Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~6~
] 60SI-809
.
DURABLE SILICONE EMULSION POLISH
BACKGROUND OF THE INVENTION
This invention relates to polishes. More
particularly, it relates to silicone emulsion polishes
and dressings which form detergent-resistant, durable
protective coatings on solid surfaces.
The present invention also relates to the
preparation of the emulsions and polishes of the
present invention by the process of emulsion
polymerization.
Silicone-emulsion polishes and dressings,
commonly used to improve the appearance of and to
protect household products, luggage, fabrics, marine
and auto vinyl, sporting goods, and the like, are
favored for their glossiness and ease of application;
however, they lack durability, especially after
detergent washing, and must be frequently reapplied.
Amine-catalyzed resinous polysiloxane wood
varnishes are disclosed in U.S. Patent 3,350,349 to Hyde
issued October 31, 1967, but their application, varnish-
like properties and the resultant hard, dry film make
them unsuitable for many polishing needs.
Sanders, U.S. Patents Nos. 4,246,029 issued
January 20, 1981 and 4,247,330 issued January 27, 1981,
disclose an aqueous emulsion containing (1) a mixture
of silicone compounds consisting of (a) an amino-
functional silicone fluid and (b) a cyclic siloxane,
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60SI-809
-- 2 ~
(2) an aliphatic alcohol having from 1 to 4 carbon atoms,
(3) sufficient carboxylic acid to neutralize the
aminofunctional groups and (4) cationic emulsifying
agents, if desired. Such aqueous emulsions are said to
be storage stable and suitable for dispensing in
automatic car washes to impart a detergent resistant
protective coating.
Martin, U.S. Patent 3,960,575 issued June 1, 1976,
teaches that improved detergent resistant polish
compositions can be prepared by adding aminofunctional
silicone fluids obtained by equilibrating with cyclic
siloxanes to conventional polish compositions.
While each of the foregoing discloses useful polish
compositions, the emulsions are prepared by mechanical
means well known to those skilled in the art and thus do
not possess properties such as durability and resistance
to washing to the extent which may be desired.
Consequently, there has been a growing need to develop an
easily applied polish, suitable for diverse polishing
needs, which will exhibit improved durability, resist
washings, and afford increased protection to polished
surfacesA
The present applicants, in an attempt to overcome
the shortcomings of the prior art, prepared emulsions by
the process known as emulsion polymerization rather than
by the heretofore accepted mechanical methods. Those
skilled in the art recognize that emulsions prepared by
emulsion polvmerization are characterized by extreme
stability and extremely fine particle size. Moreover,
those skilled in the art appreciate that the problems
associated with preparing emulsions by emulsion
polymerization are substantially different from those
associated with preparing emulsions by mechanical means.
Hyde et al., U.S~ Patent No. 2,891,920 issued June
23, 1959, were the pioneers in the field of emulsion
6a~
60SI-809
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polymerization. Hyde et al. recognized that improved
emulsions could be prepared by carrying out the
polymerization of low molecular weight siloxanes while
the siloxanes were dispersed in an aqueous media instead
of emulsifying higher molecular weight siloxanes which
were dissolved in an organic solvent. In carrying out
the method of Hyde et al. the siloxane is first
dispersed in the water, preferably with the use of an
emulsifying agent, and a suitable polymerization catalyst
is thereafter added to promote polymerization to the
desired degree. Polymerization is carried out below the
boiling point of water, although temperatures a~ove 100 C
can be employed if the polymerization is carried out in
a closed system. Hyde et al. reveal that as the
polymerization proceeds the viscosity of the siloxane
increases but the size of the emulsion droplets decreases
and it is believed that this is what causes the extremely
stable emulsions obtained by emulsion polymerization.
Oppliger, U.S~ Patent No~ 3,208,911 issued
20 September 28, 1965, discloses a method for treating hair
to improve the appearance, manageability and softness of
the hair consisting essentially of submitting the hair to
the action of an ionic oil-in-water emulsion, said emulsion
being composed of an organosiloxane in an amount of from
25 0~01 to 90 percent by weight based upon the total weight
of the emulsion and an ionic emulsifying agent in an
amount of from 2 to 25 percent by weight based upon the
weight of the organosiloxane and an alkaline catalyst in an
amount of from one alkaline molecule per 100 silicon atoms
30 to one alkaline molecule per -50,000 silicon atoms,
inclusive, and the necessary water to give the desired
solids content, said alkaline catalyst being selected from
the group consisting of (a) R4NOH and (b) R4NX admixed with
Q, wherein R is alkyl, X is an acid anion, and Q is an
alkaline compound selected fram the group consisting Of
~r~6.~
60SI-809
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ammonia, alkali metal hydroxides, alkali metal carbonates
and organic amines, said ionic oil-in-water emulsion
being prepared by polymerizing the organosiloxane in an
aqueous medium in the presence of said alkaline catalyst
until a viscosity of 6.5 cs. to 2.5 x 106 cs~ is obtained.
Findlay et al., U.S. Patent No. 3,294,725 issued
December 27, 1966, discloses an emulsion polymerization
process similar to that of Hyde et al., however, Findlay
et al. teaches the use of a surface active sulfonic acid
as a polymerization catalyst rather than a strong mineral
acid or strong alkali. A nonionic or anionic emulsifying
agent can be employed if so desired.
Axon, U.S. Patent No. 3,360,491 issued December 26,
1967, relates to emulsion polymerization of organosiloxanes
wherein the polymerization catalyst is an organic sulfate
of the general formula ROSO2OH, wherein R is a monovalent
aliphatic hydrocarbon radical of at least 6 carbon atoms.
As is the case in Findlay et al., a nonionic or anionic
emulsifying agent can be employed if so desired.
Cekada et al., U.S. Patent No. 3,532,729 issued
October 6, 1970, teaches the preparation of mercapto-
siloxanes by emulsion polymerization.
Sorkin, U.S. Patent No. 3,624,017 issued November
30, 1971, disc]oses an aqueous emulsion of a copolymer of
80 to 98 mole percent dimethylpolysiloxane and 2 to 20
mole percent R SiO3/2 in which R is methyl or vinyl, said
emulsion having been prepared by emulsion polymerization
of a mixture of dimethylpolysiloxane and R SiX3, in which
X is a hydrolyzable group producing a water soluble by-
product such as halogen.
~68Z~
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- N(Rl)2 - ON = C(R )2'
~ - 2
- ON = R
RlC ( = 0)
RlO (R20) and
- ON (R )2 in which R is a monovalent
hydrocarbon or halocarbon radical and R is a divalent
hydrocarbon or halohydrocarbon radical. It should be
noted that the nitrogen-containing radicals of Sorkin are
hydrolyzable and henee will not remain bonded to the
siloxane ehain in an aqueous medium.
Campbell, U.S. Patent No. 3,634,297 issued
January 11, 1972, provides a proeess for binding a pigment
to glass fabric whieh comprises (A) applying to the glass
fabrie an aqueous emulsion of a eopolymer eonsisting
essentially of (a) 50 to 90 mole pereent of (CH3)2SiO
units and (b) 10 to 50 mole percent of R SiO3/2 units,
wherein R is an alkyl or alkenyl radieal of 1 to 3 earbon
atoms, the 3,3,3-trifluoropropyl radieal, or a phenyl
radieal, said copolymer having been prepared by emulsion
polymerization; and a water dispersible pigment; and (B)
drying the glass fabric.
Ikoma, U.S. Patent No. 3,697,469 issued Oetober 10,
1972, deseribes an emulsion polymerization proeess
involving (i) emulsifying, in water eontaining a salt-type
anionie surfaee aetive agent, an organosiloxane of the
formula
Ra SiO 4 a
where R is a hydrogen atom or a monovalent hydroearbon
~36~3~Z
60SI-809
-- 6
radical or a halogen substituted monovalent hydrocarbon
radical, and a has an average value of 1 to 3, and then
~ii) contacting said emulsion with an acid-type cationic
exchange resin so that said surface active agent may be
ion-exchanged from salt type into acid type, thereby
acquiring catalytic power and at the same time starting
the polymerization of said organosiloxane by making said
emulsion an acid medium with a pH value of less than 4.
Backderf, U.S. Patent No. 3,706,697 issued
December 19, 1972, relates to aqueous emulsion
polymerization of acryloxyalkyl-alkoxysilane, alkyl
acrylic esters, and optionally other vinyl monomers to
provide copolymers curable at low temperatures. The
acryloxy functional site of the silane is said
unexpectedly not to hydrolyze upon polymerization and
thereby serve as a crosslinking site for reaction with
the alkyl acrylic ester.
Hilliard, U.S. Patent No. 3,898,300 issued July
29, 1975, describes an emulsion polymerization method
to produce a polymeric styrene-acrylo-nitrile-
polyorganosiloxane compositionA
Huebner et al., U.S. Patent No. 4,288,356 issued
September 8~ 1981, discloses a method of blending an
emulsion of an emulsion polymerized compolymer of an
organic monomer and an organosilicon monomer and an
emulsion of a polydiorganosiloxane to provide a reinforced
elastomeric product.
The prior art directed to emulsions prepared by
emulsion polymerization does not disclose aminofunctional
emulsion polymerized polysiloxanes or the use of such
polysiloxanes to provide improved polishes. Also, the
prior art does not disclose the use of certain ethers as
emulsifiers so as to allow utilization of higher
temperatures and faster emulsion polymerization. Nor
does the prior art disclose the use of cationic catalysts,
6~Z
60SI-809
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especially in combinations with the aforementioned ether
emulsifying agents, so that emulsion polymerized
polysiloxane emulsions can be stripped of cyclic or
other low molecular weight siloxanes from which they
were prepared. Furthermore, prior art emulsion
polymerization processes do not reveal the advantage of
including a mixture of alkoxy functional silanes and
aminofunctional silanes in the resulting emulsion
compositions.
It has now been discovered that aminofunctional
silicone polymer emulsions prepared by emulsion
polymerization can be used to form easily applied
polishes which adhere well to surfaces and resist
removal even from many detergent washings. Used as
textile finishes, the aminofunctional emulsions impart
good hand qualities and water repellency to fabrics.
SUMMAP~Y OF THE INVENTION
Accordingly, it is an object of the present
invention to provide an aminofunctional emulsion which
is resistant to removal by detergent washing from the
surface it is applied to.
It is a further object of the present invention to
provide a silicone emulsion polish composition which is
easily applied to solid surfaces and resists removal by
detergent washing.
It is a further object of the present invention to
provide a polish composition which is applicable to a
wide range of solid surfaces and which affords good
coverage of surface blemishes, good appearance and
glossiness, and furnishes a pro*ective coating thereon.
It is still another object of the present
invention to provide a method of preparing the silicone
emulsion polish compositions of the instant invention.
It is also an ob~ect of the present invention to
provide improved emulsions prepared by emulsion
682~
60SI-809
-- 8
polymerization of cyclic siloxanes by stripping
residual cyclics from the thus prepared emulsion.
These and other objects are provided herein by
an aminofunctional silicone emulsion comprising the
reaction product of (a) water; (b) an emulsifier or
combination of emulsifiers; (c) a diorganopolysiloxane
fluid; (d) an aminofunctional silane and (e) optionally,
a polymerization catalyst; said emulsion being prepared
by e,mulsion polymerization.
Other features of the present invention will
include a silicone emulsion polish comprising the
reaction product of
(I) an aminofunctional silicone emulsion
comprising:
(a) water;
(b) an emulsifier or combination of
emulsifiers;
(c) a diorganopolysiloxane fluid;
(d) an aminofunctional silane; and
(e) optionally, a polymerization catalyst;
said emulsion being prepared by emulsion
polymerization;
in intimate admixture with:
(II) a silicone emulsion comprising:
(a) a diorganopolysiloxane base polymer
fluid having a viscosity of from about
50 to 100,000 centipoise at 25C;
(b) water;
(c) an emulsifier or combination or
emulsifiersA
Processes for preparing the aminofunctional
silicone emulsions and silicone emulsion polishes of the
present invention are also contemplated.
;8~
- 8a - 60SI-809
In accordance with another aspect of the
present invention there is provided a silicone
emulsion polish comprising an admixture of:
I. an aqueous emulsion prepared by
(A) emulsion polymerizing
(a) a polydiorganosiloxane in
(b) an aqueous medium in the presence of
(c) an emulsifier or mixture of emulsifiers
and
(d) optionally, a polymerization catalyst or
mixture of polymerization catalyst, and
(B) thereafter stripping cyclic or other low
molecular weight siloxanes from said
emulsion by heating, and
II. a silicone.emulsion comprising
(a) a polydiorganosiloxane base polymer
fluid having a viscosity from about 50
to about 100,000 cps. at 25C.,
(b) water, and
20 (c) an emulsifier or mixture ~ ifi rs.
- ,~,
.,
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6OSI-809
g _
`DETAILED DESCRIPTION OF THE INVENTION
In one aspect of the present invention
aminofunctional silicone emulsions are prepared by
emulsion polymexizing an aqueous emulsion of a
relatively low molecular weight diorganopolysiloxane
and an aminofunctional silane. These aminofunctional
silicone emulsions may be used alone or combined with
conventional silicone emulsions to form easily applied,
protective polishes which will exhibit increased
adhesion to the surfaces to which they are applied.
A principal starting material for both the
aminofunctional emulsion and both components of the
silicone emulsion polish of the present invention is a
linear diorganopolysiloxane base polymer fluid having
a viscosity of up to about 100,000 cps. at 25C or a
cyclic polysiloxane of the general formula
-~- R2 SiO -~- 3 9 in which the R substituents may be,
independently, hydrogen or a hydrocarbon or substituted
hydrocarbon group. Of course, mixtures of cyclics,
linear siloxanes or both are permissible. P~referably
the substituents are aliphatic hydrocarbon groups,
including methyl, ethyl, isopropyl, vinyl, allyl, and
the like.
Those skilled in the art, of course, appreciate
that linear diorganopolysiloxanes are prepared from
cyclic polysiloxanes, preferably octamethylcyclotetra-
siloxane (referred to in the art as tetramer or methyl
tetramer). Both cyclic polysiloxanes and linear
siloxanes can readily be prepared by the artisan or be
obtained from commercial sources.
For the purposes of this invention, polydimethyl-
siloxane (PDMS) base polymer fluids are preferred. For
the silicone emulsion polish features of the present
inVention, silanol-endstopped polysiloxanes are most
preferred, for reasons to be discussed in more detail
~z~ z~
60SI-809
-- 10 --
hereinafter; however, other polysiloxane base polymer
fluids, such as, for exa~ple, methyl-endstopped and
vinyl-endstopped fluids, are also suitable.
The aminofunctional silanes suitable for
preparing the aminofunctional polysiloxane fluids and
emulsions of the present invention have the general
formula (RO)3SiR'Yn in which each R is an alkyl radical
of less than 4 carbon atoms, each R' is an aliphatic
hydrocarbon radical containing from 3 to 5 carbon atoms
and having a valence of n + 1 where n is an integer from
1 to 3 and Y is a monovalent radical attached to R' by a
carbon-nitrogen bond and ccmposed of hydrogen atoms,
nitrogen atoms and up to eight carbon atoms and
containing at least one amine group, the ratio of carbon
atoms to nitrogen atoms in Y being less than about 6:1.
The detailed discussion of these silanes and their
preparation appear in the aforementioned Hyde patent
(U.S. 3r3501349) .
The preferred aminofunctional silanes include
3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-
aminopropyltrimethodysilane, N,N-diethyl-3-
aminopropyltrimethoxysilane and the like. It should be
noted that the aminofunctional silanes within the scope
of the present invention are not hydrolyzable as are the
nitrogen-containing radicals of Sorkin, U.S. Patent No.
3,624,017 issued November 30, 1971.
Emulsification of the polymer is assisted by an
emulsifying surfactant (emulsifier) which will promote
dispersion of the silicone polymer in an aqueous phase.
For the purposes of the present invention,
alkylphenoxypolyoxyethylene glycol surfactants, such as
; octylphenoxypolyoxyethylene glycol (TRITON X405A, Rohm
& Haas) and nonylphenoxypolyoxyethylene glycol
~,n
(IGEPAL C0850~ GAF): and complex quaternary ammonium
salts, such as methylpolyoxyethylene (15) cocoammonium
8, ~
60SI-809
r~
chloride (95%, ETHOQVAD~C/25; ARMAK) and diemethylsoy-
ammonium chloride (74%, ARQUAD~25-75; ARMAK), are
preferred, though many other emulsifiers are suitable
and will suggest themselves to persons skilled in the
art. Combinations of such surfactants may also be
used. Those skilled in the art will recognize that
certain emulsifiers will also be effective as a
polymerization catalyst, e.g. if they make the
emulsion sufficiently basic.
It should be noted that the ether-type
emulsifiers are particularly preferred as when they are
utilized higher reaction temperatures may be employed,
thereby increasing the rate of polymeril~ation and
allowing stripping of volatiles.
The concentration of the siloxane with respect
to the water is not critical. All that is required is
that the siloxane be emulsified in an effective amount
of water. Thus so long as there is enough water to
give a continuous aqueous phase the polymerization will
proceed in accordance with the present invention.
Although polymerization can be carried out at siloxane
concentrations of 1% by weight or less, generally
polymerization is effected at siloxane concentrations
of 20 to 60% by weight.
The aminofunctional silicone emulsions of the
present invention may be easily prepared in one step by
an acid or base catalyzed equilibration of cyclic
polysiloxane monomers, such as octamethylcyclotetra-
siloxane, in water in the presence of an emulsifier (or
a combination of emulsifiers) and an aminofunctional
silane, i.e~ by emulsion poIymerization.
Suitable acid and base catalysts are well known
to those skilled in the art Among the preferred
catalysts are the strong mineral acids and strong
alkalis of Hyde et al. U.S. Patent ~o. 2,891,920 issued
~ ~'t~ 22
60SI-809
- 12 -
June 23, 1959; and the sulfonic acid catalysts of
Findlay et al. U.S. Patent No. 3,294,725 issued
December 27, 1966; and the organic sulfates of Axon,
U.S. Patent No. 3,360,491 issued December 26, 1967. The
artisan will appreciate that it is possible for the
emulsifier and the polymerization catalyst to be the
same compound.
As an example of a preferred emulsion
polymerization process, the emulsifier~s), water, and
acid or base catalyst, are blended in a single reaction
vessel. The polysiloxane monomers are then added and
the mixture homogenized, and thenheated (if necessary)
to begin polymerization. A silanol-endstopped poly-
siloxane is formed which will undergo a condensation
reaction with the subsequently added aminofunctional
silane to yield polymers with terminal aminofunctional
silane groups. Neutralization of the catalyst gives an
aminofunctional silicone emulsion according to the
present invention. It should be understood that the
aminofunctional silane can be added before emulsion
polymerization begins but preferably it is added
subsequently~
It is also likely that the amino-terminated
polysiloxanes formed by the emulsion polymerization
process of the instant invention further react, e.g.
condense, so as to yield polysiloxanes having amino
groups on the siloxane chain.
In addition to the foregoing required
constituents of the emulsions of the present invention,
the present applicants have found that further unexpected
results are obtained by including other constituents,
discussed more fully hereinbelow, or by stripping the
resultant emulsion of residual cyclopolysiloxanes or
other volatile polysiloxanes.
~2~6~
60SI-809
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In another aspect of the present invention it has
surprisingly been discovered that the further addition
of alkyltrialkyoxysilane or mixture of such
alkyltrialkoxysilanes, preferably such as methyltri-
methoxysilane and the like, results in emulsions whichimpart greater durability to polishes made therefrom.
While applicants are not certain of the reason for such
improved properties, it is believed that the com~ination
of amino groups and alkoxy groups results in a tighter
cure than would be had without such alkoxy groups.
Applicants have further found that it is desirable
to include in emulsions prepared by emulsion
polymerization in accordance with the present invention,
silanes such as gammamethyacryloxypropyltrimethoxysilane
or cyanoethyltrimethoxysilane. Such silanes not only
provide additional cure or crosslinking sites, but also
provide a site for adding other desired moieties to the
siloxane chain. That is, the present of such reactive
groups allows the emulsions of the present invention to
be utilized as an intermediate compound in addition to
being used as a protective coating compound. Those
skilled in the art will appreciate that such compounds
have the general formula (RO)3 SiX where R is a Cl 8
aliphatic organic radial and X is an unsaturated
organic radical. Those skilled in the art will readily
be able to determine which compounds are within the scope
of the foregoing silanes without undue experimentation.
Furthermore, it is well within the skill of the artisan
to determine how much of such compounds should be
included in the emulsion polymerizable compositions in
order to obtain the desired properties. Agahl, it is
preferred that the alkyltrialkoxysilane or the
unsaturated silance be added after the emulsion
polymerization of the polydiorganosiloxane, but if
desired it may be added prior to such emulsion
1~ b~i8'~'~
60SI-809
- 14 -
polymerization.
In still another aspect of the present invention
applicants have found that improved film properties are
imparted to polishes prepared in accordance with the
instant invention if cyclic polysiloxanes are stripped
from the emulsion prepared by emulsion polymerization.
It is necessary that the emulsion to be stripped of
cyclopolysiloxanes (or other low molecular weight
polysiloxane) in accordance with the present invention
be emulsion polymerized rather than formed by
mechanical means such as colloid milling as such
emulsions will break down at the elevated temperatures
employed for stripping.
It is further preferred that in addition to
employing cationic emulsifiers, that such cationic
emulsifiers be ether-type emulsifiers such as
alkylphenoxypolyoxyethylene glycols. Ether-type
emulsifiers are particularly preferred as they remain
effective at high temperatures (i.e. about the 100 C
temperature needed to effect stripping). Other
suitable ether-type emulsifiers are well known to the
skilled artisan~
The aminofunctional silicone emulsions of the
present invention may be used as components in
silicone emulsion polish compositions. Suitable
polishes according to the present invention would be
expected to result, for example, from combining an
aminofunctional silicone emulsion of the present
invention with an emulsified diorganopolysiloxane fluid,
such as a PDMS fluid, which is prepared by methods well
known to persons skilled in this art using conventional
surfactants and water. Furthermore, it has been
discovered herein that combination of the aminofunctional
silicone emulsions of the present invention with
silanol-endstopped polysiloxane fluid emulsions provides
12~6~3~2
60SI-809
- 15 -
a uniquely serviceable and durable protective polish
composition. This is believed to be a result of latent
condensation between the aminofunctional silane-
endstopped polysiloxane emulsion and the SiOH-containing
silanol fluid emulsion, leading to a stable, crosslinked
product. For the purposes of making silanol-containing
silicone emulsion polishes of the present invention,
silanol-terminated PDMS fluids having viscosities in the
range of about 600 to about 180,000 centistokes are most
preferred.
In preparing the silicone emulsion polishes of the
present invention, the exact formulation, i.e., the exact
proportion of aminofunctional emulsion to silicone
emulsion, will depend on several factors including type
of polysiloxane fluids used and type of amino
functionality. Simple experimentation to match the
polish formulation to a given set of conditions is
contemplated; however, in the case of aminofunctional
PDMS emulsions combined with silanol-stopped PDMS
emulsions to form a polish, excellent experimental
results have been obtained with aminofunctional emulsion
to silanol emulsion ratios in the range of about 1:7 to
about 1:12. These ratios should not be considered
limiting, however, since improved performance in terms
of detergent resistance is noted over a wider range of
formulations.
The polish compositions of the present invention,
whether of the emulsion type or curable blended fluid
type, may contain additional components to lend the
polishes desirable ~ualities which make them useful for
specific applications~ These additional components
include, for example, ultraviolet radiation screens,
thickeners, antifoaming agents, antimicrobial agents,
additional surfactants, solvents, pigments, and the like.
3X~
60SI-809
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The emulsion polishes of the present invention
offer the further advantage of being shelf stable. The
aminofunctional polymers will not crosslink and cure to
form their characteristic flexible, glossy protective
coating until broken out of the aqueous emulsion phase
by physical application to a solid substrate.
In order that those skilled in the art are better
able to practice the invention the following examples
are provided. The examples are intended to be
illustrative only and should not be construed as
limiting in any manner.
EXAMPLE 1
Five emulsion polymerized a~inofunctional silicone
emulsions and two colloid milled silicone oil emulsions
were prepared as follows:-
Cationic Pminofunctional Emulsion #l
. ~
1415 parts by weight deionized water, 100 parts byweight octylphenoxypolyoxyethylene glycol (TRITON X405,
Rohm & Haas) emulsifier, 17 parts by weight 95%
methylpolyoxyethylene(15) cocoammonium chloride
(ETHOQUAD C/25), Armak), and 3 parts by weight KOH
pellets were added to a reaction vessel and mixed
thoroughly. 875 parts by weight octamethylcyclotetra-
siloxane were added to the uniform mixture and blended.
The mixture was passed through a colloid mill (5 mil gap)
and homogenized at 6000 psig. The resulting emulsion was
heated at 95 C for 4 hours to polymerize the cyclic
tetramer. The emulsion was then cooled to 50C and 73
parts by weight of 3(2-aminoethyl)aminopropyltrimethoxy
silane, in which 8 parts by weight of the ETHOQUA~ C/25
emulsifier had been dissolved, were added to the
polymerization vessel, and the polymerization allowed to
proceed at 50 C for 1~5 hours longer. Finally, the
catalyst was neutralized with ~.2 parts by weight of
acetic acid.
~68'~
60SI-809
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Cationic Aminofunctional Emulsion #2
_
A second aminofunctional emulsion was prepared in
the same manner as Emulsion #1, except the following
ingredients and quantities were used:
1750 parts by weight cyclic tetramer
200 parts by weight TRITON X405
2750 parts by weight water
34 parts by weight ETHOQUAD C/25
The premix was blended, and 4000 parts by weight
were added to a reaction vessel along with 8.4 parts by
weight KOH pellets. The mixture was heated at 95C for
4 hours, then cooled to 50C at which point 191 parts
by weight 3(2-aminoethyl)aminopropyltrimethoxy silane
with 25 parts by weight ETHOQUAD C/25 dissolved therein
were added~ The complete mixture was held for 2 hours
at 50C, and then the catalyst was neutralized with
acetic acid.
Cationic Aminofunctional Emulsioh #3
. . .. ~
1000 parts by weight of the cyclic tetramer, 23
parts by weight isopropyl alcohol, 30 parts by weight 74
dimethylsoyaammonium chloride (ARQUAD 2S-75, Armak)
4 parts by weight KOH and 673 parts by weight water were
blended until uniform. 30 parts by weight of TRITON
25 X405, 30 parts by weight ETHOQUAD C/25 and 300 parts by
weight water were added to the premix, and the complete
emulsion heated to 90-95 C for 3 hours. 100 parts by
weight of 3(2-aminoethyl)aminopropyltrimethoxy silane
containing 10 parts by weight TRITON X405 emulsifier were
added to the reaction mixture. The reaction mixture was
held at 90C for 2 hours longer, at which time the
catalyst was neutralized with acetic acid.
6822
60SI-809
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Anionic Aminofunctional Emulsion #4
.
1050 parts by weight of the cyclic tetramer, 30
parts by weight dodecylbenzene sulfonic acid and 1719
parts by weight water were blended, then homogenized at
6000 psig. 1982 parts by weight of this homogenized
premix were added to a reaction vessel, heated to 90 C
for 2 hours then cooled to 45C for 3 hours, after which
the polymer viscosity was about 150,000 cps. The
emulsion was neutralized with 22 parts by weight
triethanol amine. 53 parts by weight TRITON X405
emulsifier followed by 90 parts by weight 3(2-a~inoethyl)
aminopropyltrimethoxy silane were added to the
neutralized emulsion at 45C. The final solids content
was 37.9%, and the emulsion dried to a cured film.
Anionia/Cationic Aminofunctional Emulsion #5
Following the procedures outlined in the preparation
of Emulsion #4, 875 parts by weight of the cyclic
tetramer, 12.5 parts by weight dodecylbenzene sulfonic
acid and 1437.5 parts by weight water were blended and
homogenized. 2105 parts by weight of the premix was
heated at 90 C for 3 hours, then cooled to 26C for 24
hours. The polymer was about 400,000 cps viscosity.
11 parts by weight of triethanol amine were added to
neutralize the catalyst, followed by 45 parts by weight
25 TRITON X435 and 80 parts by weight 3(2-aminoethyl)
aminopropyltrimethoxy silane dissolved in 23 parts by
weight ETHOQUAD C/25. The emulsion was warmed to 45 C
and stripped free of methanol under 90 mm vacuum
pressure. The resultant emulsion was 38% solids and
cured on air drying to a detergent resistant film.
~2~6~32~
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SILANOL OIL EMULSION #6
A silicone emulsion was prepared using standard
techniques from 762 parts by weight of a silanol-
terminated PDMS fluid having a viscosity of from 2550 to
3570 cstk., 760 parts by weight of a 10,000 cstk.
trimethylsiloxane-stopped dimethylpolysiloxane copolymer
(VISCASILTM 10M, General Electric Co.), 26 parts by
weight of an ultraviolet radiation screen ~UVINULTM
N539, BASF), 26 parts by weight TRITON X405, 38 parts by
weight nonylphenoxypolyoxyethylene glycol (IGEPAL C0850
GAF), 105 parts by weight water (Part I), 2.5 parts by
weight of an antimicrobial agent (DOWICILTM 200,
Mallinkrodt), 215 parts by weight sodium benzoate, 871
parts by weight water (Part II) and 0.1 part by weight
of a silicone antifoaming agent (AF72, General Electric
Co . ) .
The polysiloxane fluids, the ultraviolet radiation
screen and the emulsifiers were blended at 50C. Part I
water containing the antimicrobial agents (DOWICIL and
sodium benzoate) was added slowly to the premix. The
mixture was held at 55DC for ~ hour, then colloid milled
into Part II water. This produced a final emulsion
having a viscosity of 165 cps. With a solids content of
61.4%.
25 Silanol Oil Emulsion #7
A silanol-containing emulsion was prepared in the
same manner as Emulsion #6 using the following
ingredients and quantities:
600 parts by weight of the silanol-endstopped
fluid
600 parts by weight VISCASIL 10M
30 parts by weight IGEPAL C0850
20 parts by weight TRITON X405
1 part by weight antimicrobial agent
~,
`: i
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60SI-809
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(6-acetoxy-2,4-dimethyl-m-dioxane,
Givaudan Corp.)
2 parts by weight sodium benzoate
80 parts by weight water (Part I)
667 paLts by weight water (Part II)
0.1 parts by weight antifoam agent
The product was a silanol-containing emulsion
having a viscosity of 260 cps. and a solids content
Of 62,3%.
EX~1~PLE 2
Polish emulsions were prepared by blending
aminofunctional emulsions (Emulsion Nos. 1-5) with
silanol-containing emulsions (Emulsion ~los. 6 & 7).
To formulate the polish, 11 parts by weight of an
aminofunctional emulsion (or combination) were
combined with 89 parts by weight of a silanol-containing
emulsion.
Samples of black exterior vinyl of the type used
on automobile roofs were coated with polishes prepared
as described above. The polished surfaces had good
"gloss", covered blemishes well and showed good
detergent resistance after 4 washings. The samples
prepared with ultraviolet radiation screens are
additionally expected to protect the underlying vinyl
from the harmful effects of sunlight.
EXAMPLE 3
A number of silanol-containing and amino-
functional silicone-containing emulsions were prepared
from the following ingredients:
8~X
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Components Description
Silicone resin A a resin prepared from hydrolyzed
methyltrichlorosilane ~General
Electric Co.)
Silicone resin B a 70~ solution of a methoxy
silicone in an aromatic solvent
(General Electric Co.)
VISCASIL [see ~xample 1, above]
1~ Silanol fluid J silanol-terminated PDMS fluid,
610-900 cstk.
Aminofunctional a polymer prepared by blending
fluid X 2.6 weight percent 3-a~inopropyl-
trimethoxysilane and 2.6 weight
percent N-2-aminoethyl-3-
aminopropyltrimethoxysilane with
94.8 weight percent of a low
viscosity silanol-stopped PDMS
fluid to yield a methoxy-stopped
copolymer.
.
Silanol fluid K silanol-terminated PDMS fluid,
15,300-30,600 cstk.
Aminofunctional An aminofunctional PDMS copolymer
fluid Y prepared from a 100 cstk. silanol
PDMS fluid, N-2-aminoethyl-3-
aminopropyltrimethoxysilane and
3-aminopropyltrimethoxy silane
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Components Descri~ ion
Aminofunctional an aminofunctional PDMS copolymer
fluid Z prepared from a 2550-3570 cstk.
silanol fluid, N-2-aminoethyl-3-
aminopropyltrimethoxysilane,
mineral spirits and isopropanol
Using various of the components listed above,
several polish formulations were prepared in aluminum
dishes and allowed to cure for three days at room
temperature. The cured films were then evaluated in
terms of firmness, stickiness, oiliness, etc.
Formulation l
Parts by Weight
Components (1) (2) (3)
Silicone resin A 5.0 5.0 5.0
Silicone resin B 5.0 5.0 5.0
VISCASIL 1.0 _ _
Silanol fluid J - l.0
Aminofunctional fluid X - - 1.O
Description of Films
(1) very soft gel
(2) firmer gel
(3) firm gel
x
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Formulation 2
Parts by Weight
Components (4) (5)
Silicone resin A 0.3 0.3
Silanol fluid J 1.0
Silanol fluid K 0.6
VISCASIL - 1.6
Aminofunctional fluid X 1.0 1.0
Description of Fi_ms
(4) very firm gel
(5) very soft gel/free oil
Formulation 3
Parts by Weight
Co ponents (6) (7) (8) (9)
Aminofunctional fluid Y1.0 1.0 2.0 2.0
Aminofunctional fluid Z3.0 3.0
VISCASIL 1.0 - 1.0
Silanol fluid J - 1.0 - 1.0
.
Description of Film5
(6) soft gen (oily)
(7) firm gel
(8) soft tacky gel
(9) firm gel
Formulations 4a-4e
A series of polishes was prepared using amino-
functional fluids with silanol fluids and dimethylpoly-
siloxane fluids. Gloss, ease of rub-out or general ease
of application and removal, and detergent resistance
were measured.
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Parts by-Weight
Components (a) (b) (c) (d) (é)
Aminofunctional 1.0 1.0 4.0 4.0 4.0
5 fluid Y
Aminofunctional 6.0 6.0
fluid Z
Silanol fluid J - 1.5 - 2.5 1.5
Silanol fluid K - - - - 1.0
10 VISCASIL 1.5 - 2.5
Surfactant 1.0 1.0 1.0 1.0 1.0
Mineral Spirits22.022.022.0 22.022.0
Calcined clay 10.0 10.010.0 10.010.0
Water 58.5 58.557.5 57.557.5
The above polishes were evaluated by applying each
to a black painted surface, aging 24 hours and then
washing with a cellulose sponge plus 3% laundry
detergent solution in water. The following results
were observed:
Formu- - Applicat Detergent Resistance
lation Gloss -ion Ease 50 washes 100 washes
. _
a very good easy fair-good poor
b good easy good good
25 c good normal good fair
d good normal excellent good
e excellent normal excellent good
The polish formulations utilizing silanol fluids
showed improved resistance to detergent washing.
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EXAMPLE 4
Cationic Aminofunctional Emulsion #8
525 parts by weight of a silanol-stopped
dimethylpolysiloxane-methylpolysiloxane copolymer oil,
20.5 parts by weight N-2-aminoethyl-3-aminopropyltri-
methoxysilane, 45 parts by weight alkylaryl polyether
alcohol (TRITON X-100), 45 parts by weight trimethyl-
cocoammonium chloride (ARQUAD C-50), 15 parts by weight
ETHOQUAD C/25, 30 parts by weight glycerin and 180 parts
by weight water (Part I) were blended together in a
reaction vessel. The mixture was agitated until uniform
at 25C, then colloid milled (10 mil gap at 15 psig
pressure). The resulting soft paste was diluted with
water (Part II) to yield upon blending a 38% solids
silicone emulsion, pH 9.2, 40 cps viscosity. A 40 cc
sample of this emulsion was centrifuged for 30 minutes
at 3,000 rpm. Only a 0.25 cc sediment, indicating a
well-formed emulsion.
. . .
Cationic Emul`sion #9
20 parts by weight of N-2-aminoethyl-3-aminopropyl-
trimethoxysilane were added to 300 parts by weight of
the Emulsion #8 (above). The emulsion was agitated
rapidly to disperse the additional amino silane, bringing
the level up from 1.37% to 7.5% amino silane.
Aminofunctional Emulsion #-10
1400 parts by weight of the cyclic tetramer, 2092
parts by weight water and 4Q parts by weight
dodecylbenzene sulfonic acid were blended, then
homogenized at 8000 psig and then 4000 psig to ensure
uniformity. The e~ulsion was then heated to 75-85C and
agitated for 3 hours. The emulsion was cooled to 35 C for
35 3 hours to allow polymer viscosity to approach 300,000 cps.
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At the end of this cooling cycle the emulsifier-
catalyst was neutralized with 40 parts by weight of
triethanol amine. The resultant emulsion was pH 9.3.
380 parts by weight of colloidal silica and 5 parts by
weight formalin were added. The emulsion was blended
for l/2-hour tQ yield a 37.9% solids uniform emulsion,
pH 9.2.
Aminofunctional Emulsion #lOa
-
To 100 parts by weight of the foregoing Emulsion
#10 there was a~ded a blend consisting of 2 parts by
weight 3-(aminoethylamino)proponoic acid,
3-(trimethoxysilyl)propyl ester; 1 part by weight of an
emulsifier blend (42.5% IGEPAL C0850, 42.5~ polyethylene
glycol, trimethylnonylether (TERGITOL T~N-6 and 15%
water); and 1/2 part by weight triethanol amine. After
vigorous agitation a water white aminofunctional emulsion
resulted which was uniform and was found to be water
dispersible.
Cationic Amlnofunctional Emulsion #11
700 parts by weight of a 1000 cstk. silanol-stopped
PDMS fluid, 27.4 parts by weight N-2-aminoethyl-3-
aminopropyltrimethoxysilane, 60 parts by weight
polysorbate-80, 20 parts by weight polysorbate-85, 15
parts by weight trimethylcocoammonium chloride, 15 parts
by weight dimethyldisoyaam~onium chloride, 30 parts by
weight bis(2-hvdroxyethyl)soyamine, and 120 parts by
weight water were blended together and mixed 1/2 hour at
room temperature. This prem x was colloid milled (15 mil
gap at 15 psig) into 1000 parts by weight water, 40 parts
by weight glycerin and 20 parts by weight methylpoly-
oxyethylene(15~oleylammonium chloride, then inverted by
rapid agitation and homogenized at 8000 psi. The
resultant emulsion was found to be 42.4~ solids. When
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60SI-809
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applied to an aluminum panel, the emulsion air dried to
yield a soft cured polymer system.
Aminofunctional Emulsion #12
A polymer blend was prepared comprising 69.5 weight
percent of a 3000 cstk. silanol-stopped PDMS fluid, 24.3
weight percent of a 165 cstk. silanol-sto?ped PD~.S fluid,
4.8 weight percent N-2-aminoethyl-3-aminopropyltrimeth-
oxysilane and 1.4 weight percent 3-aminopropyltrimeth-
oxysilane. 164 parts by weight of this blend, 110 parts
by weight of a 3.5 weight percent hydroxypropyl methyl-
cellulose solution, 7 parts by weight Triton X-100, 100
parts by weight water and 80 parts by weight odorless
mineral spirits were then mixed together in a reaction
vessel. The emulsion was agitated until uniform, then
homogenized. The emulsion was coated on an aluminum
panel and cured to a hard, abrasion resistant film.
10" x 12" pieces of cotton cloth were immersed in
5% solids solutions of aminofunctional Emulsions Nos. 8,
9 and 10a. Some of the cloths were allowed to air dry,
others were dried for 10 minutes at 150C in an air
circulating oven, after being passed through a padder
to remove excess emulsion. The cloths were then allowed
to stand for 72 hours at room temperature. The samples
were found to exhibit good hand qualities and good water
resistance. The cationic emulsion samples are also
expected to have improved antistatic properties and
biocidal activity.
EXAMPLE 5
Preparation of Silanol Terminated Emulsion Polymer
To 7bo parts by weight of actamethylcyclotetra-
siloxane there was added 80 parts by weight octylphenoxy-
polyoxyethylene glycol (TRITON X405, Rohm and Haas)
emulsifier, 20 parts by weight cocomethylpolyoxy-
~3682~
60SI-809
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ethyleneglycol ammonium chloride (ETHOQUAD C/25) and
1117 parts by weight deionized water. The mixture was
blended with an air stirrer while being confined to a 4
liter stainless steel beaker. A uniform blend was
obtained in about 15 minutes. There was then added 9
parts by weight of a 45% KOH solution.
The blend was thereafter homogenized at 8000 psi
by passing through a laboratory ~lanton-5aulin
homogenizer. 1827 parts by weight of the resultant
homogenized tetramer emulsion was added to a 3 liter,
3 neck round bottom flask equipped with thermometer,
thermal controller, heating mantle, condenser and
mechanical stirrer. The emulsion was heated at 90-95 C
for 6 hours to polymerize the tetramer in situ to yield
a silanol terminated polydimethylsiloxane polymer. The
pH of the aqueous emulsion was slightly greater than 12.
After polymerization was completed the KOH
catalyst was neutralized with 4 parts by weight of
acetic acid. The resultant pH was about 6.5 and the
solids content was about 35 percent by weight.
'EX~MPLE 6
Ca-tionic Amin'ofunc-tiona'l Emulsion Containing 1
Methyltrlmethoxysilane
The emulsion of Example 5 was cooled to about 25 C
at which time there was added to 600 parts by weight of
such emulsion a blend containing 22 parts by weight
N-2-aminoethyl-3-aminopropyltrimethoxysilane, 6.3 parts
by weight methyltrimethoxysilane and 3 parts by weight
TRITON X100. The emulsion polymerization was then
allowed to proceed for about another 1.5 hours at 40-45 C.
This cationic aminofunctional emulsion is similar to
cationic aminofunctional emulsions 1, 2 and 3 of Example 1
except that it contains about 1 percent by weight
methyltrimethoxysilane.
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60SI-809
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The cationic aminofunctional emulsion was allowed
to equilibrate for 3-5 days. The emulsion cures on air
drying to yield a resinous detergent resistant film.
The cured films of this example are much tougher than
the cured films of Example 1. It is believed that this
is due to the tighter cure which results from the
presence of the methoxy groups.
EXAMPLE 7
Cationic-Aminofunc*ional Emulsion Containing
3~% Methyltrimethoxysilane
To another 600 parts by weight of the emulsion
prepared in Example 5 there was added at 25C 2 parts by
weight TRITON X405. The emulsion was blended until the
emulsifier was completely dispersed. There was then
added a blend containing 22.5 parts by weight N-2-amino
ethyl-3-aminopropyltrimethoxy-silane, 19.3 parts by
weight methyltrimethoxysilane and 4 parts by weight
TRITON X100. Emulsion polymerization was again allowed
20 to proceed at 40-45C for about 1.5 hours.
This cationic aminofunctional emulsion cures on air
drying to yield a detergent resistant film that is more
resinous than the films prepared from Examples 1 or 5.
A film prepared from the emulsion of this example by
25 drying a 5 gram sample at 120F for 24 hours was brittle
and somewhat friable.
EXAMPLE 8
.. .. . . ... ... . .. . . .
Cationic Aminofunctional Emulsion Contaihing Gamma-
Methacryloxypropyltrimethoxysilane
To the final 600 parts by weight of the emulsion
prepared in Example 5 there was added at 25C a blend
containing 21.8 parts by weight ~ -methacryloxypropyltri-
methoxysilane and 3 parts by weight TRITON X100.
Emulsion polymerization was allowed to continue for
~2~368Z2
60SI-809
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another 1.5 hours at 40-45 C.
After equilibrating for 3-5 days an emulsion was
obtained which can be cured on cloth with water-soluble
peroxides. This emulsion could also be copolymerized
with other materials such as an acrylic emulsion to
yield a novel coating.
EXAMPLE 9
Stripped Aminofunctional Ca*ionic Emulsion
of Example 6
To a 1 liter, 3 neck flask equipped with
thermometer, reflux trap, thermal controller, condenser
and mechanical stirrer there was added 286 parts by
weight of the emulsion of Example 6. The emulsion was
heated to 100C under atmospheric conditions wher~upon
12 parts by weight of unpolymerized tetramer was
removed from the emulsion.
Those skilled in the art will appreciate that it is
quite unexpected that an emulsion could be heated to such
a temperature without breaking down the emulsion.
A film prepared by drying a 5 gram sample of the
emulsion at 120 F for 24 hours was found to be
considerably harder and tougher and less elastic than
the film prepared from the emulsion of Example 6. This
is believed to be due to the removal of the cyclics which
act as a plasticizer.
EXAMPLE 10
.. .. . . ... .. . .. .. .. .. ..
StripPed'Amino'functional Cationic Emulsion
of Exa'mple'7-
To a liter, 3 neck flask equipped as in Example 9,except that a nitrogen sparge was attached at the
thermometer port, there was added about 300 parts by
weight of the emulsion of Example 7. When heated to 100 C
under nitrogen sparge, 10 parts by weight of cyclic light
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60SI-809
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ends were removed by azeotroping.
A film prepared by dryiny a 5 gram sample of the
emulsion at 120 F for 24 hours was found to be
considerably harder and tougher than the film prepared
from the emulsion of Example 7.
EXAMPLE 11
Stripped Aminofunctional Cationic'Emulsion
... . _ _ _ _ .. . _ .
Using equipment like that in Example 9, 1 pint of a
cationic aminofunctional emulsion similar to those of
Example 1 was stripped by heating to 100C and azeotroping
off cyclics. About 6 percent by weight cyclics were
isolated based upon the amount of polymer in the emulsion.
A film prepared by heating a 5 gram sample of the
emulsion at 120F for 24 hours was much tougher and more
elastic than films prepared from cationic aminofunctional
emulsions produced by emulsion polymerization which were
not stripped of cyclics.
EXAMPLE 12
.. . ... . .. . . . . .
Stripped Emulsion Containing Methyltrimethoxysilane
An emulsion was prepared as in Example 5 from 700
parts by weight methyl tetramer, 80 parts by weight
TRITON X405, 20 parts by weight ETHOQUAD C/25, 9 parts
by weight 45% ROH solution and 1117 parts by weight
water. This prer.lix was blended, homogenized and then
emulsion polymerized as in Example 5. The polymerization
temperature rose to greater than 96C causing some oil to
separate and necessitating rehomogenization. The emulsion
polymerization was continued for about 6 hours to yield a
silanol terminated polymer.
The emulsion was cooled to about 50C at which time
there was added to 1232 parts by weight of the emulsion a
blend containing 62 parts by weight methyltrimethoxysilane
and 5 parts by weight TRITON X100. Then 25 parts by
6822
60SI-809
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weight TRITON X405 WAS added and the temperature raised
to 60 C. Emulsion polymerization continue~ at this
temperature for about 3 hours to yield an emulsion having
a solids content of about 34 percent by weight.
837 parts by weight of the thus produced emulsion
was stripped by azeotroping as in Example 10. There
was removed 74 parts by weight of cyclics and water.
The solids content of the stripped emulsions was found
to be 38.8% by weight. Films were prepared by heating
5 gram samples of both the original and stripped
emulsions at 120 F for 24 hours. The film prepared from
the original emulsion was waxy and friable, and contained
some free oil. The film prepared from the stripped
emulsion was still waxy and friable, but was much tougher.
EXAMPLE 13
~ .
Cationic Aminofunctional Emulsion Cohtaining
2% Cyanoethyltrimethoxysilane
A silanol terminated polydimethylsiloxane was
prepared by emulsion polymerization. To this emulsion
there was a~ded 2.1% by weight cyanoethyltrimethoxysilane,
1% by weight methyltrimethoxysilane, 0.34% by weight
TRITON X100 and 0.34% by weight ETHOQUAD C/25 and the
emulsion polymerization continued by heating at about
50C for about 2 hours.
There resulted an extremely stable emulsion which is
curable to a detergent resistant coating.
Obviouslv, modifications and variations in the
present invention are possible in light of the foregoing
disclosure~ For example, as can be seen from the working
examples, antimicrobial agents, thickening agents,
ultraviolet light screens, antifoaming agents, and other
such conventional and functional additives may be added
to impart their particular properties to the formulations
herein. It is-understood, however, that any incidental
lX~6822
60SI-809
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changes made in the particular embodiments of the
invention as disclosed are within the full intended
scope of the invention as defined in the appended
claims.
