to carbon double bonds or
with a different unsaturated heterocarbon containing from about 3
to about 100 carbon atoms, one or more terminal carbon to carbon
double bonds and at least one oxygen or at least one silicon atom
that has replaced a carbon atom in the presence of the same or
different precious metal hydrosilylation catalyst to form an
asymmetric siloxane and with the proviso that at least one
heterocarbon containing one or more terminal carbon to carbon
double bond is a polyalkylene oxide compound with one or more
terminal carbon to carbon double bonds.
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82. A method to make an asymmetric organosiloxane comprising in a
first step, reacting a molar excess up to less than 4:1 of a
dihydridosiloxane under hydrosilylation conditions in the presence
of a rhodium hydrosilylation catalyst, with an hydrocarbon or
heterocarbon compound containing a terminal carbon to carbon double
bond to form a monohydridosiloxane, and in a second step,
hydrosilylating the monohydridosiloxane with a second and different
hydrocarbon or heterocarbon compound containing a terminal carbon
to carbon double bond and in the presence of the same or different
hydrosilylation catalyst under hydrosilylation conditions to form
an asymmetrically substituted organosiloxane, wherein the
asymmetric organosiloxane product contains at least one
polyalkylene oxide group.
83. The method of claim 82, wherein the alkylene oxide is a methyl
capped allylpolyethyleneglycol.
84. The method of claim 82, wherein the alkylene oxide comprises a
polyether defined by the general formula:
CH.sub.2.dbd.CH(R.sup.13)(R.sup.12).sub.dO(C.sub.2H.sub.4O).sub.a(C.sub.3-
H.sub.6O).sub.b(C.sub.4H.sub.8O).sub.cR.sup.16 where R.sup.13 is H
or methyl; R.sup.12 is a divalent alkyl radical of 1 to 6 carbons
where the subscript d may be 0 or 1; and R.sup.16 is H, a
monofunctional hydrocarbon radical of 1 to 6 carbons, or
acetyl.
85. The method of claim 82, wherein the alkylene oxide comprises a
polyether comprising a random or blocked configuration selected
from the group consisting of
-(oxyethylene).sub.a(oxypropylene).sub.b-,
-(oxybutylene).sub.c(oxyethylene).sub.a- and
-(oxypropylene).sub.b(oxyethylene).sub.a(oxybutylene).sub.c-.
86. The method of claim 82, wherein the alkylene oxide comprises a
polyether comprising a member selected from the group consisting of
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.8H;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.8CH.sub.3;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.4(CH.sub.2CH(CH.sub.3)O).-
sub.5H;
CH.sub.2.dbd.CHO(CH.sub.2CH.sub.2O).sub.5(CH.sub.2CH(CH.sub.3)O).s-
ub.5H;
CH.sub.2.dbd.C(CH.sub.3)CH.sub.2O(CH.sub.2CH.sub.2O).sub.4(CH.sub.2-
CH(CH.sub.3)O).sub.5C(.dbd.O)CH.sub.3; and
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.5(CH.sub.2CH(CH.sub.3)O).-
sub.2(CH.sub.2CH(CH.sub.2CH.sub.3)O).sub.2H.
87. (canceled)
88. The method of claim 82, comprising reacting the
dihydridosiloxane with a vinylsilane selected from the group
consisting of trimethylvinylsilane, triethylvinylsilane,
dimethyl-tert-butoxyvinylsilane, dimethylisopropoxyvinylsilane,
tris-(trimethylsiloxy)vinylsilane,
methyl-bis-(tert-butoxy)vinylsilane and
tris-(tert-butoxy)vinylsilane.
89. The method of claim 82, wherein the rhodium catalyst is a
complex of Rh(III) or Rh(I).
90. The method of claim 82, wherein the rhodium catalyst is
trichlorotris (dibutyl sulfide) rhodium (III).
91. (canceled)
92. The method of claim 82, the rhodium catalyst is
tris(triphenylphosphine) rhodium chloride.
93. The method of claim 82, comprising isolating the
monohydridosiloxane reaction product of the first step.
94. The method of claim 82, comprising reacting a molar excess of
dihydridosiloxane to vinyl silane of 1.3:1 to greater than 1:1.
95. The method of claim 48, wherein at least one of R.sup.1,
R.sup.2, R.sup.4 and R.sup.5 is independently a same or different
C.sub.1 to C.sub.12 alkyl radical selected from the group
consisting of methyl, ethyl, propyl, butyl, isopentyl, n-hexyl and
decyl.
96. The method of claim 48, wherein the polyalkylene oxide is a
polyether defined by the general formula:
CH.sub.2.dbd.CH(R.sup.13)(R.sup.12).sub.dO(C.sub.2H.sub.4O).sub.a(C.sub.3-
H.sub.6O).sub.b(C.sub.4H.sub.8O).sub.cR.sup.16 where R.sup.13 is H
or methyl; R.sup.12 is a divalent alkyl radial of 1 to 6 carbons
where the subscript d may be 0 or 1; and R.sup.16 is H, a
monofunctional hydrocarbon radical of 1 to 6 carbons, or
acetyl.
97. The method of claim 48, wherein the polyalkylene oxide is a
polyether comprising a random or blocked configuration selected
from the group consisting of
-(oxyethylene).sub.a(oxypropylene).sub.b-,
-(oxybutylene).sub.c(oxyethylene).sub.a- and
-(oxypropylene).sub.b(oxyethylene).sub.a(oxybutylene).sub.c-.
98. The method of claim 48, wherein the wherein the polyalkylene
oxide is a polyether comprising a member selected from the group
consisting of CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.8H;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.8CH.sub.3;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.4(CH.sub.2CH(CH.sub.3)O).-
sub.5H;
CH.sub.2.dbd.CHO(CH.sub.2CH.sub.2O).sub.5(CH.sub.2CH(CH.sub.3)O).s-
ub.5H;
CH.sub.2.dbd.C(CH.sub.3)CH.sub.2O(CH.sub.2CH.sub.2O).sub.4(CH.sub.2-
CH(CH.sub.3)O).sub.5C(.dbd.O)CH.sub.3;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.5(CH.sub.2CH(CH.sub.3)O).-
sub.2(CH.sub.2CH(CH.sub.2CH.sub.3)O).sub.2H.
99. The method of claim 48, wherein x=0 (MM').
100. The method of claim 82, comprising isolating the
monohydridsiloxane of the first step and then conducting the second
step on the isolated monohydridsiloxane.
Description
BACKGROUND OF THE INVENTION
[0001] The invention relates to a selective process for
hydrosilylation of dihydridosiloxanes in the manufacture of
asymmetric organosiloxanes containing at least one polyalkylene
oxide group. More specifically, the invention relates to a method
to make an asymmetric siloxane containing at least one polyalkylene
oxide group and novel composition.
[0002] Organosiloxanes containing polyalkylene oxide groups may be
used as dispersants, wetting agents, spreading agents and
emulsifiers in agricultural chemical formulations and in other
wetting, spreading, foaming and detergent applications.
Formulations containing organosiloxanes are commonly used in
forestry, agriculture, and horticulture as agricultural adjuvants
to improve efficacy of agrochemical active ingredients such as
micronutrients, growth regulators, biologicals, pesticides such as
herbicides, fungicides, insecticides, acaracides and miticides.
[0003] Organosiloxanes may be formed from a reaction of a
hydridosiloxane with an olefin such as an aliphatic olefin or
olefin-terminated polyalkylene oxide such as allyl-, vinyl- and
methallyl-terminated polyalkylene oxides. Likewise, olefins such as
allyl chloride or 1-octene may be reacted with a hydridosilane such
as trimethoxysilane in the presence of an appropriate precious
metal catalyst. These precious metal catalysts include complexes of
rhodium, ruthenium, palladium, osmium, iridium or platinum.
[0004] Many of these known organosiloxanes may only be used in
aqueous formulations within a narrow pH range, ranging from a
slightly acidic pH of 6 to a very mildly basic pH of 7.5. Outside
this narrow pH range, these known organosiloxanes may not be stable
to hydrolysis undergoing rapid decomposition. Recently, asymmetric
organosiloxanes that contain at least one polyalkylene oxide group
have been disclosed that provide stable performance in aqueous
formulations that are outside of this narrow pH range. However,
these asymmetric organosiloxanes are difficult to manufacture
because the processes are not selective. These processes generate
mixtures of components that have undesirable characteristics, such
as a decrease in the wetting and spreading properties of the
organosiloxanes. Therefore, a need exists for an efficient,
selective and cost effective process to make these asymmetric
organosiloxanes.
BRIEF DESCRIPTION OF THE INVENTION
[0005] The invention relates to an efficient and cost effective
process to make asymmetric organosiloxanes that contain at least
one polyalkylene oxide group.
[0006] The invention can be described as a method to make an
asymmetric organosiloxane comprising in a first step, reacting a
dihydridosiloxane under hydrosilylation conditions in the presence
of a precious metal hydrosilylation catalyst, with an hydrocarbon
or heterocarbon compound containing a terminal carbon to carbon
double bond to form a monohydridosiloxane, and in a second step,
hydrosilylating the monohydridosiloxane with a second and different
hydrocarbon or heterocarbon compound containing a terminal carbon
to carbon double bond and in the presence of the same or different
hydrosilylation catalyst under hydrosilylation conditions to form
an asymmetrically substituted organosiloxane, wherein the
asymmetric organosiloxane product contains at least one
polyalkylene oxide group.
[0007] In an embodiment, the invention is a method to form a
monohydridosiloxane, comprising effecting a hydrosilylation of a
molar excess of greater than 1:1 up to less than 4:1 of
dihydridosiloxane of the formula M.sup.HD.sub.xM'.sup.H where
M.sup.H is R.sup.1R.sup.2HSiO.sub.1/2, M'.sup.H is
R.sup.4R.sup.5HSiO.sub.1/2 and x is an integer such that
0.ltoreq.x.ltoreq.10 bond, in the presence of a rhodium
hydrosilylation catalyst with a compound having an aliphatic
unsaturated double bond; where each of R.sup.1, R.sup.2, R.sup.4
and R.sup.5 is independently the same or different and each is a
hydrocarbon radical, an alkoxy radical or alkenyloxy radical; and
recovering a monohydridosiloxane.
[0008] In another embodiment, the invention is a method to make an
asymmetric siloxane, comprising: in a first step, reacting a
silicone having the formula M.sup.HD.sub.xM'.sup.H where M.sup.H is
R.sup.1R.sup.2HSiO.sub.1/2, M'.sup.H is R.sup.4R.sup.5HSiO.sub.1/2
and x is an integer 0.ltoreq.x.ltoreq.10 under selective
hydrosilylation conditions in the presence of a rhodium catalyst,
with an olefinic compound containing one or more terminal carbon to
carbon double bonds to form a monohydridosiloxane; where each of
R.sup.1, R.sup.2, R.sup.4 and R.sup.5 is independently the same or
different and each is a hydrocarbon radical, an alkoxy radical or
alkenyloxy radical; and in a second step, hydrosilylating the
monohydridosiloxane with an polyalkylene oxide of 2 to 10 carbon
atoms and different from the first olefinic compound and having one
or more alkylene oxide groups containing one or more terminal
carbon to carbon double bonds to form an asymmetric siloxane. In
another embodiment, the invention is a method to form an asymmetric
siloxane, comprising: effecting a monoselective hydrosilylation
reaction between a molar excess of a dihydridosiloxane and a first
aliphatic unsaturated compound in the presence of a rhodium
hydrosilylation catalyst to form a monohydridosiloxane; and
hydrosilylating the monohydridosiloxane with alkylene oxide
compound containing one or more terminal carbon to carbon double
bonds to form an asymmetric siloxane.
[0009] In still another embodiment, the invention is a method to
form an asymmetric siloxane; comprising adding a molar excess of
less than 4:1 of a dihydridosiloxane to an aliphatic unsaturated
compound in the presence of a precious metal hydrosilylation
catalyst and adding an alkylene oxide containing one or more
terminal carbon to carbon double bonds to complete hydrosilylation
to form an asymmetrically substituted siloxane.
[0010] In still another embodiment, the invention is a method to
make an asymmetrically substituted organosiloxane containing at
least one polyalkylene oxide group comprising, (a) in a first step,
reacting a dihydridosiloxane having the chemical formula
M.sup.HD.sub.xM'.sup.H
in the presence of a precious metal catalysts independently
selected from the group consisting of rhodium, ruthenium,
palladium, osmium, iridium and platinum under selective
hydrosilylation conditions with an unsaturated hydrocarbon
containing from about 2 to about 100 carbon atoms, and one or more
terminal carbon to carbon double bonds or with an unsaturated
heterocarbon containing from about 3 to about 100 carbon atoms, one
or more terminal carbon to carbon double bonds and at least one
oxygen or at least one silicon atom that has replaced a carbon atom
to form a monohydridosiloxane wherein: each occurrence of M.sup.H
is independently selected from the species
R.sup.1R.sup.2HSiO.sub.1/2; each occurrence of M'.sup.H is
independently selected from the species R.sup.4R.sup.5HSiO.sub.1/2;
each occurrence of D is independently selected from the species
(R).sub.2SiO; each occurrence of the subscript x is independently
an integer from about 0 to about 10; each occurrence of R, R.sup.1,
R.sup.2, R.sup.4 and R.sup.5 is independently selected from the
group consisting of a hydrocarbon of from 1 to about 50 carbon
atoms and a heterocarbon of from about 1 to 100 carbon atoms
containing at least one oxygen or at least one silicon atom that
has replaced a carbon atom; and (b) in a second step,
hydrosilylating the monohydridosiloxane with a different
unsaturated hydrocarbon containing from about 2 to about 100 carbon
atoms and one or more terminal carbon to carbon double bonds or
with a different unsaturated heterocarbon containing from about 3
to about 100 carbon atoms, one or more terminal carbon to carbon
double bonds and at least one oxygen or at least one silicon atom
that has replaced a carbon atom in the presence of the same or
different precious metal hydrosilylation catalyst to form an
asymmetric siloxane and with the proviso that at least one
heterocarbon containing one or more terminal carbon to carbon
double bond is a polyalkylene oxide compound with one or more
terminal carbon to carbon double bonds.
[0011] In another embodiment, the invention is an asymmetric
siloxane, comprising: MD.sub.xM' where
M=R.sup.1R.sup.2R.sup.3SiO.sub.1/2 and M'=R.sup.4R.sup.5R.sup.6
SiO.sub.1/2; wherein D=(R).sub.2SiO, and x is an integer
0.ltoreq.x.ltoreq.10; each of R, R.sup.1, R.sup.2, R.sup.4 and
R.sup.5 is independently the same or different and each is a
hydrocarbon radical, an alkoxy radical or alkenyloxy radical and
each of R.sup.3 and R.sup.6 is independently a different alkylene
oxide moiety of 2 to 10 carbon atoms.
[0012] In another embodiment, the invention is an asymmetric
siloxane, comprising: the chemical of the formula MD.sub.xM'
wherein each occurrence of M is independently
R.sup.1R.sup.2R.sup.3SiO.sub.1/2; each occurrence of M' is
R.sup.4R.sup.5R.sup.6 SiO.sub.1/2; each occurrence of D is
independently (R).sub.2SiO; each occurrence of the subscript x is
independently an integer from about 0 to about 10; each occurrence
of R.sup.1, R.sup.2, R.sup.4 and R.sup.5 is independently selected
from the group consisting of the same or different monovalent
hydrocarbon radical of from 3 to 6 carbon atoms and the
R.sup.8R.sup.9R.sup.10SiR.sup.12 radical wherein each occurrence
R.sup.8, R.sup.9 and R.sup.10 is independently a monovalent
hydrocarbon radical having from 1 to 6 carbon atoms, a monovalent
aryl hydrocarbon radical having from 6 to 13 carbon atoms or a
monovalent alkaryl hydrocarbon radical having from 6 to 13 carbon
atoms and R.sup.12 is a divalent hydrocarbon radical having from 1
to 3 carbon atoms; and each occurrence of R.sup.3 and R.sup.6 is
independent a different polyalkylene oxide moiety of 3 to 10 carbon
atoms.
[0013] In another embodiment, the invention is an asymmetric
siloxane comprising
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane.
[0014] In another embodiment, the invention is pesticidal
composition, comprising at least one active pesticide and an
asymmetric siloxane.
[0015] In still another embodiment, the invention is fungicide
composition, comprising at least one active fungicide and an
asymmetric siloxane.
[0016] In still another embodiment, the invention is an
agricultural or horticultural formulation, comprising a herbicide
and an asymmetric siloxane adjuvant.
[0017] In still another embodiment, the invention is an
agricultural or horticultural formulation, comprising a pesticide
and an asymmetric siloxane adjuvant.
[0018] In still another embodiment, the invention is a coating
composition, comprising an active coating component and an
asymmetric siloxane wetting agent or surfactant.
[0019] And, in still another embodiment, the invention is a
personal care emulsion, comprising an aqueous discontinuous phase
and a continuous phase comprising an asymmetric siloxane.
[0020] And, in another embodiment, the invention is a personal care
emulsion, comprising a continuous non-aqueous hydroxylic solvent
phase and a discontinuous phase comprising an asymmetric
siloxane.
[0021] In still another embodiment, the invention is a home care
composition comprising an active cleaning, softening or polishing
component and an asymmetric siloxane.
[0022] In another embodiment, the invention is a surfactant
composition, comprising an asymmetric siloxane and an active
co-surfactant.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The invention relates to an efficient and cost effective
process to make asymmetric organosiloxanes that contains at least
one polyalkylene oxide group comprising in a first step, reacting a
dihydridosiloxane under hydrosilylation conditions in the presence
of a precious metal hydrosilylation catalysts, with an hydrocarbon
or heterocarbon compound containing a terminal carbon to carbon
double bond to form a monohydridosiloxane, and in a second step,
hydrosilylating the monohydridosiloxane with a second and different
hydrocarbon or heterocarbon compound containing a terminal carbon
to carbon double bond and in the presence of the same or different
hydrosilylation catalyst under hydrosilylation conditions to form
an asymmetrically substituted organosiloxane.
[0024] In another embodiment, the invention is a method to form a
monohydridosiloxane, comprising effecting a hydrosilylation of a
molar excess of greater than 1:1 up to less than 4:1 of
dihydridosiloxane having the chemical Formula (1):
M.sup.HD.sub.xM'.sup.H (1)
wherein M.sup.H, M'.sup.H, D and x are defined above, in the
presence of a rhodium hydrosilylation catalyst with an unsaturated
hydrocarbon containing from about 2 to about 100 carbon atoms, one
or more terminal carbon to carbon double bonds or with an
unsaturated heteroatom containing from about 3 to about 100 carbon
atoms, at least one oxygen atom or at least one silicon atom and
one or more terminal carbon to carbon double bonds to give a
monohydridosiloxane and recovering the monohydridosiloxane.
[0025] In another embodiment, the invention is a method to make an
asymmetric siloxane containing at least one polyalkylene oxide
group, comprising in a first step, reacting a dihydridosiloxane
having the chemical Formula (1):
M.sup.HD.sub.xM'.sup.H (1)
wherein M.sup.H, M'.sup.H, D and x are defined above and each
occurrence of R, R.sup.1, R.sup.2, R.sup.4 and R.sup.5 is
independently the same or different and each is a hydrocarbon
radical, an alkoxy radical or alkenyloxy radical containing from
about 1 to 50 carbon atoms, in the presence of a precious metal
catalyst, and more specifically a rhodium catalyst, under selective
hydrosilylation conditions, with an unsaturated hydrocarbon
containing from about 2 to about 50 carbon atoms and one or more
terminal carbon to carbon double bonds or with an unsaturated
heterocarbon containing from about 3 to 50 carbon atoms, at least
one silicon or oxygen atom, and one or more terminal carbon to
carbon double bonds to form a monohydridosiloxane; and in a second
step, hydrosilylating the monohydridosiloxane with an unsaturated
heterocarbon containing from about 2 to about 50 carbon atoms, at
least one oxygen atom and one or more terminal carbon to carbon
double bonds, and more specifically, an unsaturated polyalkylene
oxide containing from about 4 to about 50 carbon atoms and one or
more terminal carbon to carbon double bond and different from the
first unsaturated hydrocarbon or heterocarbon in the presence of
the same or different precious metal hydrosilylation catalyst to
form an asymmetric siloxane.
[0026] In an other embodiment, the present invention is a method to
form an asymmetric siloxane, comprising effecting a selective
hydrosilylation reaction between a dihydridosiloxane and a first
aliphatic unsaturated hydrocarbon containing one or more terminal
carbon to carbon double bonds in the presence of a precious metal
catalyst, and more specifically, a rhodium hydrosilylation
catalyst, to form a monohydridosiloxane; and, in a second step,
hydrosilylating the monohydridosiloxane with another different
aliphatic unsaturated hydrocarbon containing one or more terminal
carbon to carbon double bonds to form an asymmetric siloxane.
[0027] In another embodiment, the present invention is a method to
form an asymmetric siloxane containing at least one carbon to
carbon double bonds comprising adding a molar excess of less than
4:1 of a dihydridosiloxane to an aliphatic unsaturated hydrocarbon
containing one or more terminal carbon to carbon double bonds in
the presence of a precious metal hydrosilylation catalyst and, in a
second step, adding a alkylene oxide containing a terminal carbon
to carbon double bond to complete hydrosilylation and to form an
asymmetrically substituted siloxane.
[0028] In yet another embodiment, the invention is an asymmetric
siloxane comprising the chemical Formula (5):
MD.sub.xM' (5)
wherein M is R.sup.1R.sup.2R.sup.3SiO.sub.1/2; M' is
R.sup.4R.sup.5R.sup.6 SiO.sub.1/2; D is (R).sub.2SiO; x is
independently an integer from about 0 to about 10; each occurrence
of R, R.sup.1, R.sup.2, R.sup.4 and R.sup.5 is independently the
same or different and defined above; and each occurrence of R.sup.3
and R.sup.6 is independently a heterocarbon radical containing from
about 3 to about 10 carbon atoms, and at least one oxygen atom and
with the proviso that R.sup.3 is different from R.sup.6, and more
specifically an polyalkylene oxide moiety of 3 to 10 carbon
atoms.
[0029] In another embodiment, the invention is an asymmetric
organosiloxane comprising
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane.
[0030] Important organosiloxanes are made by one or more of the
methods described in copending and commonly assigned patent
applications Rajaraman et al. U.S. patent application Ser. No.
11/300100, filed 13 Dec. 2005, (Attorney Docket Number 199812),
U.S. patent application Ser. No. 11/350426, field 9 Feb. 2006
(Attorney Docket Number 202973) and U.S. patent Ser. No. 11/379592,
filed 21 Apr. 2006 (Attorney Docket Number 203252).
[0031] Rajaraman et al. U.S. patent application Ser. No. 11/300100,
field 13 Dec. 2005 teaches a disiloxane surfactant compositions
comprising a silicone composition comprising a silicone having the
formula, MM', wherein M is R.sup.1R.sup.2R.sup.3SiO.sub.1/2 and M'
is R.sup.4R.sup.5R.sup.6SiO.sub.1/2 with R.sup.3 selected from the
group consisting of branched monovalent hydrocarbon radical of from
3 to 6 carbon atoms and R.sup.8R.sup.9R.sup.10SiR.sup.12 radical
wherein each occurrence of R.sup.8, R.sup.9, and R.sup.10 is
independently selected from the group of monovalent hydrocarbon
radicals having from 1 to 6 carbon atoms and monovalent aryl or
aralkyl hydrocarbon radicals having from 6 to 13 carbon atoms and
R.sup.12 is a divalent hydrocarbon radical having from 1 to 3
carbon atoms, R.sup.1 and R.sup.2 are each independently selected
from the group of from 1 to 6 carbon atom monovalent hydrocarbon
radicals or R.sup.3, R.sup.6 is an polyalkylene oxide of the
general Formula (6):
R.sup.18(C.sub.2H.sub.4O).sub.a(C.sub.3H.sub.6O).sub.b(C.sub.4H.sub.8O).-
sub.cR.sup.16 (6)
R.sup.18 is a divalent linear or branched hydrocarbon radical
having the structure --CH.sub.2--CH(R.sup.13)(R.sup.12).sub.dO--
where R.sup.13 is hydrogen or methyl; R.sup.16 is a divalent alkyl
radical of 1 to 6 carbons where the subscript d may be 0 or 1;
R.sup.16 is selected from the group consisting of hydrogen,
monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and
acetyl where the subscripts a, b and c are zero or positive and
satisfy the following relationships 2.ltoreq.a+b+c.ltoreq.20 with
a.gtoreq.2, and R.sup.4 and R.sup.5 are each independently selected
from the group of monovalent hydrocarbon radicals having from 1 to
6 carbon atoms or R.sup.6.
[0032] U.S. patent application Ser. No. 11/300100 teaches a
composition comprising a siloxane having the formula, MM', wherein
M is R.sup.1R.sup.2R.sup.3SiO.sub.1/2 and M' is
R.sup.4R.sup.5R.sup.6SiO.sub.1/2; with R.sup.3 selected from the
group consisting of a branched monovalent hydrocarbon radical of
from 3 to 6 carbon atoms and R.sup.8R.sup.9R.sup.10SiR.sup.12 with
R.sup.8, R.sup.9, and R.sup.10 each independently selected from the
group of monovalent hydrocarbon radicals having from 1 to 6 carbon
atoms and monovalent aryl and aralkyl hydrocarbon radicals having
from 6 to 13 carbon atoms and R.sup.12 is a divalent hydrocarbon
radical having from 1 to 3 carbon atoms, R.sup.1 and R.sup.2 are
each independently selected from the group of from 1 to 6 carbon
atom monovalent hydrocarbon radicals or R.sup.3, R.sup.6 is a
polyalkylene oxide of the general Formula (7):
R.sup.18(C.sub.2H.sub.4O).sub.a(C.sub.3H.sub.6O).sub.b(C.sub.4H.sub.8O).-
sub.cR.sup.16 (7)
wherein each occurrence of R.sup.18 is a divalent linear or
branched hydrocarbon radical having the structure,
--CH.sub.2--CH(R.sup.13)(R.sup.12).sub.dO--, wherein R.sup.13 is
hydrogen or methyl; R.sup.12 is a divalent alkyl radical of 1 to 6
carbons where the subscript d may be 0 or 1; R.sup.16 is selected
from the group consisting of hydrogen, monovalent hydrocarbon
radicals of from 1 to 6 carbon atoms and acetyl where the
subscripts a, b and c are zero or positive and satisfy the
following relationships: 2.ltoreq.a+b+c.ltoreq.20 with a.gtoreq.2,
and R.sup.4 and R.sup.5 are each independently selected from the
group of monovalent hydrocarbon radicals having from 1 to 6 carbon
atoms or R.sup.6.
[0033] U.S. patent application Ser. No. 11/350426 teaches a
trisilicone composition comprising a silicone having the formula,
MD.sup.1M', wherein M is (R.sup.1)(R.sup.2)(R.sup.3)SiO.sub.1/2; M'
is (R.sup.4)(R.sup.5)(R.sup.6)SiO.sub.1/2; and D.sup.1 is
(R)(Z)SiO.sub.2/2 where R.sup.3 is selected from the group of
monovalent hydrocarbon radicals consisting of branched or linear
hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl
hydrocarbon group of 4 to 9 carbons containing aryl constituents of
6 to 20 carbon atoms; R, R.sup.1, R.sup.2, R.sup.4, R.sup.5, and
R.sup.6 are each independently selected from the group consisting
of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a
hydrocarbon group of 4 to 9 carbons containing an aryl group; Z is
an alkylene oxide group of the general Formula (8):
R.sup.19(C.sub.2H.sub.4O).sub.a(C.sub.3H.sub.6O).sub.b(C.sub.4H.sub.8O).-
sub.cR.sup.16 (8)
wherein R.sup.19 is a linear or branched divalent hydrocarbon
radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R.sup.16 is
selected from the group consisting of hydrogen, monovalent
hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and
the subscripts a, b and c are zero or positive and satisfy the
following relationships: 2.ltoreq.a+b+c.ltoreq.20 with
a.gtoreq.2.
[0034] U.S. patent application Ser. No. 11/379592 teaches a
composition comprising a silicon containing compound having the
Formula (9):
(R.sup.1)(R.sup.2)(R.sup.3)Si--R.sup.12--Si(R.sup.4)(R.sup.5)(R.sup.6)
(9)
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each
independently selected from the group consisting of 1 to 6
monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 7
to 10 carbons containing an aryl group; R.sup.12 is a hydrocarbon
group of 1 to 3 carbons; R.sup.6 is an alkylene oxide group of the
general Formula (7):
R.sup.18(C.sub.2H.sub.4O).sub.a(C.sub.3H.sub.6O).sub.b(C.sub.4H.sub.8O).-
sub.cR.sup.16 (7)
where R.sup.18 is a divalent linear or branched hydrocarbon radical
having the structure --CH.sub.2--CH(R.sup.13)(R.sup.12).sub.dO--
where R.sup.13 is hydrogen or methyl; R.sup.12 is a divalent alkyl
radical of 1 to 6 carbons where the subscript d may be 0 or 1;
R.sup.16 is selected from the group consisting of hydrogen,
monovalent hydrocarbon radicals of 1 to 6 carbon atoms and acetyl,
subject to the limitation that the subscripts a, b and c are zero
or positive and satisfy the following relationships:
2.ltoreq.a+b+c.ltoreq.20 with a.gtoreq.2.
[0035] In an embodiment of the present invention,
M.sup.HD.sub.xM'.sup.H is reacted under hydrosilylation conditions,
with a reactant containing one or more carbon-to-carbon double
bonds, such as a hydrocarbon or heterocarbon compound containing a
terminal carbon to carbon double bond or an olefinically modified
polyalkylene oxide. In M.sup.HD.sub.xM'.sup.H, M.sup.H and M'.sup.H
are the same or different hydride precursors to an M structural
unit where M is R.sup.1R.sup.2R.sup.3SiO.sub.1/2 and M' is
R.sup.4R.sup.5R.sup.6SiO.sub.1/2.
[0036] In an embodiment of the invention, a dihydridosiloxane of
the formula M.sup.HD.sub.xM'.sup.H is reacted in a first step
hydrosilylation reaction with a first polyalkylene oxide having one
or more alkylene oxide groups containing one or more terminal
carbon to carbon double bonds to form a monohydridosiloxane. Then,
the monohydridosiloxane from the first step is hydrosilylated with
another polyalkylene oxide different from the first polyalkylene
oxide and having one or more alkylene oxide groups containing one
or more terminal carbon-to-carbon double bonds to form an
asymmetric siloxane. In this embodiment, D is (R).sub.2SiO and x an
integer ranging from about 0 to about 10. In a specific embodiment,
x=0 and the dihydridosiloxane is M.sup.HM'.sup.H. In (R).sub.2SiO,
each R group is independently the same or different and each
represents a hydrocarbon radical or an alkoxy or polyalkenyloxy
radical.
[0037] A second step of an embodiment of the inventive process
comprises hydrosilylating the monohydridosiloxane formed in the
first step with another polyalkylene oxide different from the first
polyalkylene oxide and having one or more alkylene oxide groups
containing one or more terminal carbon to carbon double bonds to
form an asymmetric siloxane.
Dihydridosiloxane
[0038] A "dihydridosiloxane" as used herein is a compound that
contains two or more silicon-hydrogen bonds and one or more
silicon-oxygen bonds. The term is intended to include oligomeric,
cyclomeric, polymeric and copolymeric hydridosiloxanes. The term
"hydrosilylation" refers to the addition of Si--H bonds to
carbon-to-carbon double bonds like C.dbd.C. The term "selective
hydrosilylation conditions" means conditions that result in
selective hydrosilylation substantially at a single hydride
position of a dihydride starting material. The conditions may be
combinations of reactant molar ratios and catalyst.
[0039] The dihydridosiloxane starting material of the invention
process is typically a fluid with a hydrogen content of from about
25 cc/gm to about 334 cc/gm and more specifically from about 150
cc/gm to about 334 cc/gm. The dihydridosiloxane may run a range of
reactants from a monomer reactant, such as
1,1,3,3-tetramethyldisiloxane (M.sup.HM'.sup.H) to a polymer
equilibrate fluid reactant having a structure of
M.sup.HD.sub.xM'.sup.H, wherein M.sup.H is
R.sup.1R.sup.2HSiO.sub.1/2, M'.sup.H is the same or different
R.sup.4R.sup.5HSiO.sub.1/2 and D=(R).sub.2SiO where R, R.sup.1,
R.sup.2, R.sup.4 and R.sup.5 are defined above and x is an integer
such that the structures include materials of the range from about
0 to about 10, more specially from about 0 to about 2, and most
specifically, about 0. The formula given here and elsewhere herein,
such as M.sup.HD.sub.xM'.sup.H, are to be understood as
representing average compositions of statistical polymers, unless
otherwise noted.
[0040] Representative examples of suitable R, R.sup.1, R.sup.2,
R.sup.4 and R.sup.5 radicals are C.sub.1 to C.sub.12 alkyl
radicals, such as the non-limiting examples of methyl, ethyl,
propyl, butyl, isopentyl, n-hexyl, and decyl; cycloaliphatic
radicals containing 5 to 12 carbon atoms, such as the non-limiting
examples of cyclopentyl, cyclohexyl, methylcyclohexyl, norbornyl,
and cyclooctyl; aralkyl radicals, such as the non-limiting examples
of phenylethyl benzyl and 2-phenyl-1-methylethyl; and aryl
radicals, such as the non-limiting examples of phenyl and napthyl;
optionally substituted with 1 to 6 alkyl groups of up to 6 carbon
atoms, such as the non-limiting examples of tolyl and xylyl; alkoxy
radicals containing form about 1 to about 12 carbon atoms, such as
methoxy, ethoxy, propoxy, butoxy, and decyloxy and more
specifically alkoxy radical containing from about 3 to about 6
carbon atoms, such as the non-limiting examples of isopropyl,
isobutyl, neopentyl, isopentyl and neohexyl. Illustrative examples
of R also include polyalkyleneoxy radicals, such as the
non-limiting examples of
CH.sub.3O(CH.sub.2CH.sub.2O).sub.a(CH.sub.2CH(CH.sub.3)O).sub.b--CH.sub.2-
CH.sub.2CH.sub.2--,
CH.sub.3C(.dbd.O)O(CH.sub.2CH.sub.2O).sub.a(CH.sub.2CH(CH.sub.3)O).sub.b--
-CH.sub.2CH.sub.2CH.sub.2-- and
CH.sub.3CH.sub.2CH.sub.2CH.sub.2O(CH.sub.2CH.sub.2O).sub.a(CH.sub.2CH(CH.-
sub.3)O).sub.b--CH.sub.2CH.sub.2CH.sub.2--, in which the subscripts
a and b may vary from 0 to about 200 and a+b>0. A specific
example of R, R.sup.1, R.sup.2, R.sup.4 or R.sup.5 radical is
methyl.
Olefinic Reactant
[0041] The hydrocarbon or heterocarbon reactants containing one or
more terminal carbon to carbon double bonds employed in the
practice of the present invention may be any that react with a
hydridosilane or hydridosiloxane in the desired reaction. As
employed herein, the term "hydrocarbon" means any organic compound
that contains carbon and hydrogen atoms and includes unsaturated
hydrocarbons, that has an ethylenic or acetylenic unsaturation
capable of being hydrosilylated, including acetylene, allyl, and
vinyl starting materials. As employed herein, the term
"heterocarbon" means any hydrocarbon in which one or more carbon
atoms are replaced with an oxygen atom or a silicon atom.
[0042] In an embodiment of the present invention, a specific
heterocarbon containing one or more terminal carbon to carbon
double bonds for use in the practice of the first step of the
present invention is a vinylsilane, such as the non-limiting
examples trimethylvinylsilane, triethylvinylsilane,
dimethyl-tert-butoxyvinylsilane, dimethylisopropoxyvinylsilane,
tris-(trimethylsiloxy)vinylsilane,
methyl-bis-(tert-butoxy)vinylsilane and
tris-(tert-butoxy)vinylsilane, while a specific heterocarbon
containing one or more terminal carbon to carbon double bonds in
the second step is a terminally unsaturated polyalkylene oxide.
[0043] In still another embodiment, other useful hydrocarbon or
heterocarbon reactants containing one or more terminal double bonds
include but are not limited to an olefin started alkane, such as
the non-limiting examples, 1-octene, 1-hexene, amylene, and
1-octadecene; an olefin started alcohol, and an olefin substituted
epoxide, such as the non-limiting examples allyl glycidyl ether, or
vinylcyclohexene monoxide.
[0044] In yet another embodiment, heterocarbon reactants containing
one or more terminal carbon to carbon double bonds include
terminally unsaturated polyalkylene oxides corresponding to the
Formula (10):
R.sup.20(OC.sub.aH.sub.2a).sub.nOR.sup.21 (10)
wherein each occurrence of a is independently an integer from about
2 to about 4 for each unit; each occurrence of n is independently
an integer from about 1 to about 200; each occurrence of R.sup.20
is independently an alkenyl group and specifically an
alpha-olefinic group containing from about 2 to about 10 carbon
atoms and most specifically an allyl, methallyl or vinyl group; and
each occurrence of R.sup.21 is independently selected from the
group of a monovalent radical and more specifically a hydrogen, an
alkyl group containing 1 to 5 carbon atoms, an acyl group
containing 2 to 5 carbon atoms, a 2-oxacycloalkyl group of 4 to 6
carbon atoms and a trialkylsilyl group.
[0045] It is understood that the polyalkylene oxide moiety may be a
block or random copolymer of oxyethylene, oxypropylene or
oxybutylene units and is typically a blend of molecules of varying
chain length and composition and in the foregoing formula. In an
embodiment, "olefinically modified polyalkylene oxide" is a
molecule possessing one or more alkylene oxide groups containing
one or more, terminal or pendant, carbon-carbon double bonds.
Representative olefinically modified polyalkylene oxides include
allyloxypolyethylene oxide and methallyloxypolyethylene oxide and
other possible olefinically modified alkylene oxide components.
[0046] Where the olefinically modified polyalkylene oxide is a
polyether, it may be described by the general Formula (11):
CH.sub.2.dbd.CH(R.sup.13)(R.sup.12).sub.dO(C.sub.2H.sub.4O).sub.a(C.sub.-
3H.sub.6O).sub.b(C.sub.4H.sub.8O).sub.cR.sup.16 (11)
wherein R.sup.13 is hydrogen or methyl; R.sup.12 is a divalent
alkyl radical of 1 to 6 carbons where the subscript d may be 0 or
1; R.sup.16 is hydrogen, a monofunctional hydrocarbon radical of
from about 1 to about 6 carbons, or acyl radical from about 1 to
about 19 carbon atoms. When the polyether is composed of mixed
oxyalkylene groups, such as the non-limiting examples selected from
the group consisting of oxyethylene, oxypropylene and oxybutylene,
the units may be blocked, or randomly distributed. One skilled in
the art will understand the advantages of using a blocked or random
configuration. Illustrative examples of blocked configurations are:
-(oxyethylene).sub.a(oxypropylene).sub.b-;
-(oxybutylene).sub.c(oxyethylene).sub.a-; and
-(oxypropylene).sub.b(oxyethylene).sub.a(oxybutylene).sub.c-]
wherein a, b and c are zero or positive.
[0047] In an embodiment of the present invention, representative
examples of polyether reactants containing one or more carbon to
carbon double bonds are selected from the non-limiting group of
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.8H;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.8CH.sub.3;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.8CH.sub.2CH.sub.2CH.sub.2-
CH.sub.3;
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.4(CH.sub.2CH(CH.-
sub.3)O).sub.5H;
CH.sub.2.dbd.CHO(CH.sub.2CH.sub.2O).sub.5(CH.sub.2CH(CH.sub.3)O).sub.5H;
CH.sub.2.dbd.C(CH.sub.3)CH.sub.2O(CH.sub.2CH.sub.2O).sub.4(CH.sub.2CH(CH.-
sub.3)O).sub.5C(.dbd.O)CH.sub.3; and
CH.sub.2.dbd.CHCH.sub.2O(CH.sub.2CH.sub.2O).sub.5(CH.sub.2CH(CH.sub.3)O).-
sub.2(CH.sub.2CH(CH.sub.2CH.sub.3)O).sub.2H
Catalyst
[0048] In an embodiment of the present invention, suitable first
step hydrosilylation catalysts include rhodium, ruthenium,
palladium osmium, platinum and iridium complexes. More
specifically, a rhodium catalyst is a precious metal catalyst for
the first step of the inventive method giving high selectivity.
Most specifically, the rhodium catalysts employed to effect the
transformation in the first step are complexes of Rh(III) and
Rh(I). In another embodiment of the present invention, the
hydrosilylation catalysts for the first step are selected from the
group of trichlorotris (dibutyl sulfide) rhodium (III);
tri(dibutyl) rhodium chloride and tris(triphenylphosphine) rhodium
chloride and more specifically trichlorotris(dibutyl sulfide)
rhodium (III) to effect formation of the monohydridosiloxane. A
rhodium catalyzed first step reaction results in surprising
monohydridosiloxane selectivity at a dihydridosiloxane to olefin
ratio of about 1.3:1 to about 1:1.
[0049] In another embodiment of the present invention, instances
where molar ratio of the dihydridosiloxane compound to the olefin
in the first step is less than 4:1 to about 1:1, suitable precious
metal catalysts may include complexes of platinum. The platinum
catalyst may be selected from those having the formula
(PtCl.sub.2Olefin) and H(PtCl.sub.3Olefin) as described in U.S.
Pat. No. 3,159,601, hereby incorporated by reference. In still
another embodiment, platinum-containing material may be a complex
of chloroplatinic acid with up to 2 moles per gram of platinum of a
member selected from the class consisting of alcohols, ethers,
aldehydes and mixtures. In yet another embodiment,
platinum-containing materials useful in this present invention is a
Karstedt catalyst
[Pt(H.sub.2C.dbd.CSiMe.sub.2OSiMe.sub.2CH.dbd.CH.sub.2)n].
[0050] The precious metal catalysts suitable for manufacture of the
organomodified siloxanes in the second step of the method include
complexes of rhodium, ruthenium, palladium, osmium, iridium, or
platinum. Representative non-limiting examples are selected from
the group consisting of Speier's Catalyst [H.sub.2PtCl.sub.6] and
Karstedt's Catalyst
[Pt(H.sub.2C.dbd.CSiMe.sub.2OSiMe.sub.2CH.dbd.CH.sub.2)n].
[0051] The level of catalyst employed for either step of the method
may range from 1000 ppm to 0.5 ppm of the precious metal and more
specifically in a range from about 10 ppm to about 3 ppm. The level
of catalyst is based on the total charge of the dihydridosiloxane
and the olefinic compound.
Other Reaction Parameters
[0052] In an embodiment of the present invention, the molar ratio
of the dihydridosiloxane compound to the olefin in the first step
may range from about 10:1 to about 1:1, more specifically from less
than about 4:1 to about 1.1:1 most specifically, about 1.2:1.
Increasing the ratio of the hydridosiloxane to the olefin may
provide measurable increases in selectively with diminishing
returns at drastically elevated ratios. A selectivity of greater
than 90% may be achieved with the hydridosiloxane to olefin ratio
of greater than 1:1 to 1.3:1. In another embodiment, the molar
ratio of the hydrocarbon or heterocarbon containing a carbon to
carbon double bond to the monohydridosiloxane in the second step
may range from about 10:1 to about 1:1 and more specifically, a
ratio of about 1.3:1.
[0053] The hydrosilylation reaction of the invention may be
conducted over a temperature range of 0 to 120.degree. C., but it
is preferable to employ temperatures from 20-80.degree. C. for the
first step of the method and 80-100.degree. C. for the second step
to provide reasonable rates of reaction and simplicity of equipment
configuration.
[0054] Reactions may be conducted in "batch", "semi-continuous" or
"continuous" fashion with the preferred embodiment being
"semi-continuous." For step one of the method (formation of the
monohydridosiloxane), operation of the "semi-continuous" embodiment
involves a staged addition of the olefinic compound to the
hydridosiloxane or hydridosilane to permit control of the reaction
temperature. For step two of the method, operation of the
"semi-continuous" embodiment involves the staged addition of the
monohydridosiloxane or monohydridosilane to the olefin. The mode of
operation may be dependent upon the hydridosiloxane and olefinic
compound chosen as reaction constituents.
[0055] No compatibilizing agent or "solvent" is needed to carry out
the process but low levels may be added without compromising
effectiveness of the process. If a compatibilizing agent is
employed, a stripping or distillation step may need to be
incorporated in the process or the solvent may remain in the
product.
[0056] The hydrosilylation reaction may be optionally conducted in
the presence of additives or "buffering" agents, for example a
buffering salt that prevents the dehydrocondensation of hydroxyl
groups with the SiH moiety. This technology is effective for
preventing unwanted side reactions during the hydrosilylation of
uncapped polyethers, e.g., allylpolyethylene oxide glycol.
[0057] The hydrosilylation reaction may optionally be carried out
in the presence of sterically hindered nitrogen compounds.
Depending on the method of manufacture and the nature of the
reactants, one or more of these additives may already be present
during the hydrosilylation reaction. For example, a low, but
sometimes adequate, level of carboxylic acid salts or phosphate
salts may already be present in olefinically substituted
polyalkylene oxides owing to inadvertent exposure to traces of
oxygen during subsequent capping of hydroxyl groups with allylic,
methallylic, methyl, or acyl groups, or to neutralization of basic
catalysts with phosphoric acid. In such instances, the intentional
addition of the salt or other additive may be unnecessary.
Use
[0058] The asymmetric siloxanes of the invention may impart
resistance to hydrolysis over a wide pH range including an enhanced
resistance to hydrolysis outside a pH range from 6 to 7.5. Enhanced
resistance to hydrolysis may be demonstrated by a variety of tests
but as used herein enhanced resistance to hydrolysis means 50 mole
percent or more of the hydrolysis resistant composition of the
present invention remains unchanged or unreacted after a period of
a twenty-four exposure to aqueous acidic conditions where the
solution has a pH lower than 6 or after a period of a twenty-four
hour exposure to aqueous basic conditions where the solution has a
pH greater than 7.5. Under acidic conditions the compositions of
the present invention show a survival of 50 mole percent of the
original concentration or greater at a pH of 5 or less for a period
of time in excess of 48 hours; specifically the compositions of the
present invention show a survival of 50 mole percent or greater at
a pH of 5 or less for a period of time in excess of 2 weeks; more
specifically the compositions of the present invention show a
survival of 50 mole percent or greater at a pH of 5 or less for a
period of time in excess of 1 month; and most specifically the
compositions of the present invention show a survival of 50 mole
percent or greater at a pH of 5 or less for a period of time in
excess of 6 months. Under basic conditions the compositions of the
present invention show a survival of 50 mole percent or greater at
a pH of 8 or more for a period of time in excess of 2 weeks;
specifically the compositions of the present invention show a
survival of 50 mole percent or greater at a pH of 8 or more for a
period of time in excess of 4 weeks; more specifically the
compositions of the present invention show a survival of 50 mole
percent or greater at a pH of 8 or more for a period of time in
excess of 6 months; and most specifically the compositions of the
present invention show a survival of 50 mole percent or greater at
a pH of 8 or more for a period of time in excess of 1 year.
[0059] Typical uses for invention product include pesticide,
fungicide and insecticide applications and other agrochemical
applications including agricultural, horticultural, turf,
ornamental, home and garden, veterinary and forestry applications
as well as in personal and home care compositions as surfactants,
coatings, excipients, surfactants or the like.
Pesticide
[0060] Many pesticide applications require the addition of an
adjuvant to a spray mixture to provide wetting and spreading on
foliar surfaces. Often that adjuvant is a siloxane surfactant,
which may perform a variety of functions, such as increasing spray
droplet retention on difficult to wet leaf surfaces, enhance
spreading to improve spray coverage, or to provide penetration of
the herbicide into the plant cuticle. These adjuvants are provided
either as a tank-side additive or used as a component in pesticide
formulations.
[0061] The pesticidal compositions of the present invention include
at least one pesticide and the asymmetric silicone adjuvant or
surfactant, present at an amount sufficient to deliver between
0.005% and 2% to the final use concentration, either as a
concentrate or diluted in a tank mix. Optionally the pesticidal
composition may include excipients, co-surfactants, solvents, foam
control agents, deposition aids, drift retardants, biologicals,
micronutrients, fertilizers and the like. The term pesticide means
any compound used to destroy pests, e.g., rodenticides,
insecticides, miticides, fungicides, and herbicides. Illustrative
examples of pesticides, which may be employed include, but are not
limited to, growth regulators, photosynthesis inhibitors, pigment
inhibitors, mitotic disrupters, lipid biosynthesis inhibitors, cell
wall inhibitors, and cell membrane disrupters. The amount of
pesticide employed in compositions of the invention varies with the
type of pesticide employed. More specific examples of pesticide
compounds that may be used with the compositions of the invention
are, but not limited to, herbicides and growth regulators, such as:
phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric
acids, benzoic acids, triazines and s-triazines, substituted ureas,
uracils, bentazon, desmedipham, methazole, phenmedipham, pyridate,
amitrole, clomazone, fluridone, norflurazone, dinitroanilines,
isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin,
glyphosate, sulfonylureas, imidazolinones, clethodim,
diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl,
haloxyfop-methyl, quizalofop, sethoxydim, dichlorobenil, isoxaben,
and bipyridylium compounds.
Fungicide
[0062] Fungicide compositions that may be used with the present
invention include, but are not limited to, aldimorph, tridemorph,
dodemorph, dimethomorph; flusilazol, azaconazole, cyproconazole,
epoxiconazole, furconazole, propiconazole, tebuconazole and the
like; imiazalil, thiophanate, benomyl carbendazim, chlorothialonil,
dicloran, trifloxystrobin, fluoxystrobin, dimoxystrobin,
azoxystrobin, furcaranil, prochloraz, flusulfamide, famoxadone,
captan, maneb, manocozeb, dodicin, dodine, and metalaxyl.
Insecticide
[0063] Insecticide, larvacide, miticide and ovacide compounds that
may be used with the asymmetric siloxane of the invention include
Bacillus thuringiensis, spinosad, abamectin, doramectin,
lepimectin, pyrethrins, carbaryl, primicarb, aldicarb, methomyl,
amitraz, boric acid, chlordimeform, novaluron, bistrifluron,
triflumuron, diflubenzuron, imidacloprid, diazinon, acephate,
endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl,
izoxathion, chlorpyrifos, clofentezine, lambda-cyhalothrin,
permethrin, bifenthrin, cypermethrin and the like.
[0064] The pesticide may be a liquid or a solid. If a solid, it is
preferable that it is soluble in a solvent, or the asymmetric
siloxane of the invention, prior to application, and the silicone
may act as a solvent, or surfactant for such solubility or
additional surfactants may perform this function.
Other Agrochemical Compositions
[0065] Buffers, preservatives and other standard excipients known
in the art also may be included in an agricultural composition with
the asymmetrical silicone of the invention. Solvents may also be
included in compositions of the present invention. These solvents
are in a liquid state at room temperature. Examples include water,
alcohols, aromatic solvents, oils (i.e. mineral oil, vegetable oil,
silicone oil, and so forth), lower alkyl esters of vegetable oils,
fatty acids, ketones, glycols, polyethylene glycols, diols,
paraffinics, and so forth. Particular solvents would be
2,2,4-trimethyl, 1-3-pentane diol and alkoxylated (especially
ethoxylated) versions thereof as illustrated in U.S. Pat. No.
5,674,832 herein incorporated by reference, or
n-methyl-pyrrilidone.
[0066] In another useful embodiment, the agrochemical composition
of the present invention further comprises one or more agrochemical
ingredients. Suitable agrochemical ingredients include, but not
limited to, herbicides, insecticides, growth regulators,
fungicides, miticides, acaricides, fertilizers, biologicals, plant
nutritionals, micronutrients, biocides, paraffinic mineral oil,
methylated seed oils (i.e. methylsoyate or methylcanolate),
vegetable oils (such as soybean oil and canola oil), water
conditioning agents such as Choice.RTM. (Loveland Industries,
Greeley, Colo.) and Quest (Helena Chemical, Collierville, Tenn.),
modified clays such as Surround.RTM. (Englehard Corp.), foam
control agents, surfactants, wetting agents, dispersants,
emulsifiers, deposition aids, antidrift components, and water.
[0067] Suitable agrochemical compositions are made by combining
ingredients by mixing one or more of the above components with the
organomodified siloxane of the present invention, either as a
tank-mix, or as an "In-can" formulation. The term "tank-mix" means
the addition of at least one agrochemical to a spray medium, such
as water or oil, at the point of use. The term "In-can" refers to a
formulation or concentrate containing at least one agrochemical
component. The "In-can" formulation may then diluted to use
concentration at the point of use, typically in a Tank-mix, or it
may be used undiluted.
Personal Care Product
[0068] The asymmetrical silicone surfactant of the invention may be
utilized in personal care emulsions, such as lotions, and creams. A
personal care emulsion may comprise at least two immiscible phases
one of which is continuous and the other which is discontinuous.
Further emulsions may be liquids with varying viscosities or they
may be solids. Additionally the particle size of the emulsions may
be render them microemulsions and when sufficiently small
microemulsions may be transparent. Further it is also possible to
prepare emulsions of emulsions and these are generally known as
multiple emulsions. These emulsions may be: aqueous emulsions where
the discontinuous phase comprises water and the continuous phase
comprises the organomodified trisiloxane surfactant of the present
invention; aqueous emulsions where the continuous phase comprises
the organomodified trisiloxane surfactant of the present invention
and the discontinuous phase comprises water; non-aqueous emulsions
where the discontinuous phase comprises a non-aqueous hydroxylic
solvent and the continuous phase comprises the organomodified
trisiloxane surfactant of the present invention; and non-aqueous
emulsions where the continuous phase comprises a non-aqueous
hydroxylic organic solvent and the discontinuous phase comprises
the organomodified trisiloxane surfactant of the present
invention.
[0069] As used herein the term "non-aqueous hydroxylic organic
compound" means hydroxyl containing organic compounds exemplified
by alcohols, glycols, polyhydric alcohols and polymeric glycols and
mixtures thereof that are liquid at room temperature, e.g. about
25.degree. C., and about one atmosphere pressure. The non-aqueous
organic hydroxylic solvents are selected from the group consisting
of hydroxyl containing organic compounds comprising alcohols,
glycols, polyhydric alcohols and polymeric glycols and mixtures
thereof that are liquid at room temperature, e.g. about 25.degree.
C., and about one atmosphere pressure. Preferably the non-aqueous
hydroxylic organic solvent is selected from the group consisting of
ethylene glycol, ethanol, propyl alcohol, iso-propyl alcohol,
propylene glycol, dipropylene glycol, tripropylene glycol, butylene
glycol, iso-butylene glycol, methyl propane diol, glycerin,
sorbitol, polyethylene glycol, polypropylene glycol mono alkyl
ethers, polyoxyalkylene copolymers and mixtures thereof.
[0070] Once the desired form is attained whether as a silicone only
phase, any anhydrous mixture comprising the silicone phase, a
hydrous mixture comprising the silicone phase, a water-in-oil
emulsion, an oil-in-water emulsion, or either of the two
non-aqueous emulsions or variations thereon, the resulting material
is usually a cream or lotion with improved deposition properties
and good feel characteristics. It is capable of being blended into
formulations for hair care, skin care, antiperspirants, sunscreens,
cosmetics, color cosmetics, insect repellants, vitamin and hormone
carriers, fragrance carriers and the like.
[0071] Personal care applications for the inventive asymmetrical
silicone include deodorants, antiperspirants,
antiperspirant/deodorants, shaving products, skin lotions,
moisturizers, toners, bath products, cleansing products, hair care
products such as shampoos, conditioners, mousses, styling gels,
hair sprays, hair dyes, hair color products, hair bleaches, waving
products, hair straighteners, manicure products such as nail
polish, nail polish remover, nails creams and lotions, cuticle
softeners, protective creams such as sunscreen, insect repellent
and anti-aging products, color cosmetics such as lipsticks,
foundations, face powders, eye liners, eye shadows, blushes,
makeup, mascaras and other personal care formulations where
silicone components have been conventionally added, as well as drug
delivery systems for topical application of medicinal compositions
that are to be applied to the skin.
[0072] In another useful embodiment, a personal care composition of
the invention further comprises one or more personal care
ingredients. Suitable personal care ingredients include, for
example, emollients, moisturizers, humectants, pigments, including
pearlescent pigments such as, for example, bismuth oxychloride and
titanium dioxide coated mica, colorants, fragrances, biocides,
preservatives, antioxidants, anti-microbial agents, anti-fungal
agents, antiperspirant agents, exfoliants, hormones, enzymes,
medicinal compounds, vitamins, salts, electrolytes, alcohols,
polyols, absorbing agents for ultraviolet radiation, botanical
extracts, surfactants, silicone oils, organic oils, waxes, film
formers, thickening agents such as, for example, fumed silica or
hydrated silica, particulate fillers, such as for example, talc,
kaolin, starch, modified starch, mica, nylon, clays, such as, for
example, bentonite and organo-modified clays.
[0073] Suitable personal care compositions are made by mixing one
or more of the above components with the asymmetrical silicone
surfactant. Suitable personal care compositions may be in the form
of a single phase or in the form of an emulsion, including
oil-in-water, water-in-oil and anhydrous emulsions where the
silicone phase may be either the discontinuous phase or the
continuous phase, as well as multiple emulsions, such as, for
example, oil-in water-in-oil emulsions and water-in-oil-in
water-emulsions.
[0074] In one useful embodiment, an antiperspirant composition
comprises the organomodified trisiloxane surfactant of the present
invention and one or more active antiperspirant agents. Suitable
antiperspirant agents include, for example, the Category I active
antiperspirant ingredients listed in the U.S. Food and Drug
Administration's Oct. 10, 1993 Monograph on antiperspirant drug
products for over-the-counter human use, such as, for example,
aluminum halides, aluminum hydroxyhalides, for example, aluminum
chlorohydrate, and complexes or mixtures thereof with zirconyl
oxyhalides and zirconyl hydroxyhalides, such as for example,
aluminum-zirconium chlorohydrate, aluminum zirconium glycine
complexes, such as, for example, aluminum zirconium
tetrachlorohydrex glycine.
[0075] In another useful embodiment, a skin care composition
comprises the organomodified trisiloxane surfactant, and a vehicle,
such as, for example, a silicone oil or an organic oil. The skin
care composition may, optionally, further include emollients, such
as, for example, triglyceride esters, was esters, alkyl or alkenyl
esters of fatty acids or polyhydric alcohol esters and one or more
the known components conventionally used in skin care compositions,
such as, for example, pigments, vitamins, such as, for example,
Vitamin A, Vitamin C and Vitamin E, sunscreen or sunblock
compounds, such as, for example, titanium dioxide, zinc oxide,
oxybenzone, octylmethoxy cinnamate, butylmethoxy dibenzoylm ethane,
p-aminobenzoic acid and octyl dimethyl-p-aminobenzoic acid.
[0076] In another useful embodiment, a color cosmetic composition,
such as, for example, a lipstick a makeup or a mascara composition
comprises the organomodified trisiloxane surfactant, and a coloring
agent, such as a pigment, a water soluble dye or a liposoluble
dye.
[0077] In another useful embodiment, the compositions of the
present invention are utilized in conjunction with fragrant
materials. These fragrant materials may be fragrant compounds,
encapsulated fragrant compounds, or fragrance releasing compounds
that either the neat compounds or are encapsulated. Particularly
compatible with the compositions of the present invention are the
fragrance releasing silicon containing compounds as disclosed in
U.S. Pat. Nos. 6,046,156; 6,054,547; 6,075,111; 6,077,923;
6,083,901; and 6,153,578; all of which are herein and herewith
specifically incorporated by reference.
[0078] The uses of the compositions of the present invention are
not restricted to personal care compositions, other products such
as waxes, polishes and textiles treated with the compositions of
the present invention are also contemplated.
Home Care Composition
[0079] Home care applications include laundry detergent and fabric
softener, dishwashing liquids, wood and furniture polish, floor
polish, tub and tile cleaners, toilet bowl cleaners, hard surface
cleaners, window cleaners, antifog agents, drain cleaners,
auto-dish washing detergents and sheeting agents, carpet cleaners,
prewash spotters, rust cleaners and scale removers.
Coating
[0080] The asymmetrical silicone of the invention may be included
in a coating composition as a wetting agent or surfactant for the
purpose of emulsification, compatibilization of components,
leveling, flow and reduction of surface defects. Additionally, the
asymmetrical silicone may provide improvements in cured or dry
film, such as improved abrasion resistance, antiblocking,
hydrophilic, and hydrophobic properties. Coatings formulations may
exists as, Solvent-borne coatings, water-borne coatings and powder
coatings.
[0081] An asymmetrical silicone coating compositions may be
employed as an architecture coating; OEM product coating such as an
automotive coating and coil coating and as a special purpose
coating such as an industrial maintenance coating or marine
coating.
Surfactant
[0082] The asymmetrical silicone may be used as a surfactant.
Moreover, other co-surfactants, which have short chain hydrophobes
that do not interfere with superspreading. The surfactants useful
herein with the asymmetrical silicone include nonionic, cationic,
anionic, amphoteric, zwitterionic, polymeric surfactants, or any
mixture thereof. Surfactants are typically hydrocarbon based,
silicone based or fluorocarbon based. Other useful surfactants
include alkoxylates, especially ethoxylates, containing block
copolymers including copolymers of ethylene oxide, propylene oxide,
butylene oxide, and mixtures thereof; alkylarylalkoxylates,
especially ethoxylates or propoxylates and their derivatives
including alkyl phenol ethoxylate; arylarylalkoxylates, especially
ethoxylates or propoxylates and their derivatives; amine
alkoxylates, especially amine ethoxylates; fatty acid alkoxylates;
fatty alcohol alkoxylates; alkyl sulfonates; alkyl benzene and
alkyl naphthalene sulfonates; sulfated fatty alcohols, amines or
acid amides; acid esters of sodium isethionate; esters of sodium
sulfosuccinate; sulfated or sulfonated fatty acid esters; petroleum
sulfonates; N-acyl sarcosinates; alkyl polyglycosides; alkyl
ethoxylated amines; and so forth.
[0083] Specific examples include alkyl acetylenic diols
(SURFONYL--Air Products), pyrrilodone based surfactants (e.g.,
SURFADONE--LP 100--ISP), 2-ethyl hexyl sulfate, isodecyl alcohol
ethoxylates (e.g., RHODASURF DA 530--Rhodia), ethylene diamine
alkoxylates (TETRONICS--BASF), and ethylene oxide/propylene oxide
copolymers (PLURONICS--BASF) and Gemini type surfactants
(Rhodia).
[0084] Preferred surfactants with the inventive asymmetrical
silicone include ethylene oxide/propylene oxide copolymers (EO/PO);
amine ethoxylates; alkyl polyglycosides; oxo-tridecyl alcohol
ethoxylates, and so forth.
[0085] The following Examples are illustrative and should not be
construed as a limitation on the scope of the claims unless a
limitation is specifically recited.
EXAMPLES
[0086] The process of the present invention is illustrated by the
following examples. All percentages are by weight unless otherwise
indicated. In a generalized processing to form the asymmetric
organomodified siloxane a dihydridosiloxane is weighed into a
reaction vessel. The vessel is fitted with a thermocouple, dry-ice
condenser, nitrogen purge tube, addition funnel and overhead
stirrer. A desired quantity of catalyst is added to the
dihydridosiloxane in the reaction vessel. A predetermined amount of
olefin is added via an addition funnel. Agitation of the vessel
contents is initiated at ambient temperature. Addition of the
olefin is initiated at a controlled rate in order to maintain the
temperature of the reaction to less than 70.degree. C. Upon
completion of olefin addition, the material is held at 70.degree.
C. to ensure reaction completion. Depending upon the excess of the
dihydridosiloxane employed and the desired purity of the
monohydridosiloxane product, the resulting product may either be
distilled or stripped prior to the next step in the sequence.
[0087] A desired olefin for the second hydrosilylation step of the
method is weighed into a reaction vessel along with 10-15 weight
percent of the total monohydridosiloxane charge (the total
monohydridosiloxane charge is based upon the molar excess of olefin
desired). The vessel is fitted with an overhead stirrer, dry-ice
condenser, nitrogen purge tube, addition funnel and overhead
stirrer. A remaining amount of the monohydridosiloxane is then
added to the addition funnel. Agitation of the vessel contents is
initiated and the temperature of the vessel contents brought to
80.degree. C. A desired quantity of the selected second
hydrosilylation catalyst is added to the reaction vessel and the
exotherm monitored. Once the temperature of the reaction plateaus,
addition of the monohydridosiloxane is initiated at a controlled
rate in order to maintain the temperature of the reaction to less
than 110.degree. C. Upon completion of the olefin addition, the
material is held at 90.degree. C. to ensure reaction completion.
The product material is stripped to remove residual lites.
Example 1
[0088] Step 1--Formation of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (1 Mole of
TMDSO to 1 Mole of TMVS)
[0089] To a 4-necked, 1 L round bottom flask, equipped with an
overhead stirrer, dry ice/IPA condenser, temperature controller,
nitrogen purge tube and a 500 mL addition funnel, the following
materials were charged: 288.9 grams of tetramethyldisiloxane
(TMDSO; purity=97%), and 96 microliters of tris(dibutylsulfide)
rhodium trichloride (rhodium catalyst; 3% Rh; 5 ppm Rh). Next,
211.1 grams of trimethylvinylsilane (TMVS; 99% purity) was added to
the addition funnel. Agitation of the flask contents was initiated
at ambient temperature (23.degree. C.) along with the slow addition
of TMVS. An exotherm was noted within 2 minutes of the addition of
the TMVS to the flask. The TMVS was added to the agitating mixture
at a rate of 1.35 g/min in order to keep the reaction temperature
under 70.degree. C. Upon completion of the addition of TMVS, the
reaction mixture was allowed to stir for an additional 30 minutes.
The resultant product purity as analyzed by gas chromatography
contained 90.2% of the
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (Structure
1), 7.1% of the bis-adduct and 1.7% TMDSO. Isolation of the pure
product was effected via distillation. To a 2 L, 2-necked round
bottom flask equipped with a magnetic stir bar, 10-tray vacuum
jacketed Oldershaw distillation column (inner diameter=1 inch),
distillation head, 500 mL receiver, heating mantle and temperature
controller, was added 946.6 grams of the crude product. A digital
manometer, dry ice/IPA trap, and vacuum pump were then attached to
the set-up. Agitation was initiated along with heating of the flask
contents. Product was distilled overhead at 135.degree. C. and 9 mm
Hg vacuum. 810.1 grams of greater than 99% pure (via GC)
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (Structure
1) was obtained. The balance of the material was comprised of 12.6
grams of lites and 120 grams of heavies for a total recovery of
99.6% of the starting crude material.
##STR00001##
[0090] Step 2--Hydrosilylation of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
[0091] To a 4-necked, 500 mL round bottom flask, equipped with an
overhead stirrer, Friedrich condenser, temperature controller,
nitrogen purge tube and 250 mL addition funnel, were charged 211.4
grams of a methyl capped allylpolyethyleneglycol (MW.about.400
g/mole). To the addition funnel was added 89.0 grams of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane from Step
1. Under a nitrogen blanket, agitation was initiated and the
temperature of the flask contents brought to 80.degree. C. At
80.degree.0 C., the reaction was catalyzed with 0.14 mL of 3.3%
hexachloroplatinic acid solution in ethanol (5 ppm) and the
addition of 1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
was initiated. Within two minutes, the reaction exothermed. The
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane was added
to the agitating mixture at a rate that enabled control of the
reaction temperature. Upon completion of the addition
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane, the
reaction mixture was allowed to stir for an additional 90 minutes
at 80.degree. C. No residual silanic hydrogen was detected in the
product (Structure 2).
##STR00002##
Example 2
[0092] Step 1--Formation of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (1.33 Moles
of TMDSO to 1 Mole TMVS)
[0093] To a 4-necked, 1 L round bottom flask, equipped with an
overhead stirrer, dry ice/IPA condenser, temperature controller,
nitrogen purge tube and a 500 mL addition funnel, the following
materials were charged: 320.5 grams of tetramethyldisiloxane
(TMDSO; purity=97%), and 96 microliters of tris(dibutylsulfide)
rhodium trichloride (rhodium catalyst; 3% Rh; 5 ppm Rh). Next,
179.5 grams of trimethylvinylsilane (TMVS; 99% purity) was added to
the addition funnel. Agitation of the flask contents was initiated
at ambient temperature (23.degree. C.) along with the slow addition
of TMVS. An exotherm was noted within 2 minutes of the addition of
the TMVS to the flask. The TMVS was added to the agitating mixture
at a rate of 1.26 g/min in order to keep the reaction temperature
under 70.degree. C. Upon completion of the addition of TMVS, the
reaction mixture was allowed to stir for an additional 30 minutes.
The resultant product purity an analyzed by gas chromatography was
81.7% of the
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (Structure
1), 2.5% of the bis-adduct and 15.4% TMDSO. Isolation of the
product was effected via stripping. In this particular instance,
the aim of the strip was solely to remove the lites from the
mixture. To a 1 L, 4-necked round bottom flask equipped with a
pneumatic overhead stirrer, 10-tray vacuum jacketed Oldershaw
distillation column (inner diameter=1 inch), distillation head, 500
mL receiver, heating mantle and temperature controller, was added
497.3 grams of the crude product. A digital manometer, dry ice/IPA
trap, and vacuum pump were then attached to the set-up. Agitation
was initiated along with heating of the flask contents. At a
temperature of 140.degree. C. and a vigorous N.sub.2 sparge, 74.1
grams of lites (95.4% TMDSO) was removed from the flask contents.
The remaining material in the flask (414.8 grams) was comprised of
the 1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
(Structure 1) (94.8% via GC) and the bis-substituted by-product
(5.2% via GC). This represented a total recovery of 98.3% of the
starting crude material.
##STR00003##
[0094] Step 2--Hydrosilylation of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
[0095] To a 4-necked, 500 mL round bottom flask, equipped with an
overhead stirrer, Friedrich condenser, temperature controller,
nitrogen purge tube and 250 mL addition funnel, were charged 208.8
grams of a methyl capped allylpolyethyleneglycol (MW.about.400
g/mole). To the addition funnel was added 91.5 grams of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane from Step
1. Under a nitrogen blanket, agitation was initiated and the
temperature of the flask contents brought to 80.degree. C. At
80.degree. C., the reaction was catalyzed with 0.14 mL of 3.3%
hexachloroplatinic acid solution in ethanol (5 ppm) and the
addition of 1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
was initiated. Within two minutes, the reaction exothermed. The
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane was added
to the agitating mixture at a rate of 1.73 g/min in order to
control the reaction temperature. Upon completion of the addition
of 1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane, the
reaction mixture was allowed to stir for an additional 90 minutes
at 80.degree. C. No residual silanic hydrogen was detected in the
product (Structure 2).
##STR00004##
Example 3
[0096] Step 1--Formation of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane (1.5 Moles
of TMDSO to 1 Mole TMVS)
[0097] To a 4-necked, 250 mL round bottom flask, equipped with a
stirrer, dry ice/IPA condenser, temperature controller, nitrogen
purge tube and a 500 mL addition funnel, the following materials
were charged: 51.6 grams of tetramethyldisiloxane (TMDSO;
purity=97%), tris(triphenylphosphine) rhodium chloride (rhodium
catalyst; 100 ppm Rh). Next, 25.6 grams of trimethylvinylsilane
(TMVS; 99% purity) was added to the addition funnel. Agitation of
the flask contents was initiated and the temperature brought to
60.degree. C. Addition of the TMVS was initiated and an exotherm
was noted within 2 minutes of the addition of the TMVS to the
flask. The TMVS was added to the agitating mixture at a rate of 1.0
g/min in order to keep the reaction temperature under 70.degree. C.
Upon completion of the addition of TMVS, the reaction mixture was
allowed to stir for an additional hour at 65.degree. C., then
sampled for GC analysis; found residual tetramethyldisiloxane and
94:6 M'M.sup.R:M.sup.RM.sup.R). The resulting material was
distilled fractionally under vacuum (approx. 30 mm Hg) to yield
51.6 g of 1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
(Structure 1), 99.1% GC purity.
[0098] Step 2--Hydrosilylation of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
[0099] To a 4-necked, 100 mL round bottom flask, equipped with an
overhead stirrer, Friedrich condenser, temperature controller,
nitrogen purge tube and addition funnel, were charged 11.5 grams of
a methyl capped allylpolyethyleneglycol (MW.about.400 g/mole) and 3
grams of isopropanol. To the addition funnel was added 5 grams of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane from Step
1. Under a nitrogen blanket, agitation was initiated and the
temperature of the flask contents brought to 70.degree. C. At
70.degree. C., the reaction was catalyzed with 16 .mu.L of 3.3%
hexachloroplatinic acid solution in ethanol (10 ppm) and the
addition of 1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane
was initiated. Within two minutes, the reaction exothermed. The
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane was added
to the agitating mixture at a rate that enabled control of the
reaction temperature. Upon completion of the addition of
1-(2-trimethylsilylethyl)-1,1,3,3-tetramethyldisiloxane, the
reaction mixture was allowed to stir for an additional 60 minutes
at 70.degree. C. No residual silanic hydrogen was detected in the
product. The product was permitted to cool to room temperature,
neutralized with damp sodium bicarbonate, filtered with Celite, and
stripped at 70.degree. l C. and 5 mm Hg for 2 hours to yield 12.1 g
of a clear, pale yellow fluid (Structure 2).
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[0100] The invention includes changes and alterations that fall
within the purview of the following claims. The foregoing examples
are merely illustrative of the invention, serving to illustrate
only some of the features of the present invention. The appended
claims are intended to claim the invention as broadly as it has
been conceived and the examples herein presented are illustrative
of selected embodiments from a manifold of all possible
embodiments. Accordingly it is Applicants' intention that the
appended claims are not to be limited by the choice of examples
utilized to illustrate features of the present invention.
[0101] As used in the claims, the word "comprises" and its
grammatical variants logically also subtend and include phrases of
varying and differing extent such as for example, but not limited
thereto, "consisting essentially of" and "consisting of."
[0102] Where necessary, ranges have been supplied, those ranges are
inclusive of all sub-ranges there between. Such ranges may be
viewed as a Markush group or groups consisting of differing
pairwise numerical limitations which group or groups is or are
fully defined by its lower and upper bounds, increasing in a
regular fashion numerically from lower bounds to upper bounds. It
is to be expected that variations in these ranges will suggest
themselves to a practitioner having ordinary skill in the art and
where not already dedicated to the public, those variations should
where possible be construed to be covered by the appended
claims.
[0103] It is also anticipated that advances in science and
technology will make equivalents and substitutions possible that
are not now contemplated by reason of the imprecision of language
and these variations should also be construed where possible to be
covered by the appended claims.
[0104] All United States patents (and patent applications)
referenced herein are herewith and hereby specifically incorporated
by reference in their entirety as though set forth in full.
[0105] The invention includes changes and alterations that fall
within the purview of the following claims.
* * * * *