U.S. patent application number 15/060631 was filed with the patent office on 2016-06-30 for methods of making saccharide siloxane copolymers.
The applicant listed for this patent is DOW CORNING CORPORATION. Invention is credited to ERIC J. JOFFRE, ANIL K. TOMAR.
Application Number | 20160185916 15/060631 |
Document ID | / |
Family ID | 47605794 |
Filed Date | 2016-06-30 |
United States Patent
Application |
20160185916 |
Kind Code |
A1 |
JOFFRE; ERIC J. ; et
al. |
June 30, 2016 |
METHODS OF MAKING SACCHARIDE SILOXANE COPOLYMERS
Abstract
A method of making a saccharide siloxane copolymer includes
reacting an amine functional saccharide with an epoxy functional
silane containing at least one condensable or hydrolysable group.
This product is reacted with an oligomer to form the saccharide
siloxane copolymer.
Inventors: |
JOFFRE; ERIC J.; (MIDLAND,
MI) ; TOMAR; ANIL K.; (NEW HUDSON, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DOW CORNING CORPORATION |
Midland |
MI |
US |
|
|
Family ID: |
47605794 |
Appl. No.: |
15/060631 |
Filed: |
March 4, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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14371217 |
Jul 9, 2014 |
9315631 |
|
|
PCT/US2013/021537 |
Jan 15, 2013 |
|
|
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15060631 |
|
|
|
|
61587977 |
Jan 18, 2012 |
|
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Current U.S.
Class: |
527/300 |
Current CPC
Class: |
C08G 77/26 20130101 |
International
Class: |
C08G 77/26 20060101
C08G077/26 |
Claims
1. A method of making a saccharide siloxane copolymer, the method
comprising: (a) reacting an amine functional saccharide with an
epoxy functional silane containing at least one condensable or
hydrolysable group, the epoxy functional silane containing at least
one condensable or hydrolysable group being an amino radical, a
ketoxime, an ureido group, an acetoxy group, a carboxyl group, a
carboxylic amide radical, a cyano group, isocyanate group, sulfate
group, sulfate ester group, phosphate group, or a phosphate ester
group; (b) reacting the product of step (a) with an oligomer to
form the saccharide siloxane copolymer; and (c) optionally, further
including an endcapper to form the saccharide siloxane
copolymer.
2. The method of claim 1, wherein the amine functional saccharide
is selected from the group consisting of N-methylglucamine,
N-ethylglucamine and mixtures thereof.
3. The method of claim 1, wherein the amine functional saccharide
is selected from the group consisting of glucosamine,
galactosamine, muramic acid, mannosamine, chitosan, a chitosan
monomer, a chitosan oligomer, meglumine or mixtures thereof.
4. The method of claim 1, wherein the epoxy functional silane
containing at least one condensable or hydrolysable group is a
glycidoxypropyl functional silane.
5. The method of claim 1, wherein the epoxy functional silane
containing at least one condensable or hydrolysable group is an
epoxycyclohexylethyl functional silane, an epoxy alkane or a
limonene epoxide functional silane.
6. The method of claim 1, further including an endcapper to form
the saccharide siloxane copolymer, the endcapper being trimethyl
alkoxysilane.
7. The method of claim 1, wherein the oligomer is a partially
capped siloxane.
8. The method of claim 1, wherein the oligomer is a cyclic siloxane
or a disilanol siloxane.
9. The method of claim 1, wherein step (b) includes reacting the
product of step (a) with capped and uncapped oligomers.
10. The method of claim 1, wherein step (b) includes reacting the
product of step (a) with a silane endcapper and an uncapped
oligomer.
11. The method of claim 1, wherein the saccharide siloxane
copolymer is an emulsion.
12. The method of claim 1, wherein step (b) further includes using
an acid or base catalyst.
13. A method of making a saccharide siloxane copolymer, the method
comprising: (a) reacting N-methylglucamine, N-ethylglucamine or a
mixture thereof with an epoxy functional silane containing at least
one condensable or hydrolysable group being an amino radical, a
ketoxime, an ureido group, an acetoxy group, a carboxyl group, a
carboxylic amide radical, a cyano group, isocyanate group, sulfate
group, sulfate ester group, phosphate group, or a phosphate ester
group; and (b) reacting the product of step (a) with a disilanol
oligomer to form the saccharide siloxane copolymer.
14. The method of claim 2, wherein the amine functional saccharide
includes N-methylglucamine.
15. The method of claim 2, wherein the amine functional saccharide
includes M-ethylglucamine.
16. The method of claim 1, wherein the reaction of step (a) is
performed in a polar solvent.
17. The method of claim 16, wherein the polar solvent includes
methanol, ethanol, isopropanol, or any combination thereof.
18. The method of claim 1, further including an endcapper to form
the saccharide siloxane copolymer.
Description
CROSS REFERENCED TO OTHER APPLICATIONS
[0001] This application is a continuation U.S. Nonprovisional
application Ser. No. 14/371,217, filed Jul. 10, 2014, which is the
national stage entry of International Patent Application No.
PCT/US13/21537, filed Jan. 15, 2013, which claims priority to and
all the advantages of U.S. Provisional Application No. 61/587,977,
filed Jan. 18, 2012, the content of each of which are incorporated
herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] The present invention generally relates to methods of making
saccharide siloxane copolymers. More specifically, the present
invention generally relates to methods of making saccharide
siloxane copolymers that includes amine functional saccharides.
BACKGROUND OF THE INVENTION
[0003] Saccharide siloxanes are known in the art. Saccharide
siloxanes including a hydroxyl functional saccharide component and
an organosiloxane component were found to be useful when applied to
hair, skin, fabric, paper, wood and other substrates. Many
syntheses of saccharide functional siloxanes are based on an
aldonamide reaction of aminosiloxanes with gluconolactone or
lactobionolactone in a polar solvent. These polymers showed
instability due to hydrolytic cleavage of aldonamide linkage upon
aging. Other syntheses of saccharide functional siloxanes tend to
be disadvantageous because the reaction times are very sluggish. It
would be desirable to have a method of making saccharide siloxane
copolymers that significantly reduce the overall reaction time and
cost of manufacturing, while having a desired stability.
SUMMARY OF THE INVENTION
[0004] According to one method, a saccharide siloxane copolymer is
made by reacting an amine functional saccharide with an epoxy
functional silane containing at least one condensable or
hydrolysable group. The product of this reaction is reacted with an
oligomer to form the saccharide siloxane copolymer.
[0005] According to another method, a saccharide siloxane copolymer
is made by reacting N-methylglucamine or N-ethylglucamine with an
epoxy functional mono or di-alkoxy silane. The product of this
reaction is reacted with a disilanol oligomer to form the
saccharide siloxane copolymer.
DETAILED DESCRIPTION OF ILLUSTRATED EMBODIMENTS
[0006] A method of making a saccharide siloxane copolymer includes
(a) reacting an amine functional saccharide with an epoxy
functional silane containing at least one condensable or
hydrolysable group; and (b) reacting the product of step (a) with
an oligomer to form the saccharide siloxane copolymer. The method
of making the saccharide siloxane copolymers significantly reduced
the reaction times, which was unexpected. The resulting saccharide
siloxane copolymers are useful when applied to hair, skin, fabric,
paper, wood and other substrates.
[0007] Definitions and Usage of Terms
[0008] The art of "personal care" is intended to include any
topical treatment of any portion of the body that is intended to
provide a benefit to that portion of the body. The benefit may be
direct or indirect, and may be sensory, mechanical, cosmetic,
protective, preventative or therapeutic. While it is contemplated
that the human body is a particularly desirable target substrate
for the presently disclosed personal care compositions and products
formed by the methods of the present invention, it will be readily
apparent to one skilled in the art that other mammals having
similar tissues, especially keratinacious tissue such as skin and
hair, may be suitable target substrates and that therefore
veterinary applications are within the scope of the present
invention.
[0009] The personal care compositions formed by the methods of the
present invention are adapted to provide a benefit to a portion of
the body. As used herein, "adapted" means formulated in a manner
that permits safe and effective application of the benefit to the
portion of the body. As used herein, "safe and effective" means an
amount that provides a level of benefit perceivable by a consumer
seeking such a benefit without damaging or causing significant
discomfort to the consumer seeking such a benefit. A significant
discomfort is one that outweighs the benefit provided such that an
ordinary consumer will not tolerate it.
[0010] A person of ordinary skill in the personal care formulation
arts will appreciate the well-known criterion for selecting the
essential ingredients, optional additives and excipients that are
suitable according to the intended application of a particular
personal care composition. Non-limiting examples of additives that
may be formulated into the personal care compositions in addition
to the copolymers include: additional silicones, aerosols,
anti-oxidants, cleansing agents, colorants, additional conditioning
agents, deposition agents, electrolytes, emollients and oils,
exfoliating agents, foam boosters, fragrances, humectants,
occlusive agents, pediculicides, pH control agents, pigments,
preservatives, biocides, other solvents, stabilizers, sunscreening
agents, suspending agents, tanning agents, other surfactants,
thickeners, vitamins, botanicals, waxes, rheology-modifying agents,
anti-dandruff, anti-acne, anticarie and wound healing-promotion
agents.
[0011] It is not uncommon for certain benefits to be sacrificed in
personal care products formulated to provide multiple benefits in a
single product. For instance, with respect to hair, an increase in
conditioning benefit is often accompanied by a decrease in hair
"body" or volume. Addition of the copolymer may permit the
formulation of products that combine such benefits without
sacrificing the efficacy of some, and, indeed, in some formulations
it provides synergy with respect to the combination of benefits.
Personal care products formulated from the personal care
compositions comprising the copolymers formed by the methods of the
present invention may provide enhancements in benefits that
typically derive from effects which antagonize one another, for
example, enhancing both conditioning and curl retention benefits.
They also may provide thickening benefits in hair, skin, and color
cosmetics.
[0012] In addition, the addition of the copolymer formed by the
methods of the present invention to personal care compositions may
eliminate or lessen the need for certain other additives. For
example, because of the increased hydrogen bonding properties of
the copolymers, it is an effective thickening agent for cyclic
silicones and may therefore lessen the need for other thickening
additives, which may incidentally confer undesirable product
properties such as stringency, residue formation and/or
conditioning defects.
[0013] The copolymers formed by the methods of the present
invention may be a gum, waxy solid or solid at ambient conditions.
It should be noted, however, that there is a subset of the
copolymer that exists in a liquid form, and liquid dispersible
forms may also be produced by manipulating conditions such as
temperature. However, for some copolymers to achieve a viscosity
range that permits ready formation of dispersions, for example
solutions or emulsions, the copolymer must first be solubilized by
being dissolved in a suitable solvent or solvent blend.
[0014] The solubilized copolymer is then used to form a solution or
emulsion for ready delivery into the personal care composition. The
particular solvent blend is selected based upon the ionic
properties of the copolymer, and the suitability of that solvent
for the intended application. In one specific embodiment the
solvent blend comprises a mixture of paraffin and an alcohol. In a
very specific embodiment, the alcohol comprises isopropyl alcohol,
2-butyl-octanol, or a combination thereof. Alternatively, the
alcohol may comprise 2-butyl-octanol.
[0015] The term "dispersion" as used herein means a two-phase
system where a first phase comprises finally divided particles
distributed throughout a bulk second phase and the first phase
constitutes an "internal" or dispersed phase while the second phase
constitutes an "external" or continuous phase.
[0016] The term "solution" as used herein is intended broadly to
include mechanical dispersions, colloidal dispersions and true
solutions, and should not be construed as limited to the latter. A
solution is a dispersion comprising a uniformly dispersed mixture
wherein a first phase constitutes the solute and a second phase
constitutes the solvent.
[0017] The term "emulsion" as used herein means a dispersion
comprising a mixture of two immiscible liquids with the liquid
constituting the first, dispersed internal phase being suspended in
the second, continuous phase with the aid of an emulsifier.
[0018] All amounts, ratios, and percentages are by weight unless
otherwise indicated. As used herein, the articles `a` `an` and
`the` each refer to one or more, unless otherwise indicated by the
context of the application.
[0019] Methods of the Present Invention
[0020] A method of making a saccharide siloxane copolymer includes
(a) reacting an amine functional saccharide with an epoxy
functional silane containing at least one condensable or
hydrolysable group; and (b) reacting the product of step (a) with
an oligomer to form the saccharide siloxane copolymer.
[0021] The amine functional saccharide that may be used in methods
of the present invention are defined herein as including saccharide
derivatives of the same. In one embodiment, the amine functional
saccharides include at least two hydroxyl groups. The amine
functional saccharides typically include at least two or three
hydroxyl groups and at least one primary or secondary amine.
[0022] Non-limiting examples of amine functional saccharides to be
used in the methods of the present invention include, but are not
limited to, N-methylglucamine, N-ethylglucamine, glucosamine,
galactosamine, muramic acid, mannosamine, chitosan, chitosan
monomers, chitosan oligomers, meglumine and mixtures thereof. These
saccharides may contain primary or secondary amine functionality
that can react with epoxy groups of hydrolysable silane monomers or
polymers. It is contemplated that other amine functional
saccharides may be used in the methods of the present
invention.
[0023] The epoxy functional silanes to be used in the present
invention contain at least one condensable or hydrolysable group.
The term "hydrolysable" group means that these groups attached to
the silicon atom will react in the presence of moisture with
hydroxyl groups (e.g., silanols) or will react with other
hydrolyzable groups to form Si--O--Si bonds.
[0024] One example of an epoxy functional silane is an epoxy
functional mono or di-alkoxy silane. The more preferred alkoxy
groups include methoxy, ethoxy, propoxy, butoxy and mixtures
thereof. It is contemplated that other alkoxy groups may be used as
the condensable or hydrolysable groups such as isopropyl,
octadecyl, allyl, hexenyl, cyclohexyl, phenyl, benzyl,
beta-phenylethyl, any hydrocarbon ether radical such as
2-methoxyethyl, 2-ethoxyisopropyl, 2-butoxyisobutyl,
p-methoxyphenyl , --(CH.sub.2CH.sub.2O).sub.2CH.sub.3 and mixtures
thereof.
[0025] Other non-limiting examples of condensable or hydrolysable
groups that may be used in the epoxy functional silanes include,
but are not limited to, an amino radical, a ketoxime, an ureido
group, an acetoxy group, a carboxyl group, a carboxylic amide
radical, a cyano group, isocyanate group, sulfate group, sulfate
ester group, phosphate group, or a phosphate ester group. Examples
of these condensable or hydrolysable groups may be found in U.S.
Pat. No. 5,895,794.
[0026] Non-limiting examples of epoxy functionality silanes include
epoxycyclohexylethyl functional silanes, glycidoxypropyl functional
silanes, epoxy alkanes (e.g., 1,2 epoxy hexane), limonene epoxide
functional silanes and mixtures thereof.
[0027] Some non-limiting examples of glycidoxypropyl functional
silanes include 3-glycidoxypropylmethyldimethoxysilane,
3-glycidoxypropylmethyldiethoxysilane,
3-glycidoxypropylmethyldipropoxysilane,
3-glycidoxypropyldimethylmethoxysilane,
3-glycidoxypropyldimethylethoxysilane,
3-glycidoxypropyldimethylpropoxysilane and mixtures thereof. It is
contemplated that other glycidoxypropyl functional silanes may be
used.
[0028] The molar ratio of the amine functional saccharide to the
epoxy functional silane is generally from 1.2:1.0 to 0.5:1.0,
alternatively from 1.1:1.0 to 0.8:1.0, and alternatively from
1.05:1.0 to 0.95:1.0.
[0029] The reaction of an amine functional saccharide with an epoxy
functional silane containing at least one condensable or
hydrolysable group may be performed neat or in the presence of a
solvent. The reaction of an amine functional saccharide with an
epoxy functional silane may be performed in a polar solvent. Some
non-limiting examples of polar solvents that may be used include
methanol, ethanol, isopropanol or combinations thereof. It is
contemplated that other solvents may be used in the reaction of an
amine functional saccharide with an epoxy functional silane. All or
a portion of the solvent may be removed, for example, by stripping
or distillation, after this reaction is completed. This removal of
the solvents may take place using a vacuum.
[0030] The reaction of an amine functional saccharide with an epoxy
functional silane may be performed by heating. The exact
temperature depends on various factors including the specific
ingredients selected and type of solvent used. Temperatures,
however, generally range from 60 to 80.degree. C. and reaction time
may be several hours, alternatively, up to 5 hours, alternatively
with 0.5 to 2 hours.
[0031] The product of the reaction of an amine functional
saccharide with an epoxy functional silane depends on the starting
materials. Some non-limiting products include, but are not limited
to, NMG methyldimethoxysilane, NMG methyldiethoxysilane, NMG
dimethylmethoxysilane, NMG dimethylethoxysilane and NMG
triethoxysilane. The expected product mainly is a monomer but
dimers, trimers and oligomers may be possible. One non-limiting
example of a reaction between an amine functional saccharide with
an epoxy functional silane is
(3-glycidoxypropylmethyldimethoxysilane (Formula I) with
N-methylglucamine (NMG) (Formula II) to form NMG
methyldimethoxysilane (Formula III) using methanol as a
solvent.
##STR00001##
[0032] The product of the reaction between the amine functional
saccharide with the epoxy functional silane is then reacted with a
siloxane oligomer or polymer using condensation process to form the
saccharide siloxane copolymer.
[0033] The oligomers that may be used in the methods of the present
invention include disilanol functional oligomers. One non-limiting
example of a disilanol functional oligomer includes the
following:
##STR00002##
[0034] wherein m is generally from 3 to 1000, alternatively from 20
to 500, and alternatively from 30 to 200. It is contemplated that
other disilanol functional oligomers may be used in the methods of
the present invention. Useful oligomers for condensation chemistry
include disilanol siloxanes. For equilibration chemistry, cyclic
siloxanes and disilanol siloxanes may be used.
[0035] To assist in controlling the molecular weight or degree of
polymerization (DP) in the finalized saccharide siloxane copolymer,
an endcapper or endcapping agent may be reacted with the oligomer.
The endcapper typically includes a non-condensable end group and a
condensable end group.
[0036] One example of an endcapper is trimethyl alkoxysilane. The
more preferred alkoxy groups to be used in the endcapper include
methoxy, ethoxy, propoxy and mixtures thereof. Thus, examples of
endcappers include trimethyl methoxysilane, trimethyl ethoxysilane
and trimethyl propoxysilane. It is contemplated that other alkoxy
groups may be used in the endcapper.
[0037] In another example, the endcapper is hexamethyldisilazane
(HMDZ). It is contemplated that other endcappers may be used to
react with the oligomers used in the methods of the present
invention. Endcappers may include, but are not limited to, trialkyl
silanols, trialkyl chlorides, trimethylsilyl endcapped siloxanes
and hexamethyldisiloxanes.
[0038] The amount of endcapping on the oligomers is a function on
the molar ratio of endcapper to oligomer. The amount of endcapper
depends on the ratio of the DP of the final product to the DP of
the oligomer initially used. The molar ratio is also dependent on
siloxane DP and moles of silanols. The molar ratios of oligomer
silanols to endcapper is generally from 1:0.001 to 1:0.2 and
alternatively from 1:0.01 to 1:0.1.
[0039] For example, to prepare a 300 DP polymer starting with a 50
DP disilanol oligomer, the molar ratio of oligomer to a
difunctional endcapper would be 6:1. To prepare a 300 DP polymer
starting with a 10DP disilanol oligomer, the molar ratio of
oligomer to a difunctional endcapper would be 30:1. For a
monofunctional encapper, the molar ratios would be 3:1 and 15:1,
respectively. The molar ratios of disilanol oligomers to
difunctional endcappers are generally from 1:1 to 500:1,
alternatively from 2:1 to 250:1, alternatively from 3:1 to 150:1,
and alternatively from 4:1 to 30:1. The molar ratios of disilanol
oligomers to mono-functional endcappers are generally from 0.5:1 to
250:1, alternatively from 1:1 to 125:1, alternatively from 1.5:1 to
75:1, and alternatively from 2:1 to 15:1.
[0040] If the ratio of oligomer is greater than the endcapper on a
molar basis, a mixture of capped oligomers and uncapped oligomers
(e.g., disilanol oligomer) will be formed. Thus, the oligomers can
be a partially capped siloxane. The greater the amount of endcapper
used relative to the oligomer, the greater amount of endcapping
that occurs on the oligomer.
[0041] For example, using a molar ratio of 6:1 of Formula IV to
HDMZ, a mixture of Formula IV and capped oligomer (Formula V below)
would be formed.
##STR00003##
wherein m is generally from 3 to 1,000, alternatively, from 20 to
500, and alternatively from 50 to 300.
[0042] It is contemplated that other capped oligomers can be formed
than a silanol capped dimethylsiloxane.
[0043] The oligomer, whether capped, uncapped or a mixture thereof,
is then reacted with the product of the reaction between the amine
functional saccharide with the epoxy functional silane to form the
saccharide siloxane copolymer. To assist in the reaction with the
oligomer, acid or base catalysts may assist in the reaction.
Non-limiting examples of acids that may be used to assist in the
reaction with the oligomer include, but are not limited to,
octanoic acid catalyst, trifluoroacetic acid (TFAA), octanoic acid
(OA), trifluoromethanesulfonic acid, sulfuric acid, hydrochloric
acid and acetic acid.
[0044] Non-limiting examples of base catalysts that may be used to
assist in the reaction with the oligomer include, but are not
limited to, potassium hydroxide (KOH) and sodium hydroxide (NaOH),
potassium silonates, ammonia and ammonium hydroxides. When using a
base catalyst, the resulting product can be neutralized.
[0045] The reaction may be a condensation or an equilibrium
reaction. In one process, the condensation process is a silanol
condensation process.
[0046] In one example, the saccharide siloxane copolymers may be
synthesized by acid-or base-catalyzed condensation of
silanol-containing polysiloxanes with amide functional mono-or
di-condensable or hydrolyzable groups. Non-limiting examples of a
mono-or di-condensable or hydrolyzable groups are alkoxys. The
method for making the saccharide siloxane copolymers significantly
reduces the overall reaction time and cost of manufacturing.
[0047] For example, NMG methyldimethoxysilane may be reacted with
capped and uncapped oligomers using an acid based catalyst. One
non-limiting example is shown below:
##STR00004##
Formula III, which is a NMG silane, reacts with an uncapped
oligomer and a capped oligomer (Formulas IV and V, respectively)
with a catalyst to form Formula VI. Formula VI is a N-methyl
glucamine functional polysiloxane wherein x is generally from 1 to
30, alternatively from 1 to 20, and alternatively from 1 to 10; and
y is generally from 0 to 1,000, alternatively from 5 to 500, and
alternatively from 20 to 300. It is noted that water and methanol
are byproducts formed from the reaction above.
[0048] In another example, NMG methyldimethoxysilane may be reacted
with a silane endcapper and uncapped oligomer using an octanoic
acid catalyst. One non-limiting example is shown below:
##STR00005##
Formula III, which is a NMG silane, reacts with an uncapped
oligomer and a silane encapper (Formulas IV and VII, respectively)
to form Formula VIII.
[0049] The condensation reaction may be performed neat or in in
presence of a solvent. There are several types of solvents that may
be used in the condensation reaction. It is desirable to have a
solvent that would not interfere with the condensation chemistry
and would reduce the viscosity of the reaction mixture and the
product to facilitate the processing. For example, an aprotic
solvent may be used as a diluent due to very high viscosity of the
copolymer during the condensation process. Some non-limiting
examples of aprotic solvents that may be used in the condensation
reaction include ethyl acetate, butyl acetate, and toluene. Toluene
was desirable because it reduced the viscosity as well as being
compatible to the polymers. Other solvents such as alcohols may be
used, but it is desirable to remove the alcohols continuously
because they can hinder in the condensation reaction.
Alternatively, the copolymer may be left in the solvent after the
method is complete, for example, if the solvent is a suitable
carrier medium for a composition in which the copolymer will be
formulated.
[0050] The condensation reaction may be performed by heating. The
exact temperature depends on various factors including the specific
ingredients selected. Temperatures, however, generally range from
50 to 80.degree. C. and reaction time may be several hours,
alternatively, up to 10 hours, alternatively from 1 to 5 hours.
[0051] In addition to condensation routes, equilibrium processes
may be used in the methods of the present invention. In equilibrium
reactions, cyclic siloxanes and linear siloxanes are cleaved at
siloxane bonds to form reactive monomers and oligomers. Equilibrium
processes often contain a higher level of cyclic siloxanes in their
final products. A non-limiting example of a linear siloxane is a
low viscosity trimethylendblocked polydimethylsiloxane. It is
contemplated that other linear siloxanes, including
polyalkylsiloxanes, may be used in equilibrium processes.
[0052] Saccharide Siloxane Copolymer
[0053] The saccharide siloxane copolymers made by the methods of
the present invention have a desired aqueous stability. The
copolymers comprise a saccharide component and a siloxane
component. The siloxane component forms the backbone of the
copolymer molecule. Saccharide components may be bonded to the
siloxane backbone in terminal groups, pendant groups, or both
terminal and pendant groups. Alternatively, the saccharide
component may be bonded to the siloxane backbone in a pendant
group. Without wishing to be bound by theory, it is thought that
when the copolymer contains a pendant saccharide component, the
copolymer has improved stability in the presence of water. And,
when the copolymer contains pendant saccharide components and no
terminal saccharide components, the copolymer may exhibit even
further improved stability in the presence of water as compared to
a copolymer having terminal saccharide components and no pendant
saccharide components.
[0054] The saccharide siloxane copolymer may be a solid or a fluid
under ambient conditions of temperature and pressure, e.g., at
25.degree. C. and 760 mmHg. Whether the copolymer is a solid at
ambient conditions, or a fluid such as a liquid or a gum, depends
on various factors including the degree of polymerization (DP) of
the copolymers. The saccharide siloxane copolymer may have a DP
ranging from 3 to 1000, alternatively from 20 to 800, alternatively
from 50 to 500, and alternatively from 100 to 400.
[0055] The copolymer made by the methods of the present invention
described above may be formulated in a composition. The composition
may include the formed copolymer and an additional ingredient. The
additional ingredient depends on the specific formed copolymer and
the desired end use for the composition.
[0056] The composition may be a personal care composition. The
personal care composition may comprise: (1) the copolymer formed by
the methods of the present invention, and optionally (2) a carrier
medium suitable to permit topical application of the personal care
composition to a portion of the body. The personal care composition
is adapted to provide a benefit to the portion of the body to which
it is applied. In addition, the personal care composition may
optionally comprise a surfactant such as a nonionic surfactant.
[0057] Alternatively, the copolymer may be delivered to the
personal care composition as a dispersion. Diluting or dispersing
the copolymer makes it easier to process, and suitably employable
solvents include polydimethylsiloxanes, hydrocarbons, and alcohols.
Particularly suitable solvents are cyclic siloxanes,
hydrocarbon-alcohol mixtures, linear long chain alcohols and
branched long chain alcohols, and water.
[0058] Due to the compatibility of the copolymer with hydrocarbons,
silicones and alcohols, as well as with water, they may be
incorporated into both aqueous and non-aqueous based personal care
products, which provide a benefit to the portion of the body. In
embodiments where the portion of the body comprises hair, the
benefit may include increased ease and hold of hair-styling,
fixative effects and shine-enhancement.
[0059] The copolymers may be formulated into a composition in a
substantially pure form, or as a dispersion in the form of either a
solution or an emulsion. Depending on the form used, the copolymer
may be formulated into oil-in-water, water-in-oil,
water-in-silicone, and silicone-in-water systems. In the case of
some aqueous-based formulations the saccharide-siloxane copolymers
may be added directly to the formulation as a solid. In one
embodiment, the dispersion is in the form of a solution. The
solvent may be substantially aqueous or substantially non-aqueous
depending on the desired end use of the composition. In a specific
embodiment, the substantially non-aqueous solvent comprises a
volatile or non-volatile solvent and in a very specific embodiment
the substantially non-aqueous solvent comprises a volatile
hydrocarbon or a silicone or mixtures thereof. In a more specific
embodiment, the substantially non-aqueous solvent comprises a
silicone.
[0060] The term "volatile" as used herein means that the solvent
exhibits a significant vapor pressure at ambient conditions.
Examples of suitable volatile silicones include siloxanes such as
phenyl pentamethyl disiloxane, phenylethylpentamethyl disiloxane,
hexamethyldisiloxane, methoxy propylheptamethyl cyclotetrasiloxane,
chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl
disiloxane, octamethyl cyclotetrasiloxane, decamethyl
cyclopentasiloxane and mixtures thereof. Particularly suitable
silicones are the cyclomethicones. In a very specific embodiment
the volatile silicone comprises a cyclic siloxane.
[0061] The copolymer ingredient is typically added to the personal
care composition as a dispersion. Because of this, one may describe
its concentration with respect to either the dispersion component
or the personal care composition as a whole. In one embodiment
wherein the personal care composition comprises a dispersion, the
dispersion comprises from 0.1% to 50% copolymer by weight percent
and from 0.01% to 25% copolymer by weight percent of the
composition. In a more specific embodiment, the dispersion
comprises from 2% to 40% copolymer by weight percent and from 0.2%
to 10% copolymer by weight percent of the composition. In an even
more specific embodiment, the solution comprises 20% copolymer by
weight percent and 0.5 to 2% copolymer by weight of the
composition.
[0062] In one embodiment of the personal care composition, the
dispersion is in the form of an emulsion. The emulsion additionally
comprises a surfactant to maintain the dispersion, and water as the
continuous phase. The internal phase comprises the dispersed
solubilized copolymer. Nonionic, amphoteric (including
zwitterionic), anionic or cationic surfactants may all be suitable.
Oil-in-water emulsions are typically used because they are easier
to handle and disperse readily into water-based formulations.
[0063] An additional embodiment of the present invention is
directed to a copolymer emulsion. The emulsion is an oil-in-water
emulsion comprising an internal phase comprising the copolymer and
a continuous phase comprising water. The copolymer emulsion
comprises a surfactant that maintains the dispersion of the
internal phase due to its amphipathic character.
[0064] Other embodiments provide methods for preparing the
emulsions. The copolymer emulsions may be prepared either by: (1)
emulsifying preformed copolymers or (2) by polymerizing monomers
into a higher molecular weight copolymer in each individual
emulsion particle e.g., via emulsion or suspension polymerization.
In one embodiment, a surfactant-water blend is initially added to a
solubilized copolymer to establish the dispersion and fix the water
phase. Optional additional portions of water are added as required
by the desired property profile of the emulsion and/or its intended
applications.
[0065] It will be understood by one of ordinary skill in the art
that there is a continuum for the ease with which a desired
emulsion forms. Copolymer emulsions share similar constraints with
other emulsions. That is, they are thermodynamically unstable,
require a surfactant to maintain the dispersion, and need an input
of energy to initiate emulsification. Simple agitation via mixing
may be sufficient, or higher shear means including the employment
of high shear devices may be required. In other instances, a
polymer emulsification or inversion method may be needed.
[0066] A degree of agitation necessary to form the emulsion may
require employment of mixing devices. Mixing devices typically
provide the required energy input. Non-limiting examples of these
mixing devices spanning the shear range include: (1) a vessel with
an impeller, for example, propeller, pitched blade impeller,
straight blade impeller, Rushton impeller, or Cowles blade; (2)
kneading type mixers, for example, Baker-Perkins; (3) high shear
devices that use positive displacement through an orifice to
generate shear (e.g., a homogenizer, sonolator, or microfluidizer);
(4) high shear devices using a rotor and stator configuration
(e.g., colloid mills, homomic line mills, IKA, or Bematek); (5)
continuous compounders with single or dual screws; (6) change can
mixers with internal impellers or rotor/stator devices (e.g., a
Turello mixer); and (7) centrifugal mixers (e.g., Hauschild
speedmixers). Combinations of mixing devices can also provide
benefit. For example, a vessel with an impeller can be connected to
a high shear device to provide the mixing.
[0067] The choice of mixing device is based on the type of internal
phase to be emulsified. For example, low viscosity internal phases
can be emulsified using high shear devices that use positive
displacement through an orifice. However, in the case of high
viscosity internal phases, a rotor/stator device, twin screw
compounder or change can mixer are often better choices. In
addition, internal phases that contain hydrophilic groups are often
easier to emulsify and therefore a simple vessel configured with an
impeller may be sufficient.
[0068] The viscosity of the copolymer depends on various factors
including the molecular weight of the siloxane portion, the number
of saccharide units, the mole percent of saccharide units per
siloxane, and the external conditions such as temperature and
pressure. One skilled in the art would recognize that variable
internal phase viscosities may be achieved by varying proportions
in blends of copolymers with solvents or solvent mixtures.
[0069] The most desirable order of ingredient addition in the
preparation of the emulsion is determined empirically. For example,
a desirable order of addition for a thick-phase emulsification may
be: (1) solubilize the copolymer in a solvent or solvent blend to a
desired viscosity; (2) blend in a surfactant; (3) add water in
increments with shear until a thick phase emulsion forms; (4)
dilute with water to a desired concentration, with shear. A
desirable order of addition for a "pre-mix" with high shear may be:
(1) add all the water to a mixing vessel configured with an
impeller; (2) blend a surfactant with the water; (3) slowly add the
copolymer phase to the water to make a rough emulsion; and (4)
convey the rough emulsion through a high shear device until a
desired particle size is achieved.
[0070] Nonionic surfactants are suitable for making the emulsions
and include alkyl ethoxylates, alcohol ethoxylates, alkylphenol
ethoxylates, and mixtures thereof. Cationic, amphoteric and/or
anion surfactants are also suitable and are typically added in
addition to a nonionic surfactant. In a specific embodiment the
emulsion comprises a nonionic surfactant and in another specific
embodiment the emulsion comprises a cationic surfactant and a
nonionic surfactant.
[0071] In one embodiment of the personal care composition wherein
the copolymer is delivered to the composition in the form of an
emulsion, the emulsion comprises 5% to 95% copolymer by weight
percent of the emulsion and the composition comprises 0.01% to 25%
saccharide-siloxane by weight percent of the composition. In a more
specific embodiment, the emulsion comprises 10% to 60% copolymer by
weight percent of the emulsion and from 0.2% to 10% copolymer by
weight percent of the composition. In an even more specific
embodiment, the solution comprises 20 to 50% copolymer by weight
percent and 0.5 to 2% copolymer by weight of the composition.
[0072] The personal care compositions comprising the copolymer may
be formulated into personal care products. The personal care
products may be functional with respect to the portion of the body
to which they are applied, cosmetic, therapeutic, or some
combination thereof. Conventional examples of such products
include, but are not limited to: antiperspirants and deodorants,
skin creams, skin care lotions, moisturizers, facial treatments
such as acne or wrinkle removers, personal and facial cleansers,
bath oils, perfumes, colognes, sachets, sunscreens, pre-shave and
after-shave lotions, shaving soaps, and shaving lathers, hair
shampoos, hair conditioners, hair colorants, hair relaxants, hair
sprays, mousses, gels, permanents, depilatories, and cuticle coats,
make-ups, color cosmetics, foundations, concealers, blushes,
lipsticks, eyeliners, mascara, oil removers, color cosmetic
removers, wrinkle fillers, skin imperfection hiders, skin surface
smoothers, eyelash curlers, nail varnishes, hair make-up products,
eye shadows, body makeups, and powders, medicament creams, pastes
or sprays including anti-acne, dental hygienic, antibiotic, healing
promotive, nutritive and the like, which may be preventative and/or
therapeutic.
[0073] The personal care products may be generally formulated with
a carrier that permits application in any conventional form
including, but not limited to, liquids, rinses, lotions, creams,
pastes, gels, foams, mousses, ointments, sprays, aerosols, soaps,
sticks, soft solids, solid gels, and gels. What constitutes a
suitable carrier is readily apparent to one of ordinary skill in
the art.
[0074] In some personal care product embodiments comprising the
personal care composition, inclusion of the copolymer decreases the
need for other thickening agents in the formulation. In these
embodiments, desired viscosity or thickness of the product is
maintained with a lesser amount than is typical of conventional
thickeners. This is particularly desirable in products wherein the
thickening agent antagonizes a desirable effect of another benefit
agent, such as, for example, a conditioning agent. It is also
desirable in products where one or more thickening agents are
included for processing or formulation characteristics rather than
for any desired benefit they provide to the portion of the body to
which they are applied. In these cases, the copolymer may permit a
decrease in the one or more thickening agents that possess
antagonistic performance characteristics.
[0075] In some personal care product embodiments comprising the
copolymer made by methods of the present invention, inclusion of
the copolymer decreases the need for water-in-oil, and more
specifically water-in-silicone emulsifiers. The copolymer itself
may provide emulsification properties. In these embodiments,
desired emulsification of the product is maintained with a lesser
amount than is typical of conventional water-in-silicone
emulsifiers.
[0076] In a specific embodiment of the personal care product
comprising the personal care composition, the benefit comprises a
conditioning benefit and the portion of the body comprises hair.
Specific examples of the conditioning benefit include, but are not
limited to an anti-static, lubricity, shine, viscosity, tactile,
manageability, or a styling benefit. Non-limiting examples of
manageability benefits include ease of dry and/or wet combing.
Non-limiting examples of styling benefits include curl retention or
hair-relaxing benefits. The conditioner may be a rinse-off or
leave-in conditioner. In a specific embodiment, the conditioning
benefit comprises a curl-retention benefit.
[0077] Examples of suitable conditioning agents include, but are
not limited to, cationic polymers, cationic surfactants, proteins,
natural oils, silicones other than the copolymer, hydrocarbons,
nonionic surfactants, amphoteric surfactants, or mixtures thereof.
Examples of additional silicones which may be useful in the present
personal care compositions include, but are not limited to: alkyl
methyl siloxanes, cyclic siloxanes, gums, linear siloxanes, MQ
siloxane resins, MTQ siloxane resins, and polyether siloxane
copolymers.
[0078] The copolymers formed by the methods of the present
invention may assist in benefitting a portion of the body. One such
method comprises administration of a safe and effective amount of a
personal care product to a portion of the body. In one specific
embodiment, a method of treating hair comprising administering a
safe and effective amount of the personal care composition is
provided. A very specific embodiment provides a method of styling
and holding hair comprising administering a safe and effective
amount of the personal care composition. As used herein, "safe and
effective" means an amount that provides a level of benefit
perceivable by a consumer seeking such a benefit without damaging
or causing significant discomfort to the consumer seeking such a
benefit. A significant discomfort is one that outweighs the benefit
provided such that an ordinary consumer will not tolerate it.
[0079] Formulating personal care products with the personal care
composition comprising the copolymer formed by methods of the
present invention described above provides a thickening benefit. In
a specific embodiment, an antiperspirant, hair, skin and color
cosmetic products are provided. The antiperspirant product is
formulated with the personal care composition comprising the
copolymer as described above, wherein the benefit comprises a
thickening benefit sufficient to maintain suspension of
antiperspirant salts when the formulation comprises a substantially
less than typical amount of conventional thickeners. In specific
embodiments, the antiperspirant product is provided in the form of
a solid, a soft solid or a gel. In a more specific embodiment, the
solid form comprises a soft solid or a gel.
[0080] Another specific embodiment of the present invention is
directed to an emulsification benefit for water-in-oil and more
specifically, water-in-silicone formulations. The amount of
water-in-silicone formulation aids needed may be lower than typical
when the copolymer is used in the formulation. In a more specific
embodiment, an antiperspirant product is formulated with the
composition comprising the copolymer. In an even more specific
embodiment, the solid form comprises a gel.
[0081] Another specific embodiment provides a personal care product
comprising the copolymer made by the methods of the present
invention where the benefit comprises an enhanced conditioning
benefit and the portion of the body comprises skin. An embodiment
directed to a method of treating skin is provided that comprises:
(1) administration of a safe and effective amount of the personal
care product comprising the personal care composition; and (2)
rubbing the safe and effective amount into the skin.
[0082] Another specific embodiment is directed to a color cosmetic
product comprising the personal care composition where the benefit
comprises a cosmetic benefit. More specific embodiments are
directed to liquid foundations.
EXAMPLES
[0083] The following examples are included to demonstrate the
invention to one of ordinary skill. However, those of ordinary
skill in the art should, in light of the present disclosure,
appreciate that many changes can be made in the specific
embodiments which are disclosed and still obtain a like or similar
result without departing from the spirit and scope of the
invention. All amounts, ratios, and percentages are by weight
unless otherwise indicated.
[0084] The following ingredients were used in the examples. NMG
refers to N-methylglucamine. GPMDES refers to
3-glycidoxypropylmethyldiethoxysilane. GPMDMS refers to
glycidoxypropylmethyldimethoxysilane. AGE refers to allyl glycidyl
ether. Pt IV refers to a platinum catalyst in which Pt is complexed
with divinyltetramethyldisiloxane, also known as Karstedt's
catalyst. IPA refers to isopropanol. HMDZ refers to
hexamethyldisilazane. TFAA refers trifluoroacetic acid.
Example 1
Synthesis of NMG Functional Diethoxvsilane
[0085] GPMDES and NMG were obtained from SIGMA-ALDRICH.RTM. of St.
Louis, Mo. and used without any purification. The specification for
both showed >99% purity. A reaction was performed in a 200-proof
ethanol solvent using a rotary evaporator and a water bath set at
75.degree. C.
[0086] 37.27 g of GPMDES and 106 g of 200-proof ethanol were
charged in a 250-ml flask. 29.28 g of NMG powder were added to the
mixture. The molar ratio of GPMDES to NMG was 1:1. The flask
containing GPMDES, ethanol and NMG was attached to the rotary
evaporator and reacted at 75.degree. C. while mixing at 125 rpm.
The solid NMG dissolved and the reaction mixture became a clear
solution after 45 minutes. Samples were withdrawn for NMR analysis
after 1 and 3 hours and the ethanol solvent was stripped. The
product (NMG methyldiethoxysilane) was crystalline solid after the
ethanol was stripped under full vacuum. Proton Nuclear Magnetic
Resonance (H-NMR) confirmed the structure. 29Si NMR, however,
showed partial condensation of ethoxy groups. H-NMR also showed a
decrease in ethoxy CH3 protons by almost 60%.
[0087] The H-NMR of the product (NMG methyldiethoxysilane) also
showed that the ethoxy groups were intact when ethanol was present
in the product and were partially hydrolyzed when ethanol was
completely stripped. The 29Si NMR also confirmed the formation of
hydrolysis/condensation byproducts.
Example 2
Synthesis of NMG Functional Dimethoxysilane
[0088] Methoxy functional NMG-silane was prepared by reacting
3-glycidoxypropylmethyldimethoxysilane with NMG (both obtained from
SIGMA-ALDRICH.RTM. of St. Louis, Mo.) in methanol solvent. 40.0 g
of GPMDMS and 75.4 g of 200-proof methanol were charged in a 250-ml
flask. 35.4 g of NMG powder were added to the mixture. The molar
ratio of GPMDMS to NMG was 1:1. The flask containing GPMDMS,
methanol and NMG was attached to a rotary evaporator and reacted at
60.degree. C. while mixing at 125 rpm. The solid NMG dissolved and
the reaction mixture became a clear solution after 30 minutes. A
sample was withdrawn for NMR analysis after 105 minutes and the
methanol solvent was stripped. The product NMG
methyldimethoxysilane was crystalline solid after the methanol was
stripped under full vacuum. H-NMR confirmed the structure. 29Si NMR
showed partial condensation of methoxy groups.
Example 3A
NMG Siloxane Synthesis by Condensation Route
[0089] Synthesis of NMG-siloxanes was carried out by a silanol
condensation process. NMG-dialkoxy silanes were condensed with
silanol terminated polydimethylsiloxanes in the presence of acid or
base catalysts.
[0090] First, silanol fluid was reacted with HMDZ to partially cap
silanol groups. A TFAA catalyst was primarily used for silanol
capping reactions, but was also used for acid-catalyzed
silanol/alkoxysilane condensation reaction. In addition to the TFAA
catalyst, octanoic acid (OA) and trifluoromethanesulfonic acid
(TFAA) were also tested. Base-catalyzed condensation was performed
by using potassium hydroxide (KOH) as a base catalyst. Several
batches were synthesized to optimize the reaction conditions. 29Si
NMR monitored the reaction progress and molecular weight or degree
of polymerization (DP) of the sugar siloxane.
Example 3B
Acid-Catalyzed Condensation to Synthesize 300DP-2P-NMG Siloxane
[0091] Partial capping of silanol terminated 50 DP siloxane was
carried out by reacting HMDZ with silanol fluid in the presence of
a TFAA catalyst. To synthesize a 300 DP siloxane polymer from 50 DP
silanol fluid, six moles of silanol fluid were reacted with 1 mole
of HMDZ (two silanols out of twelve silanols were capped in the
reaction with HMDZ). The reaction was carried out at 80.degree. C.
for 4-5 hours, although the reaction may have completed in lesser
time (about 2 hours). The longer reaction time may also have caused
some condensation of silanols resulting in increased molecular
weight and leaving fewer free silanols for condensation with
NMG-alkoxy silanes.
Example 4
Synthesis and Testing of NMG-Siloxane Polymers
[0092] 315 g of silanol fluid having a DP of 50 with terminal
silanol functionality were charged in a 1-L flask fitted with
condenser, thermometer and a distilling receiver or distilling trap
(Dean-Stark). 2.29 g of HMDZ were added at room temperature and
mixed. The reaction mixture was heated slowly to 50.degree. C. and
TFAA catalyst (0.2 g) was added. Nitrogen gas was flushed through
the system to remove NH.sub.3 byproduct and the reaction
temperature was raised to 80.degree. C. The reaction mixture was
cooled after 5 hours and filtered for 29Si NMR analysis. The
polymer DP increased from 50 to 116 in the partially capped silanol
fluid product.
[0093] 23.0 g of NMG-methyldiethoxysilane (50% solution in ethanol)
were mixed with 255.2 g of partially capped silanol fluid in a
flask and heated to 80.degree. C. on a rotary evaporator while
mixing. The ethanol solvent was stripped at 15 mmHg vacuum. An
octanoic acid catalyst (0.9 g) was added and the condensation was
continued for 7.5 hours under vacuum. The reaction mixture slowly
became viscous due to condensation of NMG-methyldiethoxysilane with
silanol fluid. 29Si NMR analysis showed an increase in DP and
decrease in silanol contents. H-NMR also confirmed the presence of
N-methyl glucamine protons and CH.sub.2 protons attached to silicon
in the polymer.
[0094] The resulting NMG-siloxane polymer was mixed with 5 wt %
Isofol-12 (2-butyl octanol) diluent and emulsified to give a 50%
active oil-in-water emulsion. The emulsion was heat aged for 2
months at 45.degree. C. for thermal and hydrolytical stability
studies. Both room temperature and heat-aged NMG-siloxane emulsions
were evaluated for wet and dry combing force properties in hair
care application. Their performance was compared against a standard
cationic emulsion.
[0095] The hair treatment data showed that NMG-siloxane polymers
synthesized from acid condensation route performed as well as the
standard cationic emulsion. Specifically, testing was done on an
Instron device for both wet combing and dry combing. The results
were reported as an average combing force (kg) of 3 tresses times 5
pulls each. The room temperature and heat-aged NMG-siloxane
emulsions had higher wet average combing force (0.032 kg and 0.031
kg, respectively) than the standard cationic emulsion (0.021 kg).
The room temperature and heat-aged NMG-siloxane emulsions had lower
dry average combing force (each had 0.013 kg) than the standard
cationic emulsion (0.016 kg). Thus, the room temperature and
heat-aged NMG-siloxane emulsions had better dry combing forces than
the standard cationic emulsion, but not as good of wet combing
force as the standard cationic emulsion. The NMG-siloxane polymers
were also hydrolytically stable when emulsified and heat aged at
40.degree. C. for 2 months.
Example 5
Condensation Reaction of NMG-Siloxanes
[0096] NMG-siloxanes were prepared by condensation reaction of
NMG-methyldimethoxysilane with silanol fluid. 288.3 g of 50DP
silanol fluid were reacted with 2.23 g HMDZ for capping reaction in
the presence of 4-5 drops of TFAA catalyst. The reaction mixture
was slightly cloudy after 3.5 hours reaction due to the formation
of ammonium salts. The reaction mixture was filtered through a 5
micron filter press. 29Si NMR showed slightly lower capping and no
significant increase in degree of polymerization. 20.8 g
NMG-methyldimethoxysilane (50% in methanol) were mixed with capped
siloxane and heated to 80.degree. C. The methanol was stripped
under slight vacuum and 1.2 g octanoic acid catalyst was added for
silanol condensation. 1.0 g deionized water was added to enhance
hydrolysis of methoxysilane after 1.5 hours reaction. The reaction
mixture became viscous after 6 hours reaction. 29Si NMR showed
polymer DP increased to 137 and some unreacted silanols.
Example 6
One Step Synthesis of NMG Diethoxysilane
[0097] Attempts were also made to condense silanol fluid, HMDZ and
NMG-diethoxysilane in one step. 150 g silanol fluid having a DP of
50 were mixed with 1.55 g HMDZ, 9.5 g NMG-methyldiethoxysilane and
0.22 g trifluoroacetic acid. The reaction mixture was heated to
80.degree. C. and ethanol was removed under vacuum. Condensation
catalyst octanoic acid and catalytic amount of
aminoethylaminopropyl triethoxysilane were added and reacted under
15 mmHg vacuum. A polymer-like gel phase separated from the silanol
fluid after about a 1 hour reaction. It was found that HMDZ reacted
with NMG-diethoxysilane causing it to precipitate out of the
reaction mixture. The reaction mixture was a low viscosity polymer
after 5 hours condensation and no molecular weight build up was
observed.
Example 7
Condensation Reaction of Silanol Fluid
[0098] A condensation reaction between silanol fluid and
NMG-alkoxysilane was enhanced when a combination of octanoic acid
and HMDZ was used as catalyst. It is both an endcapper and a
co-catalyst with octanoic acid. 250 g of 50 DP silanol fluid were
reacted with 1.9 g of HMDZ using a TFAA catalyst at 80.degree. C.
for 4.5 hours. The siloxane DP increased to 116 and the ratio of
hydroxyl groups in each siloxane decreased. 75 g of a filtered
partially capped siloxane were then reacted with 7.0 g of
NMG-diethoxysilane in the presence of 1.0 g deionized water, 0.1 g
HMDZ and 0.2 g octanoic acid catalyst at 80.degree. C. under 15
mmHg vacuum. The polymer viscosity increased after 5 hours of
reaction time and DP increased to about 200 due to silanol
condensation.
Example 8
Condensation Reaction of Silanol Fluid
[0099] 8.9 g of NMG-diethoxysilane were directly condensed with 150
g of silanol fluid in the presence of an octanoic acid catalyst.
There was only a slight increase in siloxane molecular weight after
5 hours condensation (the siloxane DP was 85). A clear and soft
viscous polymer was obtained after 9 hours reaction at
85-90.degree. C. in the presence of TFAA catalyst. The polymer was
then capped with trimethylsilyl groups by using HMDZ. The 29Si NMR
showed that the siloxane DP was about 122 and there were still
uncondensed silanols present.
Example 9
Condensation Reaction of Silanol Fluid
[0100] 151 g of 50DP silanol and 100 g of toluene were mixed
together in a round bottom flask fitted with a condenser, a Dean
Stark receiver, mechanical stirrer and a thermometer. A clear
solution was formed after mixing. 1.15 g of HMDZ were added and
mixed at room temperature for 5 minutes before adding 4-5 drops of
TFAA catalyst. The reaction occurred at 60.degree. C. for 1 hour.
29Si NMR showed that partial capping of silanol with trimethylsilyl
group occurred without increase in polymer DP. 2.7 g of octanoic
acid were then mixed to adjust the pH to 6.5. 13.0 g of
NMG-methyldiethoxysilane were then mixed and reacted at
85-110.degree. C. for 5.5 hours. A gel-like polymer phase separated
in toluene but dissolved when 50 g IPA were added and mixed. IPA
and toluene were later stripped under full vacuum and a soft sticky
polymer was obtained having a DP of 112.
Example 10
Condensation of Silanol
[0101] 150 g of 50DP silanol and 100 g of toluene were mixed
together in a round bottom flask fitted with a condenser, a Dean
Stark receiver, mechanical stirrer and a thermometer. A clear
solution was formed. 1.80 g of HMDZ were added and mixed at room
temperature for 5 minutes before adding 2 drops of TFAA catalyst.
The reaction occurred at 80.degree. C. for 2 hours. 29Si NMR showed
that partial capping of silanol with trimethylsilyl group occurred
and polymer DP increased to 74. 1.0 g of octanoic acid was then
mixed to adjust the pH to 5.0. 13.0 g of NMG-methyldiethoxysilane
were then mixed and reacted at 85-95.degree. C. for 2.5 hours. 3-4
drops of TFAA were then added to enhance the condensation reaction.
A sticky gel-like polymer having a DP of 100 was obtained after
toluene was stripped under full vacuum. 29Si NMR analysis indicated
only a slight increase in siloxane DP with some Si-OH converting to
Si-OZ where OZ may be ethoxy or octanoic acid.
Example 11A
Synthesis of NMG Siloxane in Ethyl Acetate Solvent, Acid
Condensation
[0102] Acid-catalyzed condensation of NMG-diethoxy silane with 50DP
silanol fluid was carried out in ethyl acetate or butyl acetate
solvent. These solvents were not as effective as toluene for
condensation reaction due to compatibility. A hazy viscous polymer
was observed in the case of ethyl acetate while self-condensation
of NMG-diethoxy silane was observed when butyl acetate solvent was
used and a gel-like material precipitated out of silanol fluid.
There were also limitations of maximum reaction temperature of
77-80.degree. C. with ethyl acetate due to its lower boiling point
than toluene.
Example 11 B
Base-Catalyzed Condensation to Synthesize 300DP-2P-NMG Siloxane
[0103] Base-catalyzed condensation reactions were performed by
using 50% KOH solution as a catalyst. NMG-siloxanes polymers were
successfully prepared both by equilibrium and condensation routes.
The condensation reaction was faster with KOH than tested
acid-catalyzed condensation routes. More cyclic siloxanes, however,
were produced during an equilibrium process using KOH as a
catalyst.
Example 12
NMG-Siloxane by Base-Catalyzed Equilibrium Process
[0104] 150.7 g of silanol terminated polydimethylsiolxane, 10.48 g
of NMG-methyldimethoxysilane (50% solution in methanol) and 1.02 g.
5 cst 200-fluid, a low viscosity trimethylendblocked
polydimethylsiloxane, were mixed together and condensed using 0.60
g of KOH catalyst at about 100.degree. C. Methanol and water were
removed by using a Dean-Stark receiver. A slight increase in
viscosity was observed. Viscosity increased significantly when an
equilibrium reaction was performed at 130.degree. C. 29Si NMR
showed only a trace amount of unreacted silanols, and 3.7 mol % Da
cyclics having a DP of 168. H-NMR confirmed the NMG functionality
and dimethyl siloxane units. The product was neutralized by glacial
acetic acid after dissolving in IPA and Isofol-12. The IPA was then
stripped to get a clear high viscosity NMG-siloxane.
Example 13
NMG-Siloxane by Base-Catalyzed Equilibrium Process Without
Camping
[0105] A high viscosity polymer was obtained when 50DP silanol
fluid was condensed with NMG-methyldiethoxysilane at 85.degree. C.
in the presence of 0.2 wt % KOH. No capping agent was used for
terminal capping. 29Si NMR showed the formation of 300-DP
NMG-siloxane polymer containing pendant NMG functionality after 9
hours reaction at 80-85.degree. C. Cyclic siloxanes were also
formed as shown by the 29Si NMR peak testing.
[0106] While the present invention has been described with
reference to one or more particular embodiments, those skilled in
the art will recognize that many changes may be made thereto
without departing from the spirit and scope of the present
invention. Each of these embodiments, and obvious variations
thereof, is contemplated as falling within the spirit and scope of
the invention.
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