U.S. patent application number 17/277602 was filed with the patent office on 2022-02-10 for method for preparing a functionalized polyorganosiloxane.
The applicant listed for this patent is Dow Silicones Corporation. Invention is credited to Eric Joffre, Nanguo Liu, Michael Telgenhoff.
Application Number | 20220041812 17/277602 |
Document ID | / |
Family ID | |
Filed Date | 2022-02-10 |
United States Patent
Application |
20220041812 |
Kind Code |
A1 |
Telgenhoff; Michael ; et
al. |
February 10, 2022 |
METHOD FOR PREPARING A FUNCTIONALIZED POLYORGANOSILOXANE
Abstract
A method for preparing functionalized polyorganosiloxanes is
disclosed. The method includes 1) combining starting materials
including A) a boron--containing Lewis acid catalyst, and B) an
organosilicon compound having an average, per molecule of at least
1 silicon bonded groups of the formula --OR.sup.2; wherein each
R.sup.2 is an independently selected monovalent hydrocarbon group
of 1 to 6 carbon atoms, thereby forming a catalyzed mixture; and
thereafter 2) adding the catalyzed mixture into a starting material
including C) an organohydrogensiloxane having at least 1 silicon
bonded hydrogen atom per molecule, thereby preparing a product
comprising the functionalized polyorganosiloxane and a by-product
comprising HR.sup.2.
Inventors: |
Telgenhoff; Michael;
(Midland, MI) ; Joffre; Eric; (Midland, MI)
; Liu; Nanguo; (Midland, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Silicones Corporation |
Midland |
MI |
US |
|
|
Appl. No.: |
17/277602 |
Filed: |
December 4, 2019 |
PCT Filed: |
December 4, 2019 |
PCT NO: |
PCT/US2019/064346 |
371 Date: |
March 18, 2021 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
62783224 |
Dec 21, 2018 |
|
|
|
International
Class: |
C08G 77/38 20060101
C08G077/38; C08G 77/18 20060101 C08G077/18; C08G 77/12 20060101
C08G077/12; C08G 77/08 20060101 C08G077/08 |
Claims
1. A method for preparing a functionalized polyorganosiloxane
comprising: 1) combining starting materials comprising A) a
boron--containing Lewis acid, and B) an organosilicon compound
having an average, per molecule of at least 1 silicon bonded group
of the formula --OR.sup.2; wherein each R.sup.2 is an independently
selected monovalent hydrocarbon group of 1 to 6 carbon atoms,
thereby forming a catalyzed mixture; and thereafter 2) adding the
catalyzed mixture into a starting material comprising C) an
organohydrogensiloxane having at least 1 silicon bonded hydrogen
atom per molecule, thereby preparing a product comprising the
functionalized polyorganosiloxane and a by-product comprising
HR.sup.2.
2. The method of claim 1, further comprising: adding additional
boron--containing Lewis acid, to C) the organohydrogensiloxane
before adding the catalyzed mixture into the starting material
comprising the organohydrogensiloxane in step 2).
3. The method of claim 1, where step 2) is performed at a
temperature of 5.degree. C. to 40.degree. C.
4. The method of claim 2, where the additional boron containing
Lewis acid is present in an amount of 5 ppm to 250 ppm based on
weight of C) the organohydrogensiloxane.
5. The method of claim 1, where the boron containing Lewis acid,
and when present, and any additional boron containing Lewis acid,
is provided in a total amount of 50 ppm to 6000 ppm, based on
combined weights of B) the organosilicon compound and C) the
organohydrogensiloxane.
6. The method of claim 1, where in step 1), A) the boron containing
Lewis acid is present in an amount of 5 ppm to 600 ppm based on
weight of B) the organosilicon compound.
7. The method of claim 1, where the method is performed at a
temperature of 5.degree. C. to 70.degree. C.
8. The method of claim 1, where the catalyzed mixture in step 1) is
heated to 40.degree. C. to 70.degree. C. before step 2).
9. The method of claim 8, where the catalyzed mixture is cooled to
less than 40.degree. C. in step 2).
10. The method of claim 1, where the method is performed at a
temperature of 10.degree. C. to <25.degree. C.
11. The method claim 1, where A) the boron--containing Lewis acid
is a trivalent boron compound with at least one perfluoroaryl group
per molecule.
12. The method of claim 1, where B) the organosilicon compound is
selected from the group consisting of: an alkoxysilane of formula:
R.sup.1.sub.(4-a)SiOR.sup.2.sub.a, where each R.sup.1 is
independently selected from the group consisting of a monovalent
hydrocarbon group and a monovalent halogenated hydrocarbon group,
each R.sup.2 is a monovalent hydrocarbon group of 1 to 6 carbon
atoms, and subscript a is 1 to 4; an organosiloxane of formula:
R.sup.3.sub.2R.sup.XSiO--(R.sup.3.sub.2SiO).sub.b--SiR.sup.XR.sup.3.sub.2-
, where each R.sup.3 is independently selected from the group
consisting of a monovalent hydrocarbon group and a monovalent
halogenated hydrocarbon group, each R.sup.X is the group of formula
--OR.sup.2, and subscript b.gtoreq.1; and a resin of unit formula:
(R.sup.1SiO.sub.3/2).sub.m(R.sup.1R.sup.XSiO.sub.2/2).sub.n(R.sup.1R.sup.-
X.sub.2SiO.sub.1/2).sub.z, where subscript m is 0 to 20, subscript
n is 1 to 20, subscript z is 0 to 20, each R.sup.1 is independently
selected from the group consisting of a monovalent hydrocarbon
group and a monovalent halogenated hydrocarbon group, and each
R.sup.X is the group of formula --OR.sup.2
13. The method of claim 1, where C) the organohydrogensiloxane has
unit formula:
(HR.sup.4.sub.2SiO.sub.1/2).sub.g(R.sup.4.sub.3SiO.sub.1/2).sub-
.h(R.sup.4.sub.2SiO.sub.2/2).sub.i(HR.sup.4SiO.sub.2/2).sub.j,
where subscripts g, h, i, and j have values such that g.gtoreq.0,
h.gtoreq.0, a quantity (g+h) has an average value of 2, i.gtoreq.0,
j.gtoreq.0, and a quantity (g+j)>0, a quantity (i+j) ranges from
0 to 1000, and the quantity (g+j) has a value sufficient to provide
the polyorganohydrogensiloxane with at least 1% silicon bonded
hydrogen atoms; and each R.sup.4 is an independently selected
monovalent hydrocarbon group.
14. The method of claim 1, further comprising: neutralizing
residual boron--containing Lewis acid in the product.
15. The method of claim 1, further comprising: during and/or after
step 2), removing a by-product comprising HR.sup.2.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Patent Application No. 62/783,224 filed 21 Dec. 2018 under 35
U.S.C. .sctn. 119 (e). and U.S. Provisional Patent Application No.
62/783,224 is hereby incorporated by reference.
TECHNICAL FIELD
[0002] A method for preparing a functionalized polyorganosiloxane
is disclosed. More particularly, the method includes combining a
boron containing Lewis acid catalyst and an alkoxysilyl functional
organosilicon compound to form a catalyzed mixture and thereafter
adding the catalyzed mixture to an SiH functional organosilicon
compound.
BACKGROUND
[0003] Piers-Rubinsztajn reactions involving silicon hydride
functional organosilicon compounds and alkoxysilyl functional
organosilicon compounds have been disclosed where the
Piers-Rubinsztajn reaction catalyst, silicon hydride functional
organosilicon compound and alkoxysilyl functional compound are
combined concurrently, or where the silicon hydride functional
organosilicon compound and alkoxysilyl functional compounds are
mixed before the catalyst is added thereto. These methods suffer
from the drawback of the catalyst being deactivated, resulting in
slowing of the reaction rate and/or catalyst deactivation and/or
poor yields.
SUMMARY
[0004] A method for preparing a functionalized polyorganosiloxane
comprises:
1) combining starting materials comprising
[0005] A) a boron--containing Lewis acid, and
[0006] B) an organosilicon compound having an average, per molecule
of at least 1 silicon bonded group of the formula --OR.sup.2;
wherein each R.sup.2 is an independently selected monovalent
hydrocarbon group of 1 to 6 carbon atoms, thereby forming a
catalyzed mixture; and thereafter
2) adding the catalyzed mixture into a starting material
comprising
[0007] C) an organohydrogensiloxane having at least 1 silicon
bonded hydrogen atom per molecule, thereby preparing a product
comprising the functionalized polyorganosiloxane and a by-product
comprising a compound of formula HR.sup.2.
DETAILED DESCRIPTION OF THE INVENTION
[0008] This invention relates to the method for preparing a
functionalized polyorganosiloxane. The method comprises:
1) combining starting materials comprising
[0009] A) the boron--containing Lewis acid, and
[0010] B) the organosilicon compound having an average, per
molecule of at least 1 silicon bonded group of the formula
--OR.sup.2; wherein each R.sup.2 is an independently selected
monovalent hydrocarbon group of 1 to 6 carbon atoms, thereby
forming a catalyzed mixture; and thereafter
2) adding the catalyzed mixture into a starting material
comprising
[0011] C) the organohydrogensiloxane having at least 1 silicon
bonded hydrogen atom per molecule, thereby preparing a product
comprising the functionalized polyorganosiloxane and a by-product
comprising a compound of formula HR.sup.2. The starting materials
in step 1) are free of SiH functional organosilicon compounds. The
starting materials in step 2) may be free of alkoxysilyl functional
organosilicon compounds before beginning the addition of the
catalyzed mixture. "Free of" as used herein includes none,
alternatively an amount non-detectable by GC, and alternatively an
amount insufficient to deactivate A) the boron--containing Lewis
acid used as catalyst for reacting starting materials B) and C).
The starting materials used in the method may optionally further
comprise D) a solvent. One or more of starting materials A), B) and
C) may be dissolved in a solvent before adding in the method.
[0012] The method may optionally further comprise one or more
additional steps selected from the group consisting of:
[0013] adding additional boron--containing Lewis acid, to C) the
organohydrogensiloxane before adding the catalyzed mixture into the
starting material comprising the organohydrogensiloxane in step
2);
[0014] during and/or after step 2), removing a by-product
comprising HR.sup.2; and
[0015] neutralizing residual boron--containing Lewis acid in the
product; and
[0016] recovering the functionalized polyorganosiloxane. The
additional boron--containing Lewis acid may be the same as, or
different from, the boron--containing Lewis acid used in step
1).
[0017] The method may optionally further comprise adding additional
boron--containing Lewis acid, to C) the organohydrogensiloxane
before adding the catalyzed mixture to the organohydrogensiloxane
in step 2). The additional boron containing Lewis acid may be
present in an amount of 5 ppm to 250 ppm based on weight of C) the
organohydrogensiloxane.
[0018] In steps 1) and 2) of this method, the boron containing
Lewis acid, and when present, and any additional boron containing
Lewis acid, may be provided in a total amount of 50 ppm to 6000 ppm
(alternatively 50 to 600 ppm), based on combined weights of the
organosilicon compound and the organohydrogensiloxane. The Lewis
acid in step 1) and the additional Lewis acid, when used in step
2), may be the same or different Lewis acids, as described above
for component A). Alternatively, in step 1), the boron containing
Lewis acid may be present in an amount of 5 ppm to 600 ppm
(alternatively 15 ppm to 600 ppm and alternatively 15 ppm to 250
ppm) based on weight of B) the organosilicon compound.
[0019] The method described herein may be performed at relatively
low temperatures. The method may be performed at a temperature of
5.degree. C. to 70.degree. C., alternatively 5.degree. C. to
65.degree. C., alternatively 10.degree. C. to 60.degree. C.,
alternatively 15.degree. C. to 50.degree. C., alternatively
20.degree. C. to 35.degree. C., alternatively 5.degree. C. to
30.degree. C., and alternatively 30.degree. C. Steps 1) and 2) may
be performed at the same temperature or different temperatures.
Alternatively, the catalyzed mixture in step 1) may be heated to
40.degree. C. to 70.degree. C. before step 2). Alternatively, after
heating to 40.degree. C. to 70.degree. C., the catalyzed mixture
may be cooled to less than 40.degree. C. in step 2). Alternatively,
step 2) may be performed at a temperature of 5.degree. C. to
40.degree. C. Alternatively, the method may be performed at a
temperature of 10.degree. C. to <25.degree. C.
[0020] The method described above may optionally further comprise:
3) neutralizing residual boron--containing Lewis acid in the
product. Neutralizing can be performed by any convenient means,
such as by adding E) a neutralizing agent.
[0021] The method described above may optionally further comprise
recovering the functionalized polyorganosiloxane from the product.
The method may optionally further comprise: during and/or after
step 2), removing a by-product comprising HR.sup.2, where R.sup.2
is as described above. The by-product may be removed by any
convenient means, e.g., by stripping, liquefying, and/or burning.
For example, when R.sup.2 is methyl (the by-product is methane),
the by-product may be removed by burning. Alternatively, if a
particulate by-product is present, e.g., as a result of
neutralization, particulate by-product may be removed by any
convenient means, such as filtration.
Starting Material A) Boron--Containing Lewis Acid
[0022] Starting material A) in the method described herein is a
boron--containing Lewis acid. The boron--containing Lewis acid may
be a trivalent boron compound with at least one perfluoroaryl
group, alternatively 1 to 3 perfluoroaryl groups per molecule,
alternatively 2 to 3 perfluoroaryl groups per molecule, and
alternatively 3 perfluoroaryl groups per molecule. The
perfluoroaryl groups may have 6 to 12 carbon atoms, alternatively 6
to 10, and alternatively 6 carbon atoms. The A) the
boron--containing Lewis Acid catalyst is selected from the group
consisting of (C.sub.5F.sub.4)(C.sub.6F.sub.5).sub.2B;
(C.sub.5F.sub.4).sub.3B; (C.sub.6F.sub.5)BF.sub.2;
BF(C.sub.6F.sub.5).sub.2; B(C.sub.6F.sub.5).sub.3;
BCl.sub.2(C.sub.6F.sub.5); BCl(C.sub.6F.sub.5).sub.2;
B(C.sub.6H.sub.5)(C.sub.6F.sub.5).sub.2;
B(C.sub.6H.sub.5).sub.2(C.sub.6F.sub.5);
[C.sub.6H.sub.4(mCF.sub.3)].sub.3B;
[C.sub.6H.sub.4(pOCF.sub.3)].sub.3B; (C.sub.6F.sub.5)B(OH).sub.2;
(C.sub.6F.sub.5).sub.2BOH; (C.sub.6F.sub.5).sub.2BH;
(C.sub.6F.sub.5)BH.sub.2; (C.sub.7H.sub.11)B(C.sub.6F.sub.5).sub.2;
(C.sub.8H.sub.14)B(C.sub.6F.sub.5);
(C.sub.6F.sub.5).sub.2B(OC.sub.2H.sub.5); or
(C.sub.6F.sub.5).sub.2B--CH.sub.2CH.sub.2Si(CH.sub.3).
Alternatively, the boron--containing Lewis acid catalyst may be
tris(pentafluorophenyl)borane of formula B(C.sub.6F.sub.5).sub.3.
Such boron--containing Lewis acids are commercially available from,
e.g., Millipore Sigma of St. Louis, Mo., USA.
Starting Material B) Alkoxysilyl-Functional Organosilicon
Compound
[0023] Starting material B) in the method described herein is an
organosilicon compound having an average, per molecule, of at least
1 (alternatively 1 to 6, alternatively 1 to 4, alternatively 1 to
3, and alternatively 1 to 2) silicon bonded alkoxy groups of the
formula --OR.sup.2; wherein each R.sup.2 is an independently
selected monovalent hydrocarbon group of 1 to 6 carbon atoms.
Alternatively, each R.sup.2 may be an alkyl group such as methyl,
ethyl, propyl, butyl, pentyl and hexyl, (including branched and
linear isomers, e.g., n-propyl or iso-propyl, n-butyl, iso-butyl,
t-butyl, and sec-butyl); alternatively methyl or ethyl; and
alternatively each R.sup.2 may be methyl.
[0024] The organosilicon compound may be an alkoxysilane of formula
B-1): R.sup.1.sub.(4-a)SiOR.sup.2.sub.a, where R.sup.2 is as
described above, each R.sup.1 is independently selected from the
group consisting of a monovalent hydrocarbon group as described
hereinbelow and a monovalent halogenated hydrocarbon group as
described hereinbelow, and subscript a is 1 to 4. Suitable
monovalent hydrocarbon groups for R.sup.1 are exemplified by alkyl,
and alkenyl, as described hereinbelow. Suitable halogenated
hydrocarbon groups for R.sup.1 are exemplified by haloalkyl, as
described hereinbelow. Alternatively, alkyl groups may be selected
from the group consisting of methyl, ethyl, and propyl.
Alternatively, alkenyl groups may be selected from the group
consisting of vinyl, allyl, and hexenyl. Alternatively, haloalkyl
groups may be selected from the group consisting of chloromethyl,
chloropropyl, trifluoropropyl. Alternatively, subscript a may be 3
to 4.
[0025] Suitable alkoxysilanes are commercially available, e.g.,
suitable tetraalkoxysilanes include tetraethoxysilane and
tetramethoxysilane, which are available from Gelest, Inc. of
Morrisville, Pa., USA. Trialkoxysilanes, which are also
commercially available from Gelest include,
3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,
3-chloroisobutyltrimethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
nonfluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane,
3-bromopropyltrimethoxysilane, 7-bromoheptyltrimethoxysilane,
4-bromobutyltrimethoxysilane, 5-bromopentyltrimethoxysilane,
2-(chloromethyl)allyltrimethoxysilane, cyclohexyltrimethoxysilane,
cyclopentyltrimethoxysilane, methyltrimethoxysilane,
n-propyltrimethoxysilane, n-butyltrimethoxysilane,
t-butyltrimethoxysilane, hexyltrimethoxysilane,
isooctyltrimethoxysilane, (3,3-dimethylbutyl)triethoxysilane,
pentyltriethoxysilane, chloromethyltriethoxysilane,
5-hexenyltrimethoxysilane, 3-cyclohexenyltrimethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane, and
vinyltriisopropoxysilane, allyltrimethoxysilane,
allyltriethoxysilane, and 7-octenyltrimethoxysilane.
[0026] Alternatively, the organosilicon compound may be an
organosiloxane oligomer or polymer. The organosiloxane oligomer or
polymer may have unit formula B-2):
(R.sup.XR.sup.3.sub.2SiO.sub.1/2).sub.o(R.sup.3.sub.3SiO.sub.1/2).sub.b(-
R.sup.3.sub.2SiO.sub.2/2).sub.q(R.sup.XR.sup.3SiO.sub.2/2).sub.r(R.sup.XSi-
O.sub.3/2).sub.s(R.sup.3SiO.sub.3/2).sub.t(SiO.sub.4/2).sub.u,
where R.sup.X represents a group of the formula --OR.sup.2 as
described above, subscripts o, p, q, and r have values such that
o.gtoreq.0, p.gtoreq.0, q.gtoreq.0, r.gtoreq.0, s.gtoreq.0,
t.gtoreq.0, u.gtoreq.0, a quantity (o+r+s) has an average value of
1 or more, alternatively 1 to 6, alternatively 1 to 3, and
alternatively 1 to 2; and each R.sup.3 is an independently selected
monovalent hydrocarbon group as described hereinbelow.
Alternatively, a quantity (o+p+q+r+s+t+u) may be at least 3,
alternatively 3 to 2000. Alternatively, a quantity (q+r) may be 1
to 2,000; alternatively 1 to 50. Alternatively, a quantity (o+p)
may be 0 to 50, alternatively 0 to 2. Alternatively,
1.gtoreq.s.gtoreq.0. Alternatively, 1.gtoreq.t.gtoreq.0.
Alternatively, the quantity (o+r+s) has an average value of 1 to 6,
alternatively 1 to 3, and alternatively 1 to 2. Suitable monovalent
hydrocarbon groups for R.sup.3 are exemplified by alkyl, alkenyl,
and aryl as described hereinbelow. Suitable halogenated hydrocarbon
groups for R.sup.3 are exemplified by haloalkyl, as described
hereinbelow. Alternatively, alkyl groups may be selected from the
group consisting of methyl, ethyl, and propyl. Alternatively,
alkenyl groups may be selected from the group consisting of vinyl,
allyl, and hexenyl. Alternatively, aryl groups may be phenyl.
Alternatively, haloalkyl groups may be selected from the group
consisting of chloromethyl, chloropropyl, trifluoropropyl.
Alternatively, in formula B-2), each R.sup.X may be methoxy or
ethoxy.
[0027] Alternatively, (e.g., when o has an average value of 2, and
p=r=s=t=u=0), starting material B) may be a polydiorganosiloxane of
formula B-3):
R.sup.3.sub.2R.sup.XSiO--(R.sup.3.sub.2SiO).sub.b--OSiR.sup.XR.sup.3.sub-
.2,
where each R.sup.3 and each R.sup.X is are as described above, and
subscript b 1. Alternatively, subscript b may be 1 to 2,000,
alternatively 5 to 900, alternatively 5 to 50, and alternatively
subscript b may be 1 to 50. Alternatively, in formula B-3), each
R.sup.3 may be independently selected from the group consisting of
alkyl (e.g., methyl, ethyl, and propyl), alkenyl (e.g., vinyl,
allyl, and hexenyl), aryl (e.g., phenyl), and haloalkyl (e.g.,
chloromethyl, chloropropyl, and trifluoropropyl). Alternatively, in
formula B-3), each R.sup.X may be methoxy or ethoxy.
Polydiorganosiloxanes of formula B-3), such as methoxy terminated
polydimethylsiloxane with viscosity of 5 to 12 cSt are commercially
available from Gelest, Inc. and
1,3-diethoxy-1,1,3,3-tetramethyldisiloxane is commercially
available from Millipore Sigma.
[0028] Alternatively, starting material B) may have unit formula
B-4): (R.sup.3SiO.sub.3/2).sub.m(R.sup.XR.sup.3SiO.sub.2/2).sub.r,
where subscript m is 0 to 100, subscript r is 1 to 100, and each
R.sup.3 and each R.sup.X are as described above. Alternatively,
subscript m may be 1 to 20. Alternatively subscript r may be 1 to
20. Alternatively, in formula B-4), each R.sup.3 may be
independently selected from the group consisting of alkyl (e.g.,
methyl, ethyl, and propyl), alkenyl (e.g., vinyl, allyl, and
hexenyl), aryl (e.g., phenyl), and haloalkyl (e.g., chloromethyl,
chloropropyl, and trifluoropropyl). Alternatively, in formula B-4),
each R.sup.X may be methoxy or ethoxy. Examples of suitable
alkoxy-functional siloxane resins of unit formula B-4) include
DOWSIL.TM. US-CF2403 Resin and DOWSIL.TM. 2405 Resin from Dow
Silicones Corporation of Midland, Mich., USA.
Starting Material C) Organohydrogensiloxane
[0029] Starting material C) is an organohydrogensiloxane having at
least 1 silicon bonded hydrogen atom (SiH) per molecule. The
organohydrogensiloxane may have unit formula C-1):
(HR.sup.4.sub.2SiO.sub.1/2).sub.g(R.sup.4.sub.3SiO.sub.1/2).sub.h(R.sup.4-
.sub.2SiO.sub.2/2).sub.i(HR.sup.4SiO.sub.2/2).sub.j, where
subscripts g, h, i, and j have values such that g.gtoreq.0,
h.gtoreq.0, a quantity (g+h) has an average value of 2, i.gtoreq.0,
j.gtoreq.0, and a quantity (g+j)>0, and the quantity (g+j) has a
value sufficient to provide the polyorganohydrogensiloxane with at
least 1% silicon bonded hydrogen atoms; and each R.sup.4 is an
independently selected monovalent hydrocarbon group. Alternatively,
each R.sup.4 may be independently selected from the group
consisting of alkyl (e.g., methyl, ethyl or hexyl), and aryl (e.g.,
phenyl).
[0030] Alternatively, a bis-SiH terminated polydialkylsiloxane may
be used as starting material C) when subscript h=0, subscript j=0,
subscript g=2, and subscript i=0 to 500; and each R.sup.4 is an
alkyl group, such as methyl. This bis-SiH terminated
polydialkylsiloxane may have formula C-2):
HR.sup.4.sub.2SiO--(R.sup.4.sub.2SiO).sub.i--OSiHR.sup.4.sub.2.
[0031] Alternatively, a mono-SiH terminated polydialkylsiloxane may
be used as starting material C), when g=1, h=1, i=1 to 500, j=0 and
each R.sup.4 is an alkyl group, such as methyl, This mono-SiH
terminated organohydrogensiloxane comprises formula C-3):
HR.sup.4.sub.2SiO--(R.sup.4.sub.2SiO).sub.i--SiR.sup.4.sub.3, where
R.sup.4 is as described above, Alternatively, in formula C-3), each
R.sup.4 may be an alkyl group such as methyl. Alternatively, in
formula C-3), subscript i may be 1.
[0032] Examples of suitable organohydrogensiloxanes for starting
material C) include DOWSIL.TM. 6-3570 Polymer, which is
commercially available from Dow Silicones Corporation of Midland,
Mich., USA; and 1,1,3,5,5,5-heptamethyltrisiloxane, which is
commercially available from MiliporeSigma (Sigma-Aldrich) of St.
Louis, Mo., USA. Other suitable organohydrogensiloxanes for
starting material C) include 1,1,3,3,3-pentalmethyldisiloxane and
monohydride terminated polydimethylsiloxanes (which have formula
C-1) above, where j is 7 to 80), which are commercially available
from Gelest, Inc. of Morrisville, Pa., USA.
[0033] Starting materials B) and C) may be used in amounts
sufficient to provide an SiH:SiOH molar ratio of 0.9:1 to 10:1,
alternatively 1:1 to 5:1, and alternatively 2:1 to 3:1.
Starting Material D) Solvent
[0034] A solvent may be used in the method. The solvent may
facilitate introduction of certain starting materials, such as
starting material A) the boron containing Lewis acid. Solvents used
herein are those that help fluidize the starting materials but
essentially do not react with any of these starting materials.
Solvent may be selected based on solubility the starting materials
and volatility of the solvent. The solubility refers to the solvent
being sufficient to dissolve and/or disperse the starting
materials. Volatility refers to vapor pressure of the solvent.
[0035] Suitable solvents may be hydrocarbons. Suitable hydrocarbons
include aromatic hydrocarbons such as benzene, toluene, or xylene;
and/or aliphatic hydrocarbons such as heptane, hexane, or octane.
Alternatively, the solvent may be a halogenated hydrocarbon such as
dichloromethane, 1,1,1-trichloroethane or methylene chloride.
[0036] The amount of solvent can depend on various factors
including the type of solvent selected and the amount and type of
other starting materials selected. However, the amount of solvent
may range from 0.1% to 99%, alternatively 2% to 50%, based on
combined weights of starting materials A), B), and C).
Starting Material E) Neutralizing Agent
[0037] Starting material E) is neutralizing agent that may
optionally be used to neutralize starting material A) after the
product forms. Alumina, triphenyl amine, triphenyl phosphine, and
phenylacetylene are suitable neutralizing agents. Neutralizing
agents are known in the art and are commercially available, e.g.,
from Millipore Sigma of St. Louis, Mo., USA. The amount of
neutralizing agent used may be sufficient to provide 1 weight part
to 1000 weight parts based on total weight of boron containing
Lewis acid. Alternatively, when the neutralizing agent is triphenyl
phosphine or phenylacetylene, the E:A ratio may be 1:1 to 20:1.
Alternatively, when the neutralizing agent is alumina, the E:A
ratio may be 100:1 to 1000:1.
EXAMPLES
[0038] These examples are intended to illustrate the invention and
should not be interpreted as limiting the scope of the invention
set forth in the claims. The starting materials in Table 1 were
used in the examples herein.
TABLE-US-00001 TABLE 1 Starting Material Description C Bis-H
1,1,3,5,5,5-heptamethyltrisiloxane, which is commercially available
from MiliporeSigma (Sigma-Aldrich) of St. Louis, Missouri, USA. C
6-3570 DOWSIL .TM. 6-3570 Polymer, which is commercially available
from Dow Silicones Corporation of Midland, Michigan, USA. C MH-1109
DOWSIL .TM. MH-1109, MeH cyclics, is commercially available from
Dow Silicones Corporation of Midland, Michigan, USA, having
formula(MeHSiO2/2)n, where each subscript n = 4, 5, or 6, and n has
an average value of 4.5. B VTM vinyltrimethoxysilane which is
commercially available from MiliporeSigma (Sigma-Aldrich) of St.
Louis, Missouri, USA. B CPTM 3-chloropropyltrimethoxysilane, which
is commercially available from MiliporeSigma (Sigma-Aldrich) of St.
Louis, Missouri, USA. B TMOS tetramethoxysilane, which is
commercially available from MiliporeSigma (Sigma-Aldrich) of St.
Louis, Missouri, USA. B CF-2403 A silsesquioxane resin commercially
available from Dow Silicones Corporation of Midland, Michigan USA
having unit formula:
(MeSiO.sub.3/2).sub.x(Me(MeO)SiO.sub.2/2).sub.y(Me(MeO).sub.2SiO.sub.1/2-
).sub.z, where subscripts x, y, and z are mole fractions with
values such that (y + 2z)/(x + y + z) is 1.0 to 1.2 A BCF
tris(pentafluorophenyl)borane, which is commercially available from
MiliporeSigma (Sigma-Aldrich) of St. Louis, Missouri, USA. Silanol
Fluid OH terminated polydimethylsiloxane with DP of 35, is
commercially available from Dow Silicones Corporation of Midland,
Michigan, USA Activated commercially available from Millipore Sigma
Alumina, neutral
[0039] In this Comparative Example 1, Bis-H and initial 201 ppm BCF
was loaded and held at 50.degree. C. for three hours while the
reactor completed a steady state heat balance. When the reactor was
initially charged with 14 grams (5%) of CPTM, no reaction occurred.
An additional 52 ppm BCF, followed by 54 ppm more was then added
and the reaction started and continued. After 180 grams of CPTM
were added (65%), the reaction slowed significantly, so another 50
ppm BCF was added. At this time, the reaction exothermed to
59.degree. C. and restarted. The reaction continued to slow
throughout the rest of the addition of CPTM, but did not stop where
additional BCF was required. At the end of the run, it took 45
minutes for all discernable exotherm to complete. The reaction was
then held for another 50 minutes to complete a heat balance on the
system. The final analysis indicated only partial conversion of the
methoxysilane in CPTM to Si--O--Si linkages with a residual
composition containing alkoxysilanes, with 0.4% with two residual
methoxy groups and 8.5% with one residual methoxy group.
[0040] In this Working Example #1, Bis-H was loaded into a reactor
and heated to 45.degree. C., and then 19 ppm of BCF was loaded to
the Bis-H. In the feed vessel, CPTM was also mixed with BCF in an
amount sufficient to provide 125 ppm to the entire run. For this
run, the feed tube was placed down into the reactor (underneath the
surface of Bis-H) 5 centimeters above the agitator. The CPTM feed
was started with an initial 20 grams (6%) and the reaction
initiated without issue. After 50 grams of CPTM were fed, the
temperature was dropped to 30.degree. C. for the duration of the
CPTM feed. The reaction continued throughout the entire run showing
a steady heat of reaction with no evidence of the reaction slowing
throughout the run. Therefore, no additional catalyst was loaded to
the reactor. At the end of the CPTM feed, the reactor contents were
held at 30.degree. C. and it took 33 minutes for the discernable
exotherm to complete. The reactor contents were then held for
another 2.5 hours at 30.degree. C. to complete the reaction and
analyzed. The analysis indicated full conversion of the
methoxysilane to Si--O--Si linkages.
[0041] Comparative Example 1 and Working Example 1 show that
combining the BCF with CPTMS before beginning the reaction resulted
in the benefits of catalyst not deactivating over the course of a
run, and more complete reaction of the methoxy groups of CPTMS with
the silicon bonded hydrogen atoms of Bis-H under the conditions
tested in these examples.
[0042] In this Comparative Example #2, Bis-H was mixed with 205 ppm
BCF and heated to 40.degree. C. The VTM feed was started with an
initial 10 grams (5%) and the reaction initiated. After 68% of the
VTM was added, the reaction stopped, and an additional 42 ppm BCF
was added. The reaction continued and then stopped again after 98%
of the VTM was added. An additional 40 ppm of BCF was added, and
VTM the feed was finished. At the end of the VTM feed, the reaction
was held at 40.degree. C. and it took 30 minutes for the
discernable exotherm to complete. The analysis indicated full
conversion of the methoxysilane to Si--O--Si linkages.
[0043] In this Working Example #2, Bis-H was loaded into a reactor
and heated to 40.degree. C., and then 60 ppm of BCF was loaded to
the Bis-H. The feed vessel of VTM was also mixed with BCF in an
amount sufficient to provide 120 ppm to the entire run. The VTM
feed was started with an initial 10 grams (5%), and the reaction
initiated. The reaction continued throughout the rest of the run
showing a steady heat of reaction with no evidence of the reaction
slowing throughout the run. Therefore, no additional BCF was loaded
to the reactor. At the end of the VTM feed, the reactor contents
were held at 40.degree. C., and it took 30 minutes for the
discernable exotherm to complete. The analysis indicated full
conversion of the methoxysilane to Si--O--Si linkages.
[0044] Comparative Example 2 and Working Example 2 show that
combining the BCF catalyst with VTM before beginning the reaction
resulted in the benefits of catalyst not deactivating over the
course of a run, and complete reaction of the methoxy groups of VTM
with the silicon bonded hydrogen atoms of Bis-H using lower
catalyst loading overall under the conditions tested in these
examples.
[0045] In this Working Example #3, 37.9 g of 6-3570 and 38 g of
toluene were mixed at RT in a 500 mL 4 neck flask equipped with
thermal couple, mechanical stirrer, and water-cooled condenser
adapted to a N.sub.2 bubbler. 24.8 g of CPTM was premixed with 150
ppm of BCF and slowly added into the flask under vigorous stirring
within 24 minutes. No additional BCF was added into the reaction,
and there were no signs of the reaction slow down. Pot temperature
was controlled below 35.degree. C. using an ice bath. The reaction
mixture (clear liquid) was stirred at RT for another one hour.
Volatiles were removed via rotary evaporator at 80.degree. C. and
<1 mmHg for 30 minutes. The product was a white solid resin.
[0046] In this Working Example #4, Bis-H was loaded into a reactor,
and 50 ppm of BCF was added thereto. In a feed vessel, a catalyzed
mixture was prepared by mixing CPTM and BCF in an amount sufficient
to provide a total amount of BCF of 161 ppm to the entire run. The
catalyzed mixture feed was started with an initial 20 grams (6%)
and the reaction initiated without issue. The reaction was run at
15.degree. C. The reaction continued throughout the entire run
showing a steady heat of reaction with no evidence of the reaction
slowing throughout the run. Therefore, no additional BCF was loaded
to the material. At the end of the catalyzed mixture feed, the
reaction was held at 15.degree. C., and it took 30 minutes for the
discernable exotherm to complete. The analysis indicated full
conversion of the methoxysilane to Si--O--Si linkages. Working
Example 4 shows that the reaction can run at low temperatures.
[0047] In this Working Example #5, 132 g Bis-H was charged to a 500
mL 4 neck flask equipped with thermal couple, mechanical stirrer,
and water-cooled condenser adapted to a N.sub.2 bubbler. 25 ppm of
BCF was added to the flask. 40.5 g CF-2403 resin and 175 ppm of BCF
were mixed in an addition funnel to form a catalyzed mixture. The
catalyzed mixture was slowly added into the flask within 32
minutes. An ice water bath was used to remove heat and control the
pot temperature below 30.degree. C. After 1 hour stirring at RT,
.sup.1H NMR indicated that the methoxy groups in the CF-2403 resin
had been completely reacted. Volatiles were removed via rotary
evaporator at 150.degree. C. for 1.5 hours. The product was a clear
colorless liquid.
[0048] In this Working Example #6, 157.3 g Bis-H was charged to a
500 mL 4 neck flask equipped with thermal couple, mechanical
stirrer, and water-cooled condenser adapted to a N.sub.2 bubbler.
25 ppm of BCF was added to the flask. 25.0 g TMOS and 175 ppm of
BCF were mixed in an addition funnel to form a catalyzed mixture.
The catalyzed mixture was slowly added into the flask within 40
minutes. An ice water bath was used to remove heat and control the
pot temperature below 30.degree. C. After 1 hours stirring at RT,
.sup.1H NMR indicated that Si--OMe residual content was 0.3%.
Continued stirring for another 1.5 hours. Then 7.3 g of alumina was
added to the flask and stirred for 2 hours at RT. After filtration
through a 0.45 .mu.m filter membrane, the volatiles were removed
via rotary evaporator at 150.degree. C. for 50 minutes. The product
was a clear colorless soft gel having a melting point higher than
80.degree. C.
[0049] In this Working Example #7, Bis-H was charged to a 4 neck
flask and heated to 40.degree. C., and then 22 ppm of BCF was
loaded to the Bis-H. The feed vessel of CPTM was also mixed with
BCF accounting for 96 ppm to the entire run. The CPTM feed was
started continuously and initiated fine. The reaction continued
throughout the entire run showing a steady heat of reaction with
the reaction only starting to slow near the very end but still
having a good rate. Therefore, no additional BCF was loaded to the
reaction mixture. At the end of the CPTM feed, a temperature ramp
to 70.degree. C. over 1 hour was started, an estimate indicated the
discernable exotherm stopped after 30 minutes. The reaction mixture
was then held for 1 hour at 70.degree. C. after the ramp to
complete the reaction and analyzed. The analysis indicated
>99.5% conversion of the methoxysilane to Si--O--Si
linkages.
[0050] In this Comparative Example #3, MH-1109 was combined with 50
ppm BCF in a flask. Silanol Fluid (DP 35) was combined with 50 ppm
BCF in a feed vessel. After feeding half the mixture of silanol
fluid containing 50 ppm BCF into the catalyzed mixture of MH-1109
and 50 ppm BCF, the reaction mixture in the flask gelled. This
comparative example showed that the order of addition is not
effective for the OH functional polyorganosiloxane (silanol fluid)
tested under these conditions.
INDUSTRIAL APPLICABILITY
[0051] Boron--containing Lewis acids, such as
tris(pentafluorophenyl)borane, may be quickly deactivated in the
presence of silicon hydrides. The inventors surprisingly found that
the boron--containing Lewis acid may be combined with an
alkoxysilyl functional organosilicon compound to form a catalyzed
mixture, and thereafter the catalyzed mixture can be fed into a
reactor containing a silicon hydride functional organosilicon
compound, thereby controlling the resulting the exotherm and
obtaining complete reaction (higher yields) with lower catalyst
levels and more control than using a different order of addition.
Furthermore, the inventors surprisingly found that lower
temperatures increase the reactivity as well as catalyst
lifetime.
[0052] The polyorganosiloxanes prepared by the method describe
herein find use in various applications as, including, but not
limited to, a dispersant, a wetting agent, an antiblocking
additive, a surface tension modifier, a surface treating agent, an
additive for agricultural compositions, an additive for coatings,
an additive for paints, a cosmetic ingredient, or a siloxane
modifier.
Definitions and Usage of Terms
[0053] Abbreviations used in the specification have the definitions
in Table 5, below.
TABLE-US-00002 TABLE 5 Abbreviations Abbreviation Definition DP
degree of polymerization g gram GC gas chromatography Me methyl mL
milliliters NMR nuclear magnetic resonance ppm parts per million RT
room temperature of 25.degree. C. .mu.m micrometer
[0054] All amounts, ratios, and percentages are by weight unless
otherwise indicated. The amounts of all starting materials in a
composition total 100% by weight. The SUMMARY and ABSTRACT are
hereby incorporated by reference. The articles `a`, `an`, and `the`
each refer to one or more, unless otherwise indicated by the
context of specification. The singular includes the plural unless
otherwise indicated. The disclosure of ranges includes the range
itself and also anything subsumed therein, as well as endpoints.
For example, disclosure of a range of 2.0 to 4.0 includes not only
the range of 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0
individually, as well as any other number subsumed in the range.
Furthermore, disclosure of a range of, for example, 2.0 to 4.0
includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6
to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the
range. Similarly, the disclosure of Markush groups includes the
entire group and also any individual members and subgroups subsumed
therein. For example, disclosure of the Markush group a hydrogen
atom, an alkyl group, an alkenyl group, or an aryl group, includes
the member alkyl individually; the subgroup alkyl and aryl; and any
other individual member and subgroup subsumed therein.
[0055] "Alkyl" means a branched or unbranched, saturated monovalent
hydrocarbon group. Examples of alkyl groups include methyl, ethyl,
propyl (including n-propyl and/or iso-propyl), butyl (including
iso-butyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl
(including, iso-pentyl, neopentyl, and/or tert-pentyl); and
n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl, as well as
branched saturated monovalent hydrocarbon groups of 6 or more
carbon atoms. Alkyl groups have at least one carbon atom.
Alternatively, alkyl groups may have 1 to 12 carbon atoms,
alternatively 1 to 10 carbon atoms, alternatively 1 to 6 carbon
atoms, alternatively 1 to 4 carbon atoms, alternatively 1 to 2
carbon atoms, and alternatively 1 carbon atom.
[0056] "Aralkyl" and "alkaryl" each refer to an alkyl group having
a pendant and/or terminal aryl group or an aryl group having a
pendant alkyl group. Exemplary aralkyl groups include benzyl,
tolyl, xylyl, phenylmethyl, phenylethyl, phenyl propyl, and phenyl
butyl. Aralkyl groups have at least 7 carbon atoms. Monocyclic
aralkyl groups may have 7 to 12 carbon atoms, alternatively 7 to 9
carbon atoms, and alternatively 7 to 8 carbon atoms. Polycyclic
aralkyl groups may have 7 to 17 carbon atoms, alternatively 7 to 14
carbon atoms, and alternatively 9 to 10 carbon atoms.
[0057] "Alkenyl" means a branched, or unbranched monovalent
hydrocarbon group, where the monovalent hydrocarbon group has a
double bond. Alkenyl groups include vinyl, allyl, and hexenyl.
Alkenyl groups have at least 2 carbon atoms. Alternatively, alkenyl
groups may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon
atoms, alternatively 2 to 6 carbon atoms, alternatively 2 to 4
carbon atoms, and alternatively 2 carbon atoms.
[0058] "Alkynyl" means a branched, or unbranched monovalent
hydrocarbon group, where the monovalent hydrocarbon group has a
triple bond. Alkynyl groups include ethynyl and propynyl. Alkynyl
groups have at least 2 carbon atoms. Alternatively, alkynyl groups
may have 2 to 12 carbon atoms, alternatively 2 to 10 carbon atoms,
alternatively 2 to 6 carbon atoms, alternatively 2 to 4 carbon
atoms, and alternatively 2 carbon atoms.
[0059] "Aryl" means a hydrocarbon group derived from an arene by
removal of a hydrogen atom from a ring carbon atom. Aryl is
exemplified by, but not limited to, phenyl and naphthyl. Aryl
groups have at least 5 carbon atoms. Monocyclic aryl groups may
have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and
alternatively 6 carbon atoms. Polycyclic aryl groups may have 10 to
17 carbon atoms, alternatively 10 to 14 carbon atoms, and
alternatively 12 to 14 carbon atoms.
[0060] "Carbocycle" and "carbocyclic" refer to a hydrocarbon ring.
Carbocycles may be monocyclic or polycyclic, e.g., bicyclic or with
more than two rings. Bicyclic carbocycles may be fused, bridged, or
spiro polycyclic rings. Carbocycles have at least 3 carbon atoms.
Monocyclic carbocycles may have 3 to 9 carbon atoms, alternatively
4 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
Polycyclic carbocycles may have 7 to 17 carbon atoms, alternatively
7 to 14 carbon atoms, and alternatively 9 to 10 carbon atoms.
Carbocycles may be saturated (e.g., cyclopentane or cyclohexane),
partially unsaturated (e.g., cyclopentene or cyclohexene), or fully
unsaturated (e.g., cyclopentadiene or cycloheptatriene).
[0061] "Cycloalkyl" refers to a saturated hydrocarbon group
including a carbocycle. Cycloalkyl groups are exemplified by
cyclobutyl, cyclopentyl, cyclohexyl, and methylcyclohexyl.
Cycloalkyl groups have at least 3 carbon atoms. Monocyclic
cycloalkyl groups may have 3 to 9 carbon atoms, alternatively 4 to
7 carbon atoms, and alternatively 5 to 6 carbon atoms. Polycyclic
cycloalkyl groups may have 7 to 17 carbon atoms, alternatively 7 to
14 carbon atoms, and alternatively 9 to 10 carbon atoms.
[0062] "Monovalent hydrocarbon group" means a univalent group made
up of hydrogen and carbon atoms. Monovalent hydrocarbon groups
include alkyl, aralkyl, alkenyl, alkynyl, and cycloalkyl groups as
defined above.
[0063] "Monovalent halogenated hydrocarbon group" means a
monovalent hydrocarbon group where one or more hydrogen atoms
bonded to a carbon atom have been formally replaced with a halogen
atom. Halogenated hydrocarbon groups include haloalkyl groups,
halogenated carbocyclic groups, and haloalkenyl groups. Haloalkyl
groups include fluorinated alkyl groups and fluorinated cycloalkyl
groups such as trifluoromethyl (CF.sub.3), fluoromethyl,
trifluoroethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl,
4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl,
5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl,
8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl,
2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and
3,4-difluoro-5-methylcycloheptyl; and chlorinated alkyl and
chlorinated cycloalkyl groups such as chloromethyl, 3-chloropropyl
2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl. Haloalkenyl
groups include chloroallyl.
[0064] The term "comprising" and derivatives thereof, such as
"comprise" and "comprises" are used herein in their broadest sense
to mean and encompass the notions of "including," "include,"
"consist(ing) essentially of," and "consist(ing) of". The term
"consisting of" and derivatives thereof, such as "consist of" and
"consists of" are used herein to mean be composed or made up of the
recited elements and excludes additional elements. The term
"consisting essentially of" and derivatives thereof, such as
"consist essentially of" and "consists essentially of" means and
encompasses "consist(ing) of" means including the recited elements
and may include additional elements that are not essential, e.g.,
to the invention. The use of "for example," "e.g.," "such as," and
"including" to list illustrative examples does not limit to only
the listed examples. Thus, "for example" or "such as" means "for
example, but not limited to" or "such as, but not limited to" and
encompasses other similar or equivalent examples.
[0065] Generally, as used herein a hyphen "-" or dash "-" in a
range of values is "to" or "through"; a ">" is "above" or
"greater-than"; a ".gtoreq." is "at least" or "greater-than or
equal to"; a "<" is "below" or "less-than"; and a ".ltoreq." is
"at most" or "less-than or equal to." On an individual basis, each
of the aforementioned applications for patent, patents, and/or
patent application publications, is expressly incorporated herein
by reference in its entirety in one or more non-limiting
embodiments.
[0066] It is to be understood that the appended claims are not
limited to express and particular compounds, compositions, or
methods described in the detailed description, which may vary
between particular embodiments which fall within the scope of the
appended claims.
EMBODIMENTS OF THE INVENTION
[0067] In a first embodiment, a method for preparing a
functionalized polyorganosiloxane comprises:
1) combining starting materials consisting essentially of
[0068] A) a boron--containing Lewis acid catalyst, and
[0069] B) an organosilicon compound having an average, per molecule
of at least 1 (alternatively 1 to 6, alternatively 1 to 4,
alternatively 1 to 3, and alternatively 1 to 2) silicon bonded
groups of the formula --OR.sup.2; wherein each R.sup.2 is an
independently selected monovalent hydrocarbon group of 1 to 6
carbon atoms, thereby forming a catalyzed mixture; and thereafter
2) adding the catalyzed mixture into a starting material
comprising
[0070] C) an organohydrogensiloxane having at least 1 silicon
bonded hydrogen atom per molecule, thereby preparing a product
comprising the functionalized polyorganosiloxane and a by-product
comprising HR.sup.2.
[0071] In a second embodiment, the method of the first embodiment
further comprises: adding additional boron--containing Lewis acid
catalyst, to C) the organohydrogensiloxane before adding the
catalyzed mixture to the organohydrogensiloxane in step 2).
[0072] In a third embodiment, he additional boron containing Lewis
acid catalyst in the second embodiment is present in an amount of 5
ppm to 250 ppm based on weight of C) the
organohydrogensiloxane.
[0073] In a fourth embodiment, in the method of any one of the
first to third embodiments, step 2) is performed at a temperature
of 5.degree. C. to 40.degree. C.
[0074] In a fifth embodiment, in the method of any one of the first
to fourth embodiments, A) the boron containing Lewis acid catalyst,
and when present, and any additional boron containing Lewis acid
catalyst, is provided in a total amount of 50 ppm to 6000 ppm
(alternatively 50 to 600 ppm), based on combined weights of B) the
organosilicon compound and C) the organohydrogensiloxane.
[0075] In a sixth embodiment, in step 1) of the method of any one
of the first to fifth embodiments, A) the boron containing Lewis
acid catalyst is present in an amount of 5 ppm to 600 ppm
(alternatively 15 ppm to 600 ppm and alternatively 15 ppm to 250
ppm) based on weight of B) the organosilicon compound.
[0076] In a seventh embodiment, the method of the first embodiment
is performed at a temperature of 5.degree. C. to 70.degree. C.
(alternatively 5.degree. C. to 65.degree. C., alternatively
10.degree. C. to 60.degree. C., alternatively 15.degree. C. to
50.degree. C., alternatively 20.degree. C. to 35.degree. C.,
alternatively 5.degree. C. to 30.degree. C., and alternatively
30.degree. C.).
[0077] In an eighth embodiment, the catalyzed mixture in step 1) is
heated to 40.degree. C. to 70.degree. C. before step 2) in the
method of the first embodiment.
[0078] In a ninth embodiment, the catalyzed mixture is cooled to
less than 40.degree. C. in step 2) of the method of the eighth
embodiment.
[0079] In a tenth embodiment, the method of the first embodiment is
performed at a temperature of 10.degree. C. to <25.degree.
C.
[0080] In an eleventh embodiment, the boron-containing Lewis acid
is a trivalent boron compound with at least one perfluoroaryl group
in the method of any one of the preceding embodiments.
[0081] In a twelfth embodiment, the boron-containing Lewis acid is
a trivalent boron compound with 1 to 3 perfluoroaryl groups per
molecule in the method of any one of the preceding embodiments.
[0082] In a thirteenth embodiment, the boron-containing Lewis acid
is selected from the group consisting of
(C.sub.5F.sub.4)(C.sub.6F.sub.5).sub.2B; (C.sub.5F.sub.4).sub.3B;
(C.sub.6F.sub.5)BF.sub.2; BF(C.sub.6F.sub.5).sub.2;
B(C.sub.6F.sub.5).sub.3; BCl.sub.2(C.sub.6F.sub.5);
BCl(C.sub.6F.sub.5).sub.2; B(C.sub.6H.sub.5)(C.sub.6F.sub.5).sub.2;
B(C.sub.6H.sub.5).sub.2(C.sub.6F.sub.5);
[C.sub.6H.sub.4(mCF.sub.3)].sub.3B;
[C.sub.6H.sub.4(pOCF.sub.3)].sub.3B; (C.sub.6F.sub.5)B(OH).sub.2;
(C.sub.6F.sub.5).sub.2BOH; (C.sub.6F.sub.5).sub.2BH;
(C.sub.6F.sub.5)BH.sub.2; (C.sub.7H.sub.11)B(C.sub.6F.sub.5).sub.2;
(C.sub.8H.sub.14)B(C.sub.6F.sub.5);
(C.sub.6F.sub.5).sub.2B(OC.sub.2H.sub.5); or
(C.sub.6F.sub.5).sub.2B--CH.sub.2CH.sub.2Si(CH.sub.3) in any one of
the first to twelfth embodiments.
[0083] In a fourteenth embodiment the boron containing Lewis acid
catalyst is tris(pentafluorophenyl)borane in the method of any one
of the preceding embodiments.
[0084] In a fifteenth embodiment, B) the organosilicon compound is
an alkoxysilane of formula: R.sup.1.sub.(4-a)SiOR.sup.2.sub.a,
where each R.sup.1 is independently selected from the group
consisting of a monovalent hydrocarbon group and a monovalent
halogenated hydrocarbon group, each R.sup.2 is a monovalent
hydrocarbon group of 1 to 6 carbon atoms, and subscript a is 1 to 4
(alternatively 3 to 4) in the method of any one of the preceding
embodiments.
[0085] In a sixteenth embodiment, the alkoxysilane in the fifteenth
embodiment has each R.sup.1 independently selected from the group
consisting of alkyl (e.g., methyl, ethyl, and propyl), alkenyl
(e.g., vinyl, allyl, and hexenyl), and haloalkyl (e.g.,
chloromethyl, chloropropyl, and trifluoropropyl).
[0086] In a seventeenth embodiment, B) the organosilicon compound
is an organosiloxane of formula:
R.sup.3.sub.2R.sup.XSiO--(R.sup.3.sub.2SiO).sub.b(--OSiR.sup.XR.sup.3.sub-
.2), where each R.sup.3 is independently selected from the group
consisting of a monovalent hydrocarbon group and a monovalent
halogenated hydrocarbon group, each R.sup.X is the group of formula
--OR.sup.2, and subscript b.gtoreq.1 (alternatively 1 to 2,000;
alternatively 1 to 50) in the method of any one of the first to
fourteenth embodiments.
[0087] In an eighteenth embodiment, the organosiloxane of the
seventeenth embodiment has each R.sup.3 independently selected from
the group consisting of alkyl (e.g., methyl, ethyl, propyl),
alkenyl (e.g., vinyl, allyl, hexenyl), aryl (e.g., phenyl), and
haloalkyl (e.g., chloromethyl, chloropropyl, trifluoropropyl).
[0088] In a nineteenth embodiment, starting material B) has unit
formula:
(R.sup.1SiO.sub.3/2).sub.m(R.sup.1R.sup.XSiO.sub.2/2).sub.n(R.sup.1R.sup.-
X.sub.2SiO.sub.1/2).sub.z, where subscript m is 0 to 20, subscript
n is 1 to 20, subscript z is 0 to 20 each R.sup.1 is independently
selected from the group consisting of a monovalent hydrocarbon
group and a monovalent halogenated hydrocarbon group, and each
R.sup.X is the group of formula --OR.sup.2 in the method of any one
of the first to fourteenth embodiments.
[0089] In a twentieth embodiment, C) the organohydrogensiloxane has
unit formula:
(HR.sup.4.sub.2SiO.sub.1/2).sub.g(R.sup.4.sub.3SiO.sub.1/2).sub.-
h(R.sup.4.sub.2SiO.sub.2/2).sub.i(HR.sup.4SiO.sub.2/2).sub.j, where
subscripts g, h, i, and j have values such that g.gtoreq.0,
h.gtoreq.0, a quantity (g+h) has an average value of 2, i.gtoreq.0,
j.gtoreq.0, and a quantity (g+j)>0, and the quantity (g+j) has a
value sufficient to provide the polyorganohydrogensiloxane with at
least 1% silicon bonded hydrogen atoms; and each R.sup.4 is an
independently selected monovalent hydrocarbon group (e.g., alkyl
such as methyl, aryl such as phenyl) in the method of any one of
the preceding embodiments. Alternatively, a quantity (i+j) is 0 to
1000.
[0090] In a twenty-first embodiment, subscript h=0, subscript j=0,
subscript g=2, subscript j is 0 to 500; and each R.sup.4 is an
alkyl group, such as methyl, in the organohydrogensiloxane in the
twentieth embodiment.
[0091] In a twenty-second embodiment, g=1, h=1, i=1, and j=0, and
the organohydrogensiloxane comprises formula:
HR.sup.4.sub.2SiO--(R.sup.4.sub.2SiO)--SiR.sup.4.sub.3, in the
organohydrogensiloxane in the twentieth embodiment.
[0092] In a twenty-third embodiment, the method of any one of the
preceding embodiments further comprises during and/or after step
2), removing a by-product comprising HR.sup.2 (e.g., by
burning).
[0093] In a twenty-fourth embodiment, the method of any one of the
preceding embodiments further comprises: 3) neutralizing residual
catalyst in the product (e.g., by adding alumina).
* * * * *