Note: Descriptions are shown in the official language in which they were submitted.
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DESCRIPTION
WATER-STABILIZED ORGANOSILANE COMPOUNDS AND THEIR US
Background of the Invention
Field of the Invention:
The invention relates to organosilane compounds, products and methods for
their use.
In particular, this invention provides water-stable organosilane compounds,
products, and
compositions for treating various substrates; articles treated with the
compounds, products and
compositions; and methods of treatment using the compounds, products and
compositions.
Background:
Organosiianesof the general formula R"SiX;,_~ where n is an integer of from 0
to 3, but
more generally from 0 to 2 (where when n is 3 the organosilanes may only
dimerize); R is a
nonhydrolyzable organic group, such as, but not limited to, alkyl, aromatic,
organofunctional,
or a combination thereof, and X is alkoxy, such as methoxy or ethoxy, are
prone to self
condensation rendering such organosilanesunstable in water over
commercialiyrelevantperiods
of time. Additionally, X can be a halogen, such as CI, Br, or I, and is
similarly liberated as HC1,
HBr, or HI. For such organosilanes, the X moiety reacts with various hydroxyl
containing
molecules in aqueous media to liberate methanol, ethanol, HC1, HBr, HI, H,O,
acetic acid, or
an unsubstituted or substituted carboxylic acid and to form the hydroxylated,
but condensation-
prone compound.
For organosilanesR"SiX4_", where n is an integer from 0 to 2, hydrolysis of
the first two
X groups with water produces a species bearing-Si(OH)~- units which can self
condensethrough
the hydroxyl moieties to linear and/or cyclic oligomers possessing the partial
structure HO-Si-
(O-Si)mm-O-Si-O-Si-O-Si-OH, where mm is an integer such that an oligomer is
formed. For
those cases, RSiX3, hydrolysis of the third X group generates a silanetriol
(RSi(OH);) which
produces insoluble organosilicon polymers through linear and/or cyclic self
condensation of the
Si(OH) units. This water induced self condensation generally precludes storage
of most
organosilanes R"SiX4_", where n ranges from 0 to 2, inclusive, in water.
Except for some
organosilanes which can be stable in very dilute solutions at specific pH
ranges, the use of water
solutions of most organosilanes require the use of freshly prepared solutions.
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One commerciallyrelevant example of an organosilane suffering from such
undesirable
self condensation is the antimicrobial Dow Corning 5700 (Dow Corning
Corporation, Midland,
MI). The literature describes the active ingredient of Dow Corning 5700 as 3-
(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride. However, in
aqueous media,
it is believed that the correct active ingredient is more likely 3-
(trihydroxysilyl)propyl-
dimethyloctadecyl ammonium chloride. Nonetheless, Dow Corning 5700 is a water
activated
antimicrobial integrated system which is capable of binding to a wide variety
of natural and
synthetic substrates, including fibers and fabrics, to produce a durable
surface or fabric coating.
3-(Trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride is prepared by
quaternization
of dimethyloctadecylamine with 3-chloropropyl trimethoxysilane.
The C,g hydrocarbon chain quaternary ammonium portion of the molecule
possesses
long-acting antimicrobial properties and provides initial association with the
surface of the
substrate through ionic bonds and/or electrostatic interaction. Preferably,
the treated surface
becomes permanently coated with a covalently bound octadecylammonium ion,
providing a
durable, long-actingantimicrobial coating that is able to destroy m icrobes
that come into contact
with the surface.
Unfortunately, as noted above, organosilanesin water, such as the activated
mixture of
3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride and water, are
generally
unstable and prone to self condensation. For instance, the m fixture of 3-
(trimethoxysilyl)propyl-
dimethyloctadecylammonium chloride and water begins to lose effectiveness in
as little as four
to eight hours. Gel formation in this and similar silane formulations in water
begins to occur in
evenshortertimes. The
limitationsofsuchorganosilanesinaqueousmediaarefurtherdescribed
in United States Patent No. 5,411,585, the contents of which are hereby
incorporated by this
reference. Moreover, such products are notorious for agitation difficulty
during the addition of
the silane to water.
The use of quaternary ammonium silicon compounds as antimicrobial agents in
accordance with the prior art is well known and taught in a wide variety of
United States Patents,
e.g., 3,560,385; 3,794,736; 3,814,739, the contents of which are hereby
incorporated by this
reference. It is also taught that these compounds possess certain
antimicrobial properties which
make them valuable and very useful for a variety of surfaces, substrates,
instruments and
applications (see, e.g., United States Patent Nos. 3,730,701; 3,794,736;
3,860,709; 4,282,366;
4,504,541; 4,615,937; 4,692,374; 4,408,996; and 4,414,268, the contents of
which are hereby
incorporated by this reference). While these quaternary ammonium silicon
compounds have
been employed to sterilize or disinfect many surfaces, their employment is
still limited because
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of their toxicity often as a result of the solvent system used to deliver the
compound, the
necessity for a solvent solution (for instance, Dow Corning antimicrobial
agent 5700 contains
over 49% methanol}, short term stability (stability of aqueous silane
solutions varies from hours
to several weeks only), and poor water solubility. For instance, while 3-
(trimethoxysilyl)propyl-
dimethyloctadecylammonium chloride does not suffer from water insolubility, it
is difficult to
dissolve in water and tends to form lumps before it slowly dissolves. It is
unstable in water, and,
because it is shipped in 50% methanol, it is overly toxic and flammable. Many
other
antimicrobial organosilanes, especially quaternary ammonium silicon compounds,
also suffer
from problems associated with physical health hazards, e.g., precautions must
be taken to avoid
contact with both skin and eyes, accidental spills to the surrounding area,
flammability, and the
added manufacturing steps needed in order to incorporate the such
antimicrobial agents into
other articles and surfaces, resulting in much higher manufacturing costs.
Therefore, there exists a need for extended shelf life, water-stable
organosilane
compounds, products and compositions whereby, upon application, the active
portion of the
organosilaneis operative for the selected application. Moreover, there exists
a need for water-
stable, organosilane compounds, products and compositions which are
essentially non-toxic,
non-flammable, uniformly dispersable, and simple and economical to use.
There also exists a need for highly concentrated organosilane compositions
which are
essentially non-toxic or of low toxicity, non-flammable, uniformly dispersable
and simple and
economical to use and stable in water when further diluted with water.
In the instant application we disclose the finding that compounds having at
least one
carbonate group stabilize aqueousorganosilanesolutions. The archetypal
exampleofcarbonates
useful according to the instant invention is propylene carbonate.
Brief Summary of the Invention
The present invention fulfills these needs by providing water-stable
organosilane
compounds, products (i.e., the compounds or compositions formed from
performing a specified
reaction) and compositions, methods for their use, and articles prepared using
the compounds,
products, and compositions.
In particular, the present invention provides the product formed from mixing
an
organosilaneof the formula R"SiX4_" where n is an integer of from 0 to 3,
preferably0 to 2; each
R is, independently, a nonhydrolyzable organic group; and each X is,
independently, a
hydrolyzable group (hereinafter, "organosilane of interest"); with an organic
carbonate,
preferably propylene carbonate.
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Accordingly, in one embodiment, this invention provides a water-stable
composition,
comprising the product or composition of the invention and water.
In a further embodiment, the present invention provides a composition for
treating a
substrate, comprising a carrier and an effective amount of the product or
compound of the
invention.
In yet another embodiment, the present invention provides a method of treating
a
substrate, comprising mixing the substrate with a sufficient amount ofthe
product, compound,
or composition of the invention for a period of time sufficient for treatment
of the substrate.
In a further embodiment, the present invention provides a composition for
treating a
substrate by incorporation in the substrate.
In a further embodiment, the present invention provides a composition for
treating a
substrate by incorporation into a polymer backbone.
In a further embodiment, the present inventionprovidesa composition as a
concentrated
solution, easily diluted with water, providing a water stable composition.
I 5 In a further embodiment, the present invention provides a composition as a
concentrated
solution which is the product of the synthesis of the compounds it comprises.
In a further embodiment, the present invention provides a treated substrate
having
adhered thereto or dispersed therein the product, compound, or composition of
the invention.
In addition, the present invention provides a method of dyeing and treating a
substrate,
comprising contactingthe substrate with an aqueous composition comprising an
aqueous soluble
dye suitable for dyeing a substrate and the product formed from mixing an
organosilane of
interest with an organic carbonate.
A further embodiment of the present invention provides a method of
antimicrobialiy
treating a substrate selected from the group consisting of a concrete pipe, a
tooth brush, a food
article, fluid container, latex medical article, gloves, shoes, a comb, a hair
brush, a denture, an
orthodontic retainer, a spa or pool filter, an air filter, an HVAC air system,
a cabin air system,
a marble article, a statue, an exposed work of art, a PE, PP or polyester
plastic cover, a silicone
or TEFLON~ coated fiberglass article, a Dryvitt finish, a stucco finish,
blended cotton, a bio-
fiIm, a bio-adhesive, a single ply roofing, a roofing shingle, and a
fiberglass reinforcement
product, comprising contacting the substrate with an effective amount of the
product formed
from mixing an antimicrobiai organosilane of interest with an organic
carbonate.
In addition, the present invention also provides a method of antimicrobially
enhancing
a product of rubbing alcohol, a flower preservative, or a waterproofing
solution, comprising
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admixing with the product an effective amount of the product formed from
mixing an
antimicrobial organosilane of interest with an organic carbonate.
A further embodiment of this invention is a method for making an organosilane
of
interest from starting materials in an aqueous solution in the presence of an
organic carbonate.
5 Additional advantages of the invention will be set forth in part in the
description which
follows, and in part will be obvious from the description, or may be learned
by practice of the
invention. The advantages of the invention will be realized and attained by
means of the
elements and combinations particularly pointed out in the appended claims. It
is to be
understood that both the foregoing general description and the following
detailed description are
exemplary and explanatory only and are not restrictive of the invention, as
claimed.
Detailed Disclosure of the Invention
The present invention may be understood more readily by reference to the
following
detailed description of preferred embodiments of the invention.
Before the present compounds, products, compositions, and methods are
disclosed and
described, it is to be understood that the terminology used herein is for the
purpose of describing
particular embodiments only and is not intended to be limiting. It is also to
be understood that
subject matter covered under the definition of certain terms, may, in some
instances, fall under
another term as well. It must be noted that, as used in the specification and
the appended claims,
the singular forms "a," "an" and "the" include plural referents unless the
contextclearly dictates
otherwise.
Throughout this application,wherepublicationsare referenced, the disclosures
ofthese
publications in their entireties are hereby incorporated by reference into
this application.
The term "alkyl" as used herein refers to a branched or unbranched saturated
hydrocarbon group of 1 to 24 carbon atoms, such as methyl ("Me"), ethyl
("Et"), n-propyl,
isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl,
eicosyl, tetracosyl, and
the like.
"Alkyl alcohol" as used herein refers to an alkyl having attached thereto one
or more
w hydroxy moieties, such as, but not limited to, -CHzCH,OH, CH~CH(OH)CH,,
CHzOH,
CH=CHZCH,OH, CH~CHZCH(OH)CH,, CH,CH~CH(OH)CHzOH, or CH,CH(OH)CH(OH)CH3.
The term "alkoxy" as used herein intends an alkyl group bound through a single
terminal
ether linkage; that is, an "alkoxy" group may be defined as -OR where R is
alkyl as defined
above.
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"Glycol" as used herein refers to glycol compounds, which includes, but is not
limited
to, ethylene glycol, propylene glycol, butylene glycol, isobutylene glycol or
hexylene glycol.
"Polyglycol"as used herein refers to a compound or moiety which takes the
polymeric
form of glycol, such as, but not limited to, polyethylene glycol or poly
propylene glycol.
Polyglycol would also include, for example, block and copolymers of ethylene
glycol and
propylene glycol. Polyglycols useful in the subject invention may have an
average molecular
weight of up to about 10,000 glmol.
"Polyalkylethers" refers to alkyls or alkyl alcohols interconnected by or
otherwise
possessingmuitipleetherlinkages. Polyalkylethersuseful in the subject
invention may have an
average molecular weight of up to about 10,000 g/mol.
"Alkyl glycol" as used herein refers to an alkyl connected to a glycol through
an ether
linkage. An example of an alkyl glycol includes, but is not limited to, butyl
glycol.
"Alkyl polygiycol" as used herein refers to alkyl connected to a polyglycol
through and
ether linkage. Alkyl polyglycol compounds useful in the subject invention may
have an average
molecular weight of up to 10,000 g/mol.
As used herein, "optional"or "optionally" means that the subsequently
described event
or circumstance may or may not occur, and that the description includes
instances where said
event or circumstance occurs and instances where it does not. For example, the
phrase
"optionally substituted lower alkyl" means that the lower alkyl group may or
may not be
substituted and that the description includes both unsubstituted lower alkyls
and lower alkyls
where there is substitution.
By the term "effective amount" of a compound, product, or composition as
provided
herein is meant a sufficient amount of the compound, product, or composition
to provide the
desired result. As will be pointed out below, the exact amount required will
vary from substrate
to substrate, depending on the particular compound, product, or composition
used, its mode of
administration, and the like. Thus, it is not always practical to specify an
exact "effective
amount," especially because a range of amounts or concentrations will usually
be effective.
However, an appropriate effective amount may be determ fined by one of
ordinary skill in the art
using only routine experimentation as a matter of optimization.
The term "cyclic" is used to refer to all aliphatic or aromatic hydrocarbons
having one
or more closed rings, whether unsaturated or saturated. Preferably, cyclic
compounds possess
rings of from 5 to 7 atoms, preferably 6 carbon atoms. Such rings fall into
three classes:
alicyclic, aromatic ("arene"), and heterocyclic. Moreover, when used with
respect to cyclic
compounds or moieties, the term "unsaturated" refers to such compound or
moiety possessing
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at least one double or triple bond or otherwise constituting an aromatic
compound or moiety.
Moreover, the term "saturated" refers to compounds or moieties possessing no
double or triple
. bonds within the ring, i.e., where all available valence bonds of an atom,
especially carbon, are
attached to other atoms.
The term "heterocyclic" refers to a cyclic compound or moiety where one or
more of
the carbon atoms of the ring has been substituted with a heteroatom,
including, but not limited
to O, N, or S.
The term "aryl" and "aromatic" are used interchangeably herein and refer to a
compound or moiety whose molecules have a ring or multiple (poly) ring
structure characteristic
of benzene, naphthalene, phenanthrene, anthracene, etc. Examples of aryls or
aromatics also
include, but are not limited to, phenyl, benzyl, naphthyl, benzylidine, xylil,
styrene, styryl,
phenethyl, phenylene, benzenetriyl, etc.
The term "heteroaryl" and "heteroaromatic" are used interchangeably and refer
to an
aryl where one or more of the carbon atoms of a ring have been substituted
with a heteroatom,
including, but not limited to, O, N, or S.
The term "cyclic alcohol" as used herein refers to a cyclic molecule
substituted with one
or more hydroxy moieties. Examples include, but are not limited to, Phenol and
cyclohexanol.
As used herein, especially in reference to alkyl and alkoxy, the term "lower"
refers to
a moiety having from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
As used herein, the term "suitable" is used to refer a moiety which is
compatible with
the compounds, products, or compositions as provided herein for the stated
purpose. Suitability
for the stated purpose may be determined by one of ordinary skill in the art
using only routine
experimentation.
As used herein, "substituted" is used to refer, generally, to a carbon or
suitable
heteroatom having a hydrogen or other atom removed and replaced with a further
moiety. In one
embodiment, halogen, hydroxy, and nitrogen based substitutions of hydrocarbon
hydrogens are
contemplated as within the scope of the present invention for the claimed
structures. Moreover,
it is intended that "substituted" refers to substitutions which do not change
the basic and novel
utility of the underlying compounds, products, or compositions of the present
invention.
"Unsubstituted" refers to a structure wherein the reference atom does not have
any further
moieties attached thereto or substituted therefor.
As used herein, "branched" is used to refer, generally, to a moiety having a
carbon chain
backbone, e.g., alkyl or alkoxy, wherein the backbone may contain one or more
subordinate
carbon chain branches. For example, isobutyl, t-butyl, isopropyl,
CH,CHzC(CH3)(H)CH,CH3,
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CH,C(CH,CH3)(H~HzCH3, CHZCHLC(CH, )CH,, and CH, CIA C(Cl-~ ) would all be
considered
branched moieties. Moreover, it is intended that ''branched" variations of the
moieties herein
described refer to variations which do not change the basic and novel utility
of the underlying
compounds, products, or compositions of the present invention. "Unbranched"
refers to a
structure wherein the carbon chain does not have any branches thereon, i.e.,
where the carbon
chain extends in a direct line.
As used herein, the term "acyI" refers to organic acid derived moieties of the
formula
RCO where R is an organic molecule. The free valance on C is used to bond to
other groups or
atoms.
As used herein, the term "acyloxy" refers to organic acid derived moieties of
the formula
RCOX where R is an organic molecule and X, instead of being hydroxy,
represents oxygen
attached to another group or atom.
As used herein, the term "perfluoro" or ''perfluoro- analog" refers to a
hydrocarbon
where the hydrogen atoms attached to carbons have been replaced with F atoms.
Preferably, but
not necessarily, in perfluoro- analogs, most if not all of the H atoms are
replaced with F atoms.
A "fluoro-"analog is contemplated to indicate a hydrocarbon where at least one
hydrogen atom
attached to a carbon is replaced with an F atom.
As used herein, "substrate" refers to any article, product, or surface that
can be treated
with the inventive compounds, preferably as enumerated hereinbelow under the
heading ''Uses,"
as described in the Examples hereto, and as specified in the relevant claims
appended hereto.
Suitable substrates are generally characterized by either having a negatively
charged surface of
oxygen atoms, or any surface capable of electrostatically, ionicaily, or
covalently adhering or
binding to the compounds, products, or compositions of the present invention.
Preferably the
adhering or binding occurs at the silicon atoms of the organosifane portion of
the compounds,
products, or compositions of the present invention, but such binding is not a
requirement.
"Substrate" also refers to materials that are treated by incorporation of the
compounds and/or
compositions of the present invention. Incorporation in this case includes the
process of
blending and mixing, and incorporation by becoming part of the material, i.e.,
poiymerbackbone
and cement. As used herein, the term "adhere" is meant to refer to ionic,
covalent, electrostatic,
or other chemical attachment of a compound, product, or composition to a
substrate.
As used herein, the term "antimicrobial lyenhancing" refers to the use of the
compounds,
products, or compositions of the present invention, preferably those wherein
the organosilane
has antimicrobial activity, along with other ingredients, surfactants,
fillers, wetting agents,
pigments, dyes, antimigrants, etc., to create a composition or solution
capable of fulfilling its
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original purpose, based upon the other ingredients, and also of providing
antimicrobial
protection during the particular application. The term "enhance" refers to the
addition of
antimicrobial activity to such compositions or solutions where no such
activity previously
existed, or to the increase of antimicrobial activity where the starting
compositions or solutions
already possessed antimicrobial activity.
As used herein, "hydrolyzable" refers to whether the moiety is capable of or
prone to
hydrolysis (i.e., splitting of the molecule or moiety into two or more new
molecules or moieties}
in aqueous or other suitable media. Conversely, "nonhydrolyzable" refers to
moieties that are
not prone to or capable of hydrolysis in aqueous or other suitable media.
As used herein, "cationic" is used to refer to any compound, ion, or moiety
possessing
a positive charge. Moreover, "anionic" is used to refer to any compound, ion,
or moiety
possessing a negative charge. Furthermore, "monovalent" and "divalent" are
used to refer to
moieties having valances of one and two, respectively. As used herein, the
term "salt" is meant
to apply in its generally defined sense as "compound formed by replacing all
or part of the
hydrogen ions of an acid with one or more rations of a base." ,See, e.g.,
American Heritage
Dictionary, Definition of "Salt" ( 1981 ). Therefore, suitable salts for the
present invention may
be formed by replacing a hydrogen ion of a moiety with a ration, such as K',
Na+, Ca'-', MgZ',
etc. In addition, other suitable methods of generating salts are specified
throughout this
specification and are within the scope of the present definition. For the
purposes of the present
invention, the specific identityofthe ration used for forming the salt is of
lesser importance than
the chemical structure of the anion of which the salt is formed.
As used herein, "food article" refers to perishable or nonperishable foods
such as meats,
fruits and vegetables, and also refers to other foods such as grains and dairy
products. In
preferable embodiments, the food articles referred to herein are those which
are perishable or
prone to spoilage upon exposure to microbes or other pathogens. In addition, a
"consumable
product" is meant to refer to food articles, fluids for drinking, medicines
for ingestion, or any
other product introduced internally via any means into a human or animal.
As used herein, the term "antimicrobial" is used in its general sense to refer
to the
property of the described compound, product, composition, or article to
prevent or reduce the
growth, spread, formation, or other livelihood of organisms such as bacteria,
viruses, protozoa,
molds, or other organisms likely to cause spoilage or infection.
As used herein, the term "medical article" is used to refer to any suitable
substrate which
is or may come into contact with medical patients (human or animal), medical
caregivers, bodily
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fluids, or any other source of contamination or infection generally associated
with hospitals,
clinics, physician's offices, etc.
As used herein, the term "stabilizer" is used to refer to carbonates. Such
compounds
have been found to stabilize the organosilanesofthe invention by preventing
self condensation
5 or other inactivation of the resulting compounds and products and
simplifying transportation,
dilution with water, and stabilization in water.
With these definitions in mind, the present invention provides the product
formed from
mixing an organosilaneofthe formulaR"SiX4_~ where n is an integer of from 0 to
3, preferably
0 to 2; each R is, independently,a nonhydrolyzableorganic group; and each X
is, independently,
10 a hydrolyzable group; with an organic carbonate.
More preferably, in the above product, n is an integer from 0 to 2, preferably
l; each R
is, independently, alkyl, preferably of from 1 to 22 carbon atoms branched or
unbranched,
substituted or unsubstituted, more preferably of from 1 to 6 carbon atoms or
from 10 to 20
carbon atoms, most preferably of from 1 to 4 carbon atoms or of from 14 to 18
carbon atoms;
alkyl alcohol of similar carbon lengths, branching, and substitution, or
aromatic, such as benzyl,
phenyl, etc.; each X is, independently,hydroxy, afkoxy, halogen (such as, but
not limited to, Ci,
Br, I, or F), acetyl, acetoxy, acyl, acyloxy, a hydroxylated solid or liquid
polymeric moiety,
polyglycolor polyalkylether;and carbonatestabiiizersaccording to the invention
are described
by formula Ia and Ib:
O
R-O"O-R (Ia)
R
O ~ ~O (Ib)
where each R is, independently,
alkyl; of from 1 to 24 carbon atoms,
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ethylene glycol, propylene glycol, butyl glycol, pentyl glycol, hexyl glycol,
alkyl glycol
with 2 to 24 carbon atoms,
aromatic, heteroaromatic, saturated and unsaturated aliphatic cyclic molecule,
each with
ring sizes of from 3 to 8 carbon atoms and in addition in hetero-cycles N, O,
S in place
of carbon atoms in any number and combination,
alkyl alcohol, polyethylene glycol, polypropylene glycol, block and
co-polymers of ethylene and propylene glycol and
block and copolymers of
ethylene glycol, propylene glycol, butyl glycol, peaty! glycol, hexyl glycol,
alkyl glycol
with 2 to 24 carbon atoms,
alkyl triol with 3 to 24 carbon atoms, alkyl tetrol with 4 to 24 carbon atoms,
and alkyl
pentol with 5 to 24 carbon atoms and alkyl hexol with 6 to 24 carbon atoms,
aromatic alcohol, heteroaromatic alcohol, saturated and unsaturated aliphatic
cyclic
alcohol, each with ring sizes of from 3 to 8 carbon atoms and in addition in
hetero-cycles N, O,
S in place of carbon atoms in any number and combination, with from 1 to 6
hydroxyl groups
on the cyclic alcohol, and substitution on the ring by (R,)x with x being an
integer from 0 to 3,
where R3 is independently, a (OH)Y substituted alkyl from 1 to 24 carbon atoms
where y is an
integer from 0 to 6.
The molecularweightofthe carbonate is up to approximately 10,000 grams/mol
average
molecular weight.
In a further embodimentofthe invention, the invention provides the product
described
above, wherein the organosilane is of the formula II, 1I1, I V or V
(R,)3SiR,N'(R3)(R4)(RS)Y- (II)
(Ry,SiRZN(R3)(R4) (III)
(RI)3SIRZR35 (IV)
(R1)3S~(R36)(R37) (V)
wherein each R, is independently, halogen or R60, where Rd is H, alkyl of from
1 to
. about 24 carbon atoms, acetyl, acetoxy, acyl, acyloxy, propylene glycol,
ethylene glycol,
polyethylene glycol, polypropylene glycol, block and copolymers of ethylene
and propylene
glycol, the alkyl monoether of from 1 to 24 carbons of the following:
propylene glycol, ethylene
glycol, polyethylene glycol, polypropylene glycol, block and copolymers of
ethylene and
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propylene glycol; or the monoester of a carbonic acid of from 1 to 24 carbons
and at least one
of the following: propylene glycol, ethylene glycol, polyethylene glycol,
polypropylene glycol,
block and copolymers of ethylene and propylene glycol; sorbitan esters and
their ethers;
phenolic compounds substituted with an alkyl of from about 1 to 24 carbons,
such as octyphenol,
and nonylphenol, and their ethers;
R35 is R6, H, halogen (such as Cl, Br, F, or I), NH2(CHz)ZNHR,, NHZR2,
C,HSOZRZ,
C4HSO,Rz, Na0(CH30)P(O)RZ, or C1CH,C6H4R2;
R36 and R3, are, independently, R35, halogen, H, alkyl, preferably of from 1
to 4 carbon
atoms, more preferably of from 1 to 2 carbon atoms, isobutyl, phenyl, or n-
octyl;
R, is R6, benzyl, vinyl or alkyl;
R, and R4 are, independently, R35, alkyl alcohol, alkoxy, alkyl of from 1 to
24 carbon
atoms, preferably 1 to about 10 carbon atoms, more preferably alkyl of from 1
to 4 carbon
atoms, or more preferably of from 1 to 2 carbon atoms;
R3 and R4 can, together, form a morpholine or cyclic or heterocyclic,
unsaturated or
saturated, five to seven-membered ring ofthe formula VI:
-R3-(R~)k-R4- (VI)
where k in an integer from 0 to 2, preferably 0 to 1, most preferably 1,
R,, where the ring is saturated is CH3, O, S, NH, NH,+, NCH,CH,NH,,
NCH,CH,NH;',NCH,CH,N(R8)(R9), NCHzCH=N'(R8)(R9)(R,o), N(alkyl), N(aryl),
N(benzyl),
where each R8, R9, and R,o is independently, benzyl, R3,, polyglycol,
preferably of from 1 to 4
carbon atoms, alkyl alcohol, preferably of from 1 to 4 carbon atoms, alkoxy,
preferably of from
1 to 4 carbon atoms, or alkyl, from 1 to 24 carbon atoms, preferably 1 to
about 10 carbon atoms,
and the "alkyl'' specified above is of from 1 to 3 carbon atoms, the "aryl" is
more preferably
phenyl or benzyl, and R,, where the ring is unsaturated is CH, N, N'H,
N'(aIkyl), N'(aryI),
N'(benzyl), N-CH,-N, N+H-CH,-N, N+(alkyl)-CH=-N, or N+(benzyl)-CH,-N, where
the alkyl,
aryl, or benzyl is as described above; wherein the ring is unsubstituted or
substituted with alkyl
of from 1 to 24 carbon atoms, more preferably of from 1 to 10 carbon atoms,
most preferably
of from 1 to 3 carbon atoms, ester, aldehyde, carboxylate (preferably acetoxy,
acetyl, acyl,
acyloxy or perfluorocarboxylate)amide, thionamide, vitro, amine, or halide,
most preferably Cl,
Br, or I. Alternatively, the ring provided by formula VI represents R3 or R,,
independently. The nitrogen in formula II or III that is part of the ring
structure of formula VI
is replaced by CH or CHZ or saturated with hydrogen or alkyl substitution of
from 1 to about 24
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13
carbons by removal of a positive charge. This ring is attached to the nitrogen
in structure II or
III, by removing any one hydrogen from the structure and placing a bond from
the nitrogen of
II or III to the atom missing the hydrogen.
RS is alkyl alcohol, preferably of from 1 to 6 carbon atoms, more preferably
of from 1
to 4 carbon atoms, R35, CH,C6H5, polyglycol, such as a polyethylene glycol or
a polypropylene
glycol, alkyl of from 1 to 24 carbon atoms, preferably of from I to 10 carbon
atoms, most
preferably of from I to 6 carbon atoms, alkoxy, of from 1 to 24 carbon atoms,
more preferably
of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms,
perfluoroalkyl, of
from 1 to 24 carbon atoms, more preferably of from 1 to 10 carbon atoms, most
preferably of
from 1 to 6 carbon atoms, perfluoroalkylsulfonate, of from 1 to 24 carbon
atoms, more
preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon
atoms,
perfluoroalkylcarboxylate, or is a five to seven-membered ring of formula VI
as described
above; and Y' is a suitable anionic moiety to form salts of the compound of
formula II, III, IV,
and V.
This invention provides a water stable composition, comprising water and an
organosilane of interest, mixed with carbonate.
The present invention provides a composition for treating a substrate,
comprising a
carrier and an effective amount of an organosiiane of interest and a carbonate
as described
herein. The carrier may be water, or in further embodiments, the carrier is
other than water.
Moreover, the present invention also provides a product resulting from mixing
an
organosilane ofthe formula II, III, IV, or V:
(R,)3SiR2N'(R3)(R4)(Rs)1'- (II)
(R,)3SiRZN(R3)(RQ) (III)
(R,)3SiR,RsS (IV)
(R,)aSi(R36)(R3O (V)
as substantially previously described with reference to the formula numbers
II, III, IV and V,
with carbonate stabilizers according to the invention as described above.
In addition, the present invention also provides a method of treating a
substrate,
comprising contacting the substrate with a sufficient amount of the
composition as described
above for a period of time sufficient for treatment of the substrate.
Moreover, in an alternate
embodiment, the present invention provides a method of treating a substrate,
comprising
CA 02296395 2000-O1-14
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contacting the substrate with a sufficient amount of the compound as described
above for a
period of time sufficient for treatment of the substrate.
In addition, the present invention provides a treated substrate having adhered
thereto the
product produced by contacting the organosilane and the carbonate as described
above.
S Alternatively, the present invention provides a treated substrate having
adhered thereto a
compound produced by contacting the organosilane and the carbonate as
described above.
In yet another embodiment, the present invention provides a method of dyeing
and
treating a substrate,comprisingcontactingthe substrate with an aqueous(i.e.,
substantiallywater
soluble) composition comprising an aqueous soluble dye suitable for dyeing a
substrate and the
product formed from mixing an organosilane of interest with an organic
carbonate.
In yet another embodiment, the present invention provides a method of
antimicrobially
treating a substrate selected from the group consisting of a concrete pipe,
food article, fluid
container, glove, shower curtain, shower door, latex medical artic le, a tooth
brush, a comb, a hair
brush, a denture, an orthodontic retainer, a spa or pool filter, an air
filter, an HVAC air system,
a cabin air system, a marble article, a statue, an exposed work of art, a PP,
PE or polyester
plastic cover, a silicone or TEFLON~ coated fiberglass article, a Dryvitt
finish, a stucco finish,
blended cotton, a bio-film, a bio-adhesive, a single ply roofing, a roofing
shingle, and a
fiberglass reinforcementproduct, comprising contacting the substrate with an
effective amount
of the product formed from mixing an antimicrobial organosilane of interest
with an organic
carbonate.
A further embodiment of the present invention provides a method of
antimicrobially
enhancing a product of rubbing alcohol, a flower preservative, or a
waterproofing solution,
comprising admixing with the product an effective amount of the product formed
from mixing
an antimicrobial organosilane of interest with an organic carbonate.
The present invention provides water-stabilized and solubilized organosilane
compounds, products, and compositions, methods of their use, and articles
prepared using the
compounds, products, and compositions. In particular, the present invention is
useful in
stabilizing a broad variety of organosilanesof the general formula R"SiXd_"
where n is an integer
offrom 0 to 3, preferably0 to 2; R is a nonhydrolyzable organic group, such as
but not limited
to, alkyl, aromatic, organofunctional,or a combination thereof; and X is
halogen, such as but not
limited to, CI, Br, or I, or X is hydroxy, alkoxy such as methoxy or ethoxy,
acetoxy, or
unsubstituted or substituted acyl or acyloxy. For such organosilanes, X is
prone to react with
various hydroxyl containing molecules.
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In a further embodiment, the present invention employs a carbonate as solvent.
The
silane and carbonate mixture are stable. The carbonate si lane mixtures often
are less flammable
than methanol mixtures and are easier to dissolve in water than many silanes
in methanol.
Alternatively, where the stabilizersare not sufficientlywater-
soluble,additional stability
5 is achieved by mixing the organosilanewith the stabilizer in a non-aqueous
solvent. In such an
alternative preparation,the remaining solvent (e.g., methanol) is liberated
via distillation, freeze
drying, evaporation or other methods known in the art for removal of volatile
organic solvents.
For carbonates within this invention that are themselves not very soluble in
water, an
organosilane-stabilizing effect in water may still be achieved by admixing the
organosilanewith,
10 for example, a carbonate in water, followed by filtration.
The solutions are stable for extended periods, from several days to several
months. It
will also be recognized that while aqueous silane stock solutions of up to 45%
silane may be
stabilized by carbonates disclosed herein, working siiane concentrationstend
to be in the 0.001-
10% silane range where the stabilization effects of the herein disclosed
stabilizers are less
15 challenged by the higher silane concentrations required in stock solutions.
Acid pHs appear to
be preferred, but not required, for stability of the solutions of the subject
invention.
The solutions of the present invention are, in certain preferred embodiments,
useful for
the applicationofvariousorganosilane coupling agents to surfaces in industrial
and household
uses without the use of toxic and/or flammable organic solvents. One of
ordinary skill in the art
would recognizethat the above preparation steps are merely guidelines and such
a person would,
without undue experimentation, be able to prepare the composition by varying
the parameters
for contacting or mixing the organosilane and the polyol and order of
introduction of reagents
and starting materials without deviating from the basic and novel
characteristics of the present
invention.
Silanes
The present invention is useful for stabilizing organosilanes of the general
formula
R"SiX,~" where n is an integer of from 0 to 3, preferably 0 to 2; R is a
nonhydrolyzable organic
group (alkyl, aromatic, organofunctional or a combination thereof); and X is
hydroxy, alkoxy,
preferably methoxy or ethoxy, halogen, preferably Cl, Br, or I, acetoxy, acyl
or substituted acyl,
acyloxy, or a hydrolyzable polymer or other moiety prone to hydrolysis and/or
environmental
harmfulness.
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The organosilanes used in the practice of the present invention need not be,
and often
are not, water soluble. By varying the stabilizer and preparation method, the
organosilanes
selected for use in the present invention are solubilized in water by the
stabilizer.
Numerous art-known organosilanesare suitable for the present stabilization
procedures
to produce water-stabilized compounds, products and compositions. United
States Patents
5,411,585; 5,064,613; 5,145,592, and the publication entitled "A Guide to DC
Silane Coupling
Agent" (Dow Corning, 1990) disclose many suitable organosilanes. The contents
of these
references are hereby incorporated in their entirety herein by this reference
for the teachings of
suitableorganosilanes. Theseorganosilanesaresuitablefortheformationofthewater-
stabilized
organosilanecompounds, products and compositions of the present invention. In
addition, the
disclosure of U.S. Patent No. 4,390,712 is hereby incorporated by reference
for its teaching of
siloxane synthesis in an aqueous medium. Per the instant disclosure, those
skilled in the art will
appreciate that the aqueous siloxane synthesis methods of the 4,390,712 patent
are modified to
advantage by performing the siloxane synthesis in the presence of the
carbonate stabilizer as
defined herein, thereby forming a stabilized siloxane-water composition while
still taking
advantage of the accelerated kinetics of siloxane formation in aqueous media
noted in the
4,390,712patent. Accordingly,a further embodiment of this invention is a
method for making
an organosilaneof the formula R"S1?C4_~ where n is an integer of from 0 to 3,
preferably 0 to 2;
each R is, independently, a nonhydrolyzable organic group; and each X is,
Independently, a
hydrolyzable group; from starting materials in an aqueous solution in the
presence of an
effective amount of carbonate sufficient to stabilize the organosilane as it
is formed from the
reactants. In the instant application we disclose the finding that compounds
having at least one
carbonate group stabilize aqueous organosilane solutions. The archetypal
example of carbonate
of the instant invention is propylene carbonate with an organic carbonate.
Preferred silanes for use in the compounds, products and compositions and
methods of
the present invention include silanes of the following formula:
(Ri)sSiR,N+(R3)(RaxRs)~'~ or (R~)3SiR~N+CSHSY-
wherein each R, is, independently, halogen [C1, Br, I, F] or R60, where R6 is
H, alkyl of from
1 to about 6 carbon atoms, unsubstituted or substituted, preferably from I to
about 2 carbon
atoms and more preferably 1 carbon atom, or acetyl- or other acyl, including
substituted acy) and
acyloxy; or R60 can be derived from any hydroxylated polymer, hydroxylated
liquid, or
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hydroxyiated solid regardless of water solubility; or R60 can be derived from
any polyglycol
such as, but not limited to, polyethyieneglycols or polypropyienegiycois, such
as
poly(propyleneglycol)triol(glycerol propoxylate); R, is unsubstituted or
substituted benzyl- or
an unsubstitutedor substituted alkyl of from 1 to about 3 carbon atoms,
preferably alkyl of from
S 1 to 3 carbon atoms; R3 and R4 are, independently, lower alkoxy of from 1 to
4 carbon atoms,
preferably of 2 carbon atoms, such as CHZCHZOH, CH,CH(OH)CH3, alkyl of from 1
to about
22 carbon atoms, preferably from 1 to about 10 carbon atoms and most
preferably from I to 2
carbon atoms or R3 and R4 can, together, form a morpholine ar other cyclic or
heterocyclic,
unsaturated or saturated, five to seven-membered ring of the formula:
-R3-(R~)k-R4_
where k is an integer from 0 to 2 and R,, where the ring is saturated, is CH,,
O, S, NI-I, NH,~,
NCHZCH,NH,, NCHzCH,NH3+, NCHZCH~N(R$)(R9), NCH,CH,N'(Rg)(R9)(R,o), N(alkyl),
N(aryl), N(benzyl), and R,, where the ring is unsaturated is, N, N'H,
N+(alkyl), N'(aryl),
N'(benzyl), N-CH,-N, N+H-CHz-N, N'(alkyl)-CH,-N, N'(aryl)-CH,-N, or N'(benzyl)-
CH,-N
where R8, R9, and R,o are, independently, benzyl, polygiycol, lower alkyl
alcohol of from 1 to
4 carbon atoms, lower alkoxy of from 1 to 4 carbon atoms, or alkyl of from 1
to about 22 carbon
atoms, preferably 1 to about 10 carbon atoms; RS is CH,C6H5, CH,CHZOH,
CHZCH(OH)CH3,
a polyglycol such as polyethyieneglycol: -(CH~CH,O)aH, polypropyleneglycol: -
(CH,CH(CH3)O)eH, or alkyiated polyoxyethylene: -(CI-I=CH~O)aB where B is alkyl
of from 1
to 22 carbon atoms, unsubstituted or substituted, and where each a is,
independently, an integer
of from 1 to 12, more preferably of from about I to about 5, or RS is alkyl or
perfluoroalkyl of
from 1 to about 22 carbon atoms, preferably from about 12 to about 20 carbon
atoms and even
more preferably from 14 to about 18 carbon atoms; and Y is halogen (such as
Cl, Br, I), acetate,
sulfate, tosylate or carboxylate, such as acetate, polycarboxylate salts,
alcoholates,
functionalized carboxylate, such as trifluoroacetate and
perfluoroalkylcarboxylates, or other
alkyl and arylsulfonate salts, including trifluoromethylsulfonate and anionic
metal oxides,
perfluoroalkylsulfonate salts, phosphate and phosphonate salts, borate and
boronate salts,
benzoates or any other suitable anionic moiety and the ring provided for
formula V represents
R3 or R4, independently, with the ring nitrogen of formula I I or III replaced
by CH or CHZ. This
ring is attached to the nitrogen in structure II or III, by removing any one
hydrogen from the
structure and placing a bond from the nitrogen of II or III to the atom
missing the hydrogen.
Preferred organosilanes include, but are not limited to:
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WO 99/03866 PCT/US98/14985
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3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride,
3-(trimethoxysilyl)propylmethyldi(decyl) ammonium chloride,
3-chloropropyltrimethylsilane,
octadecyltrimethoxysilane,
perfluorooctyltriethoxysilane,
(CH30)3Si(CHz)3N+(CH3)zC,sH3,C1-,
(CH30)3Si(CHz)3N+(CH3)zC,aH3~Br
(CH30)3Si(CHz)3N'(C,oHz,)CH3C1',
(CH30)3Si(CHz)3N+(C,oHz,)CH3Bt,
(CH3O),St(CI-Iz),N+(CH3)3C1-,
(CH30)3Si(CHz)3N'(CH3)zCaH"Cl-,
(CH30),Si(CHz)3N+(CH3)zC,oHz, C1',
(CH30)3Si(CHz)3N+(CH3)zC,zHzsCl-~
(CH30)3Si(CHz)3N+{CH3)zC,aHz9Cl-,
(CH3O)3Si(CHz)3N+(CH3)zC16H33C1
(CH30)3Si(CHz)3N'(CH3)zC,oH4,Cl',
(CH3O)3Si(CHz)3N+(C41-I9)3C1
(CH30)3Si(CHz)3N+(C.,Hs)3C1-,
(CH3CHz0),Si(CHz)3N+(CH3)zC,gHz,Cl',
{CH30)3Si(CHz)3NHC(O)(CFz)6CF3,
(CH30)3Si(CHz)3NHC(O)(CFz)8CF3,
(CH30)3Si(CHz)3NHC(O)(CFz),oCF3,
(CH30)3Si(CHz)3NHC(O)(CFz),zCF3,
(CH30)3Si(CHz)3NHC(O)(CFz),4CF3,
(CH30)3Si(CHz)3NHC(O)(CFz),6CF3,
(CH30)3Si(CHz)3NHSOz(CFz),CF3,
(CH30)3Si(CHz)3N+(CH3)z(CHz)3NHC{O)(CHz)6CH3,
(CH30)3Si(CHz)3N+(CH3)z(CHz)3NHC(O)(CHz)BCH;,
(CH30)3Si(CHz)3N+(CH3)z(CHz)3NHC(O)(CHz),oCH3,
(CH30)3Si(CHz)3N+(CH3)z(CHz)3NHC(O)(CHz),zCH,,
(CH30)3Si(CHz)3N+(CH3)z(CHz)3NHC(O)(CHz),aCH3,
(CH30)3Si(CHz)sN+(CH3)z(CHz)3NHC(O)(CHZ),6CH3,
(CH30)3Si(CHz)sN+(CH3),(CHz)3NHC(O)(CFz)6CF3,
(CH30)3Si(CHz)3N+(CH3),(CHz)3NHC(O)(CFz)8CF3,
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(CH30)3Si(CHz)3N+(CH3)z(CHz)3NHC(O)(CFz),oCF3,
(CH30)3Si(CHz);N+(CH3)z(CHz)3NHC(O)(CFz),zCF3,
(CH30)3Si(CHz)sN+(CH3)z(CHz)sNHC(O)(CFz),oCF3,
(CH30)3Si(CHz)sN+(CH3)z(CHz)3NHC(O)(CFz),6CF3,
(CH30)3Si(CHz)sN+(CH3)z(CHz)3NHSOz(CFzOCF3,
(CH30)3Si(CHz)sN+(CH3)z(CHz)3NHSOz(CFz)9CF3,
(CH30)3Si(CHz)sN+(CH3)z(CHz)3NHSOz(CFz)nCFs,
(CH;O)3Si(CHz)sN+(CH3)z(CHz)3NHSOz(CFZ),3CF3,
(CH30)3Si(CHz)3N'(CH3)z(CHz)3NHS02(CFz)isCF3,
(CH30)3Si(CHz) _3N+(CH3),(CHz)3NHSOz(CFz),6CF3,
aminoethylaminopropyltrimethoxysilane: NH,(CHz)zNH(CHz)3Si(OCH3)3,
3-aminopropyltrimethoxysilane: NHz(CHz)3Si(OCH3),,
3-aminopropyltriethoxysilane: NHz(CHz)3Si(OCH,CH3)3,
3-chloropropyltrimethoxysilane: CI(CHz),SI(OCH,)3,
3-chloropropyltriethoxysilane: CI(CHz),Si(OCH,CH3)3,
3-chloropropyltrichlorosiiane: CI(CHz)3SiCl3,
3-glycidoxypropyltrimethoxysilane: C3HsOz(CH=),SI(OCH3)3,
3-glycidoxypropyltriethoxysilane: C,HSOz(CHz)3S1(OCH,CH,}3,
3-methacryloxypropyltrimethoxysilane: C4HSO,(CH,)3S1(OCH3)3,
3-methacryloxypropyltriethoxysilane: C4HSOz(CHz)3Si(OCH,CH,)3,
methyldichlorosilane: CH,SiHCIz,
silane-modified melamine: Dow Corning Ql-6106,
sodium (trihydroxysilyl)propylmethylphosphonate: Na0(CI-130)P(O)(CHz)3Si(OH)3,
trichlorosilane, SiHCI,,
n-2-vinylbenzylamino-ethyl-3-aminopropyltrimethoxysilane HCL: Dow Corning Z-
6032,
vinyltriacetoxysilane: HZC=CHSi(OCOCH3)3,
vinyltrimethoxysilane: H2C=CHSi(OCH,)3,
vinyltriethoxysilane: HZC=CHSi(OCHzCH3)s>
vinyltrichlorosilane: HZC=CHSiCl3,
dimethyldichlorosilane: (CH,)zSiClz,
dimethyldimethoxysilane: (CH3)zSi(OCH,)z,
diphenyldichlorosilane: (C6Hs)zSiClz,
ethyltrichlorosilane: (C,Hs}SiCl3,
ethyltrimethoxysilane: (CzHs)Si(OCH3)3,
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ethyltriethoxysilane: (CZHS)Si(OCH,CH3)3,
isobutyttrimethoxysiiane,
n-octyltriethoxysilane,
methylphenyldichlorosilane: CH3(C6H5)SiClz,
5 methyltrichlorosilane: CH3SiC13,
methyltrimethoxysilane: CH3S1(OCH3)3,
phenyltrichlorosilane: C6HSSiCl3,
phenyltrimethoxysilane: C6HSSi(OCH3)3,
n-propyltrichlorosilane: C3H,SiCl3,
10 n-propyltrimethoxysilane: C3H.,S1(OCH3)3,
silicon tetrachloride: SiCl4,
C1CH,C6HQCH,CH,SiCl3",
C1CHZC6H4CH,CHZSi(OCH3)3,
CICH,C6H4CH,CH,Si(OCHzCH3)3,
IS decyltrichlorosilane,
dichloromethyl(4-methylphenethyl)silane,
diethoxymethylphenylsilane,
[3-(diethylam ino)propyl]trimethoxysilane,
3-(d imethoxymethylsi lyl)- I -propanethiol,
20 dimethoxymethylvinylsilane,
3-[tris(trimethylsilyloxy)silyl]propyl methacrylate,
trichloro[4-(chloromethyt)phenyl]silane,
methylbis(trimethylsilyloxy)vinylsilane,
methyltripropoxysilane, and
trichlorocyclopentylsilane.
In one particular embodiment of this invention, namely the use of the
organosilane as
a UV protectant, for example, in a sun-tan lotion, para-amino benzoic acid,
cinnamic acid,
benzoic acid and benzophenone are active ingredients. These compounds and
their alkyl
derivatives attached to a siloxane are part of this invention. Some examples
are:
(CH30)3Si(CHZ)3NHC6H4COOH
(CH30)3Si(CH2)3NHC6H4COOCH3
(CH30),Si(CHz)3NHC6H4COOCzHS
(CH30)3Si(CHZ)3NHC6HQCOOC3H,
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(CH3O),Si(CHz)3NHC6H4COOC,H9
(CH30)3Si(CHz)3NHC6H4COOCHZC6H5
(CH30)3Si(CHz)3NHC6H,COOCHZC6H4NH2
(CH30)3Si(CHZ)3NHC6H,COOCHZC6HQN(CH3)z
(CH30)3Si(CHZ)3NHC6H4COOCHZC6H4N(CHZCH3)2
(CH30)3Si(CHZ)3NHC6H4COOCHZC6H4N+(CH3)3 Y_
(CH30)3Si(CHZ),NHC6H,COOCHzC6H4N'(CHZCH3)3 Y_
(CH30),Si(CH,),NCH3C6H4COOH
(CH,O)3Si(CHz)3NCH3C6HQCOOCH3
(CH30)3Si(CHZ)3NCH3C6HQCOOCzHS
(CH3O)3S1(CHZ),NCH,C6H4COOC3H,
(CH3O)3S1(CH,)3NCH3C6H4COOC4H9
(CH3O)3Si(CHZ),NCH,CbH4COOCH2C6H5
(CH30)3Si(CHZ)3NCH3C6H4COOCH,C6HQNH,
(CH30)3Si(CH,),NCH3C6H4COOCHZC6H4N(CH3)2
(CH30)3Si(CHz)3NCH3C6HQCOOCHZC6H4N(CH,CH3)~
(CH30)3Si(CHz)3NCH,C6H4COOCHZC6H4N'(CH3), Y_
(CH30)3Si(CHZ),NCH3C6H4COOCH,C6H4N'(CH,CH3), Y-
(CH30),Si(CH2),N'(CH,)ZC6H4COOH Y_
(CH30)3S1(CHz);N+(CH3),C6H4COOCH, Y_
(CH30)3SI(CHZ)3N+(CH3)=C6H4COOC,HS Y-
(CH,O)3SI(CHZ);N'(CH,),C6H4COOC,H, Y-
(CH3O)3SI(CHz)3N+(CH3),C6H4COOC4H9 Y
(CH3O)3SI(CHzON+(CH3)2CeHaCOOCH2C6H5 Y
(CH30)3Si(CHZ)3N+(CH3)ZC6H4COOCH,C6H4NH, Y
(CH30),Si{CHz)3N'(CH3)ZC6H4COOCHZC6HQN(CH3), Y-
(CH30)3Si(CH,)3N'(CH3)ZC6H4COOCHzC6H4N(CH,CH3), Y'
(CH3O)3S1(CH2)3N+(CH3)2C6H4COOCHzC6H~N+(CH3)3 Y_Y_
(CH30)3Si(CHI),N'{CH3)zC6H4COOCH,C6H4Ni(CH,CH3)3 Y_Y_
(CH30)3Si(CHz)3NCzH5C6H4COOH
(CH30),Si(CHZ)3NCzH5C6H4COOCH,
(CH,O),Si(CH,),NC~HSC6H,COOC4H9
(CH3O)3SI(CHZ),NCZHSC6H,COOC3H,
(CH,O),SI(CHZ),NCZHSC6H,COOC,H9
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WO 99/03866 PCT/US98/14985
22
(CH3O)3S1(CHz)3NC2HSC6H4COOCHzC6Hs
(CH30)3Si(CHz)3NCzHsC6H4COOCHzC6H4NHz
(CH30)3Si(CHz)3NCZH5C6H,~COOCHZC6H,~N(CH3)z
(CH30)3Si(CHz)3NCZHSC6H4COOCHZC6H4N(CH,CH3)z
(CH30)3Si(CHz)sNCzHsCbHaCOOCHzC6H4N+(CH3)s Y_
(CH30),Si(CHz)3NCzH5C6H4COOCHzC6H,N+(CH,CH,), Y-
(CH30)3Si(CHz)3N+(CZHs)zC6HaCOOH Y_
(CH30)3Si(CHz)3N'(CzHs)zC6H4COOCH3 Y_
(CH30)3Si(CHz)sN+(C,Hs)zC6HaCOOC2Hs Y_
(CH30)3Si(CHz),N~(C,Hs)zC6H4COOC3H, Y_
(CH30)3Si(CH2);N+(CzHs)zCeH4COOC4H9 Y_
(CH30)3Si(CHz)3N'(CzHs)zC6H4COOCHZC6Hs Y_
(CH30)3Si{CHz)3N'(C,Hs)zC6HaCOOCHZC6H,~N, Y_
(CH30)3Si(CHz)3N~{C,Hs)zC6H,COOCH,C6H,,N(CH3)z Y_
(CH30)3Si(CHz);N'(CzHs)zC6H4COOCH2C6H4N(CH,CH,)z Y_
(CH30)3Si(CHz)3N+(C,Hs)zC6H4COOCH,C6H4N'(CH;)3 Y_Y_
(CH30)3Si(CHz)3N+(CzHs)zC6HaCOOCHzC6H4N'(CH,CH3)3 Y_Y_
(CH3CHz0),Si(CHz)3NHC6H4COOH
(CH3CH20)3Si(CHz)3NHC6H4COOCH3
(CH3CHz0)3Si(CHz)3NHC6HQCOOCZHs
(CH3CH,0)3Si(CHz}3NHC6HQCOOC3H,
(CH3CH,0),Si(CHz),NHC6HQCOOC4H9
(CH3CHz0)3Si(CHz)3NHC6HQCOOCHzC6Hs
(CH3CHz0)3Si(CHz)3NHC6H4COOCHZC6H4NHz
(CH3CHz0),Si(CH,)3NHC6HQCOOCHzC6H4N(CH3)z
(CH3CHZ0)3Si(CHZ)3NHC6H4COOCHZC6HQN(CHzCH3)z
(CH3CHzO)3Si(CH.,)3NHC6HQCOOCHZC6H4N'(CH3), Y_
(CH,CHzO)3Si(CHz);NHC6HQCOOCH,C6H4N+(CH,CH3)3 Y_
(CH3CH,0)3Si(CHz)3NCH,C6HQCOOH
(CH3CH20)3Si(CHz)3NCH3C6HQCOOCH3
(CH3CH20)3Si(CHz},NCH3C6H4COOCzHs
(CH,CH20)3Si(CH~)3NCH3C6HQCOOC3H,
(CH3CH,0),Sl(CHz)3NCH3C6H4COOCQHg
(CH3CHz0)3Si(CHz)3NCH3C6H4COOCHZC6Hs
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WO 99/03866 PCT/US98/14985
23
(CH3CHz0)3Si(CHz)3NCH3C6H4COOCH2C6H4NHz
(CH3CH20)3Si(CHz)3NCH3C6H4COOCHzC6H,,N(CH3)z
(CH3CHz0)3Si(CHz),NCH3C6H,COOCHzC6H4N(CHZCH3)z
(CH3CH,O)3SI(CHz),NCH3C6H4COOCH,C6H4N+(CH3)3 Y-
(CH,CH20)3Si(CHz),NCH3C6HaCOOCHzC6H4N+(CHzCH3)3 Y-
(CH3CH20)3Si(CHz)3N+(CH3)zC6H,COOH Y-
(CH3CHz0)3Si(CHz)3N+(CH3)zC6H4COOCH3 Y-
(CH3CH.,O)3S1(CHz)3N+(CH3)zC6H4COOCZHS Y'
(CH3CH20)3Si(CHz)3N+(CH3)zC6H4COOC3H, Y'
(CH3CHZO)3S1(CHz)3N+(CH3)zC6H4COOC4H9 Y'
{CH3CH=O)3Si(CHz)3N~(CH3)ZC6H,COOCHZC6H5 Y-
(CH3CH,0)3Si(CHz)3N+(CH3)zC6HaCOOCH.,C6H4NHz Y-
(CH3CH,0)3Si(CH,)3N+(CH,)zC6H4COOCH,C~H~N(CH,), Y-
{CH3CH20),Si(CHz)3N'(CH3)zC6H4COOCH2C6H,,N(CH,CH3)z Y'
(CH3CH,0)3Si(CHz)3N+(CH3)zC6H4COOCH2C6HyN'(CH3)3 Y'Y-
(CH3CH20)3Si(CHz)3N'(CH3)zC6H4COOCHZC6HdN'(CH,CH3)3 Y'Y'
(CH3CHz0)3Si(CHz)3NCZHSC6H,COOH
(CH3CH,0)~,Si(CHz)3NCZHSC6H4COOCH3
(CH3CH20),Si(CHz)3NCzH5C6H4COOC2H5
(CH3CH20)3Si(CHz)3NC,HSC6HQCOOC3H,
(CH3CHz0),SI(CHz),NCZHSC6H4COOC4H9
(CH3CHz0)3Si(CHz)3NC,HSC6H4COOCHZC6H5
(CH3CH20),Si(CHz)3NC,HSC6H4COOCH,C6H4NH,
(CH3CHz0)3Si(CHz)3NC,HSC6H4COOCHZC6H4N(CH3)z
(CH3CHzO)3Si(CHz)3NCZHSC6H4COOCHZC6HqN(CH,CH3)z
(CH3CHzO)3Si(CHz),NC,HSC6HQCOOCHZC6H4N+(CH3), Y'
(CH3CHz0),Si(CHz)3NCzH5C6H4COOCH2C6H4N'(CH,CH,)3 Y-
(CH3CHz0),Si(CHz)3N+(CzHS)zC6H4COOH Y'
(CH3CHz0)3Si(CHz)3N+(C2H5)zC6H4COOCH3 Y'
(CH3CHz0)3Si(CHz)3N+(CZHs)zCeHaCOOCZHs Y'
(CH3CH20)3Si(CHz)3N'(CzHs)zCeHaCOOC3H, Y-
(CH3CH20)3Si(CHz)3N'(C,HS)zC6H,COOC4H9 Y'
(CH3CHz0)3Si(CHz)sN+(CzHs)zC6HaCOOCH.,C6H5 Y'
(CH3CHz0)3Si(CHz)3N'(C,HS)zC6H4COOCHzC6H4NHz Y'
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24
(CH3CHz0)3Si(CHZ)3N+(CZHs)zC6H4COOCHzC6H4N(CH3)z Y.
(CH3CH20)3Si(CHz}3N+(CZHs)zC6HaCOOCH2C6I-I4N(CH,CH3)z Y
(CH3CH20)3Si(CHz)3N'(CZI-IS)zC6I-14COOCH,C6H4N'(CH3)3 Y-Y-, and
(CH3CHZO)3S1(CHZ)3N'(C2I-IS)2C6H4COOCHZC6H4N+(CHZCH3)3 Y~Y~.
Stabilizers
Carbonate stabilizers according to the invention are described by formula Ia
and Ib:
R-O O-R (Ia)
R
O w i0 ~Ib~
O
where R is, independently,
alkyl; of from 1 to 24 carbon atoms,
ethylene glycol, propylene glycol, butyl glycol, pentyl glycol, hexyl glycol,
alkyl glyco!
with 2 to 24 carbon atoms,
aromatic, heteroaromatic, or saturated and unsaturated aliphatic cyclic
molecule, each
with ring sizes of from 3 to 8 carbon atoms and in addition in hetero-cycles
N, O, S in
place of carbon atoms in any number and combination,
alkyl polyol, polyethylene glycol, polypropylene glycol, block and
co-polymers of ethylene and propylene glycol and
block and copolymers of
ethylene glycol, propylene glycol, butyl glycol, pentyl glycol, hexyl glycol,
alkyl glycol
with 2 to 24 carbon atoms,
alkyl triol with 3 to 24 carbon atoms, alkyl tetrol with 4 to 24 carbon atoms,
and alkyl
pentol with 5 to 24 carbon atoms and alkyl hexol with 6 to 24 carbon atoms,
aromatic alcohol, heteroaromatic alcohol, or saturated and unsaturated
aliphatic cyclic
alcohol, each with ring sizes of from 3 to 8 carbon atoms and in addition in
hetero-cycles N, O,
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S in place of carbon atoms in any number and combination, with from I to 6
hydroxyl groups
on the cyclic alcohol, and substitution on the ring by (R3)~ with x being an
integer from 0 to 3,
where R3 is independently, a (OH)y substituted alkyl from 1 to 24 carbon atoms
where y is an
integer from 0 to 6.
5 The molecularweight of the carbonate is up to approximately 10,000 grams/mol
average
molecular weight.
ses
The compounds, products and compositions of the present invention are useful
for a
10 multitude of purposes. Such purposes include any known use for the
preferred starting material
organosilanesofthe above-described general formula. In preferred embodiments,
the presently
described, water-stabilized, organosilane compounds, products, and
compositions are suitable
to applications such as: I) treatment of surfaces, including fillers and
pigments, 2) additives to
coatings such as dyes, 3) as additives to organic monomers (such as acrylics)
prior to formation
15 ofthe respectivepoIymer,4) addition to the polymer prior to processing into
final products, or
5) incorporation into polymer or substrate backbone, such as polyester or
concrete.
Therefore, in addition to the utility of prior organosilane quaternary
ammonium
compounds such as 3-(trimethoxysilyl)propyl-dimethyloctadecylimmonium chloride
as surface
bonding antimicrobial agents, numerous other uses of organofunctionalsilanes
are contemplated,
20 such as the use of the compounds, products and compositions of the
invention in coating
applications which include the treatment of surfaces or particles (pigments or
fillers), in primers,
in paints, inks, dyes and adhesives, and as reactive intermediates for
silicone resin synthesis.
The present invention can be used to prepare, inter alia, agricultural
products, cleaning
compositions, antimicrobial sponges, antimicrobial bleaching agents,
antimicrobial fillers for
25 paints, plastics, or concrete, and to treat concrete structures such as
livestock shelters, where
microbial infestation is a problem.
In various embodiment, surfaces and substrates treatable with the compounds,
products
and compositions of the invention solution include, but are not limited to,
textiles, carpet, carpet
backing, upholstery,clothing, sponges, plastics, metals, surgical dressings,
masonry, silica, sand,
alumina, aluminum chlorohydrate, titanium dioxide, calcium carbonate, wood,
glass beads,
containers, tiles, floors, curtains, marine products, tents, backpacks,
roofing, siding, fencing,
trim, insulation,wall-board,trash receptacles, outdoor gear, water
purification systems, and soil.
Furthermore, articles treatable with the compounds, products and compositions
of the invention
include, but are not limited to, air filters and materials used for the
manufacture thereof,
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26
aquarium filters, buffer pads, fiberfill for upholstery, fiberglass ductboard,
underwear and
outerwear apparel, polyurethane and polyethylene foam, sand bags, tarpaulins,
sails, ropes,
shoes, socks, towels, disposal wipes, hosiery and intimate apparel; cosmetics,
lotions, creams,
ointments, disinfectant sanitizers, wood preservatives, plastics, adhesives,
paints, pulp, paper,
cooling water, and laundry additives and non-food or food contacting surfaces
in general.
For the above described substrates, mixtures and applications, treatment
generally
involves contacting or mixing the article to be treated with a water-
stabilized organosilane
solution of the present invention, comprising the organosilane-stabilizer
derived compound in
an aqueous solution, for a period of time sufficient for permanent bonding of
the active
organosilane ingredient (or portion thereof) to the article. In alternative
embodiments,
organosilane-carbonate mixtures according to the invention can be used
directiywithout dilution
with water, or, alternatively, dilutions with solvents other than water can be
used according to
the invention Generally, treatment begins immediately upon contact, but
preferably requires
from about 15 seconds to about48 hours. Many examples and guidelinesare shown
for efficient
silane surface treatment and incorporation, for example "Applying A Silane
Coupling Agent",
page 49, Gelest Catalog, by Gelest, Inc. Tullytown, PA, 1995. Further general
guidelines for
application are as follows: For dipping a large object, it is preferred that 1-
2 minutes of
submersion is allowed in the solution and then the object is permitted to dry
or is dried.
However, some objects will benefit from very short dipping, mixing or
contacting times, for
example, fabric may pass through an aqueous bath of the composition at a rate
of 40 yards per
minute or more. After dipping, excess solution may be gently wiped or rinsed
off.
Alternatively,the solution may be sprayed on the substrate. Moreover, the
composition of the
invention may be placed in a high intensity solid mixer and formed into a
powder which is then
dried. The dried powder may then be used in a sprayer, if desired. In
addition, the solutions
may be wiped onto the substrate and applied using sponges or cloths, etc.
Moreover, the
solutions of the present invention can be added to pigments and fillers and
stirred therewith for
several (2-3) minutes. In addition, the solutions can be added to an emulsion
or other existing
formulation prior to use. Also, the solutions can be used in addition to, with
or as a spray
coolant for extruded fibers. However, one of ordinary skill in the art would
recognize that
numerous other uses and modes of application are readily apparent from the
stabilized
organosilane compounds, products and compositionsof the present invention and
would, without
undue experimentation, be able to determine effective application methods and
treating times
for any particular substrate, article, or other application. In addition, the
compositions can be
used in padding processes as are known in textile mills.
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27
Moreover, after treating a surface or fabric with the compound, product or
compositions
of the present invention, the surface or fabric may, optionally, be heated to
further complete
bonding of the compound, product, or composition to the surface or substrate.
The water-stable organosilane compounds, products and compositions of the
present
invention are, therefore, advantageous in treating a variety of substrates
without the use of toxic
organic solvents, and provide for the safe, long-term storage of activated
organosilanol
compound which can be used without further preparation. Moreover, the
stabilization scheme
described herein does not interfere with the binding of the organosilane (or
at least the core,
operative portion thereof] to the substrate. In addition, the present
invention provides a
generally applicable scheme for solvating some water insoluble organosilanes.
Also apparent will be those applications where organosilanes R"SiX,,_" are
prepared,
dissolved, stored, applied, and in any way used in water. In addition, also
apparent will be those
applications of organosilanes R"SIXy_", in other solvents or mixed in other
media (solids,
polymer mixes, fillers, pigments, powders, dyes or emulsions) where exposure
to water occurs
but could be detrimental due to undesired or untimely self condensation of the
silanol.
Moreover, the stabilizing compounds and methods could be used in addition to
or in
conjunction with various art-known stabilization methods for organosilanes,
such as the use of
ionic or non-ionic surfactants and detergents.
Moreover, the present compounds, products and compositions can be used in the
incorporation of an organosilane antimicrobial agent in most textile goods
(woven and non-
woven) and yarns (synthetic and natural). The process provides articles that
are durable and the
process itself is effective and does not require additional manufacturing
steps or increase
manufacturing cost.
Further, as is well known in the art, certain classes of organosilanes have
properties
which can repel water and other liquids. Accordingly, one embodiment of the
subject invention
is directed toward a method of treating a substrate to render the substrate
resistant to stains.
Incorporating the compounds, products and compositionsof the present invention
during
the dye process yields a textile material with a built-in antimicrobial
activity or other desired
property with the organosilane characteristics. The incorporation process 1 )
does not add any
additional step in the manufacturingprocess and does not require any equipment
modification;
and 2) is believed not to lose its antimicrobialcharacteristicsand its
effectivenessduring further
production of the textile goods. By incorporating the water-stable compounds,
products and
compositions of the present invention during the dye process, not only would
the organosilane
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antimicrobial agent remain unaffected by the dying agent, but the end-product
textile goods
would also exhibit excellent dyeing properties.
The water-stabiiizedorganosilane compounds, products and compositions of the
present
invention are useful for a number of applications where the previous
instability, insolubility
S prevented or, at least, hindered or restricted use of some organosilane
agents. For example:
Treating food crops (e.g., perishables such as vegetables, fruits, or grains)
after removal
(pickled/harvested) with the compounds, products and compositions of the
present invention
imparts antimicrobial protection to the outer surface of the food crop. It is
believed that such
protection occurs without diffusing, migrating or leaching the antimicrobial
agent from the
bonded antimicrobial coating of the food item, and provides prolonged, safe
and non-toxic
antimicrobial protection. The method involves treating fruits and vegetables
in the rinse cycle,
during or after the normal cleaning/water spraying or during or after
blanching. Thorough
cleaning of fruits and vegetables at the processing plant is preferred for
initially removing
microorganisms. As one of ordinary skill in the art would recognize, machines
are used initially
I S to remove soil, chemicals used in growing, spoilage bacteria, and other
foreign materials. These
machines also use high velocity water sprays to clean the products. After the
cleaning, raw
foods or other crop materials are prepared for further processing such
blanching (i.e., the food
is immersed in water at 190 to 210 degrees F. or exposed to steam).
Microorganismsare controlled by the production plant up until the fruit or
vegetable is
removed. But once it is removed, organisms such as yeast, mold, and bacteria,
begin to
multiply, causing the food to loose flavor and change in color and texture. To
keep the food
from spoiling, a number of methods have been employed, such as refrigerators,
to slow down
the microorganisms and decay deterioration. Unfortunately, such known methods
will preserve
raw foods for few weeks at the most. The compounds, products and compositions
of the present
invention can preserve these items for extended periods. For instance, the
compositions,
products, or compounds may be added to an existing water line feeding the
sprayers for the
foods, where such sprayers are used. Otherwise, a simple dipping process may
be used, where
the dipping requires only a few seconds to impart antimicrobial protection.
Low concentrations
of 0.1 to 1 % aqueous solution (0.1 to 1 % by volume) of the compositions
provide satisfactory
results. In addition, it is believed that the presently described method can
also control pathogens
on poultry carcasses and in other susceptible meat and fish.
Treating baby milk/juice bottles, nipples, pacifiers and toys with the
compounds,
products and compositions of the present invention in the factory or leaching
the agent from the
bonded surface, can provide prolonged and safelnon-toxic antimicrobial
protection. Treating
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such articles also eliminates odors caused by microbial contamination. A
dipping method as
described above may be used to treat these articles.
To date, parents have used soaps, detergents, and surface cleaners to
alleviate the
problems of contamination of these articles. However, these and other similar
treatments have,
for the most part, been inadequate and required repeated treatment. In
addition, these treatments
have been found to be limited in their ability to offer broad spectrum control
of microorganisms.
Therefore, the present compounds, products and compositionscan be used to
treat these articles
to prevent microbial growth and contamination by coating an effective amount
of the products
and compounds of the invention thereon. The articles employed can be coated by
allowing for
1 to 2 minutes submersion (e.g., by dipping), and thereafter, the treated
surface is allowed to dry
at room temperature. The article is then rinsed of any excess antimicrobial
agent. Thorough
cieaningand sterilization is a preferred step in removing the microorganisms
on the surface of
the article prior to "coating" the said articles. In addition, concentrations
of 10% or less by
weight of the compounds, products and compositions of the invention in water
are used for long
lasting protection.
Treating surgical gloves with the compounds, products and compositions of the
present
invention before or during a surgical procedure can kill microorganisms on
contact . It is
believed that the treated gloves do not diffuse or leach the antimicrobial
agent from the glove
surface and provide prolonged antimicrobial activity with safe and non-toxic
antimicrobial
protection. Surgical gloves are treated, preferably, by submerging in the
solution of Example
1, diluted to 1% W/V for at least 30 seconds. This method will permit doctors
to use and, if
necessary, re-use the same gloves (even without removing them) without undue
fear of
contamination. Treating polymers and other materials such as concrete by
incorporation into
the bulk material protects from deterioration, odor build-up and potentially
harmful
contamination of the surface. Incorporation of a sun protection into polymers
andlor application
of sun protection to the surface extends the life of the product and reduces
damage to products
and skin.
Moreover, one of ordinary skill in the art would be able to implement numerous
other
end uses based upon the disclosure of the compounds, products and compositions
of the present
invention. Not all uses require aqueous solutions and some require non-aqueous
environments,
both applications are part of the invention. Furthermore antimicrobial
properties of the silane
compounds according to the invention is only one of many possible properties.
Mixtures of
silanes according to the invention often provide additional benefits.
For instance, the following uses, applications and substrates, are
contemplated:
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1. Concrete, Concrete Water Conduits, Storm and Sewer Pipes treated with the
compounds, products and compositions of the present invention. Agents to kill
microorganism on contact and provide prolonged antimicrobial protection to
prevent deterioration of the concrete and its coatings.
5 2. Tooth Brushes, Combs, Hair Brushes, Dentures and Retainers
3. Spa and Pool Filters meeting stringent requirementsthat no other
antimicrobial
agent can meet and protection for Air Filtration such as air conditioning
filters,
HVAC applications and cabin air
4. Marble Slabs (building facia, tombs, floors) treated with the compounds,
10 products and compositions of the present invention
5. Rubbing Alcohol
b. Statues and exposed art work
7. HDP, high density polyester fabric plastic covers for dump sites, water
reservoirs and generally for soil protection
15 8. Liquid Additive (as flower water preservative for potted plants and cut
flowers)
9. Silicone and Teflon coated Fiberglass with antimicrobial protection
including
acrylic backing wall covering
10. Dryvitt and Stucco finish
11. Waterproofing treated with the compounds, products and compositions of the
20 present invention
12. A method of treating blended cotton before or after picking machines make
the
cotton into rolls or taps
13. Food packaging and containers
14. Bio-films and adhesives (tapes and silicone wafers)
25 15. Single Ply Roofing and Roof shingles
16. Fiberglass reinforcement product
The preferred embodiments of the above-described water-stabilized
antimicrobial
compounds, products, compositions, and methods are set forth in the following
examples. Other
30 features of the invention will become apparent from the following examples,
which are for
illustrative purposes only and are not intended as a limitation upon the
present invention.
The silane in the following examples is Dow Corning 5772 or a silane of
similar
composition as Dow Corning 5772. Both are collectively referred to as silane
concentrate. A
solution or mixture is considered stable if an aqueous solution can be
produced and remain
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31
without precipitation of the silane for a longer time than would be expected
for the non-
stabilized silane. If the silane itself is insoluble in water then the
formation of an aqueous
solution is a benefit within the scope of the invention.
Example 1
Water dilutions of a mixture containing 20.049 g silane concentrate and 20.788
g
ethylene carbonate have been stable at 25.9 weight % mixture in water. At 41.4
weight % the
water diluted mixture appeared unstable.
The following table lists examples of mixtures and their stability. The
entries are in
weight percent of total mixture. Concentrated solutions were prepared and then
diluted with
water accordingly. A) 24.694 g silane concentrate, 11.596 g glycol ether DB,
13.593 g
propylene carbonate. B) 25.028 g silane concentrate, 5.895 g glycol ether DB,
19.379 g
propylene carbonate.
# concentrateDI WaterStable (YIN)
A l .6 98.4 y
A 7.4 92.6 y
A 14.4 85.6 y
A 28.0 72.0 n
A 41.9 58.1 y
A 55.3 44.7 y
B 1.4 98.6 y
B 7.1 92.9 y
B 13.7 86.3 y
B 26.6 73.4 n
B 42.0 58.0 y
B 54.7 45.3 y
Example 2
The following table lists examples of mixtures and their stability. The
entries are in weight
percent of total mixture. A solution 50 weight percent silane concentrate and
50 weight
percent propylenecarbonate was prepared and then diluted with water
accordingto the table.
concentrateDI WaterStable (Y/N)
7.5 92.5 y
14.1 85.9 y
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32
28.5 71.5 n
42.0 58.0 y
54.9 45.1 y
Example 3
In a flask were heated and stirred 54.109 g dimethyl octadecyl amine and
53.871 g 3-
chloropropyltrimethoxysilaneand 14.960 g propylene carbonate. The temperature
was held at
130 to 135 °C, when the mixture began to darken, the temperaturewas
reduced to 125 °C. After
21 hours, titration ofthe mixture revealed an amine content of I .3% and an
ammonium content
of 72.0 %. The product was a light brown, soft solid when at room temperature.
The reaction product of the previous example was dissolved in water, to
prepare stable
silane water mixtures.
# concentrateDI WaterStable
(Y/N)
I S 1 2.0 98.0 y
2 6.8 93.2 y
3 14.5 85.5 y
4 22.2 77.8 n
5 28.7 71.3 n
~ 35.3 64.7 n
6
Example 4
Sample 2 of the previous example was after 35 days diluted further with 4
parts water
and applied to white textile fabric. After drying, the fabric was hand washed
in running water
20 times. The sample was again allowed to dry and then tested according to Dow
Corning
Corporate Test Method 0923. In this test method the fabric sample is placed
together with an
inoculated nutrient solution into an erlenmeyer flask. For this experiment the
procedure was
slightly modified, the mixture was shaken for 24 hours instead of 1 hour and
the organism used
was aspergillus niger instead of klebsiella pneumoniae. Percent reduction is
determined by
counting the organisms at zero time and at the end of the experiment. The
percent reduction
found in this example was 99.98%.
It will be apparent to those skilled in the art that various modifications and
variations
can be made in the present invention without departing from the scope or
spirit of the invention.
Other embodiments of the invention will be apparent to those skilled in the
art from
CA 02296395 2000-O1-14
WO 99103866 PCT/US98/I4985
33
considerationofthe specification and practice ofthe invention disclosed
herein. It is intended
that the specification and examples be considered as exemplary only, with the
true scope and
spirit of the invention being indicated by the claims.
It should be understood that the examples and embodiments described herein are
for
illustrative purposes only and that various modifications or changes in light
thereof will be
suggested to persons skilled in the art and are to be included within the
spirit and purview of this
application and the scope of the claims.
