CA2236893A1

CA2236893A1 - Water-stabilized organosilane compounds and methods for using the same

Info

Publication number: CA2236893A1
Application number: CA002236893A
Authority: CA
Inventors: Jacques E. Elfersy; Joachim Berkner; Timothy C. Moses
Original assignee: BioShield Technologies Inc
Current assignee: BioShield Technologies Inc
Priority date: 1997-05-07
Filing date: 1998-05-04
Publication date: 1998-11-07
Also published as: BR9806344A; AR015647A1; IL124316A0; EP0877027A3; JPH10330383A; US6469120B1; EP0877027A2; US6120587A; US5954869A; NZ330379A

Abstract

The composition formed by mixing an organosilane, optionally having a nonhydrolizable organic group, but having one or more hydrolyzable groups, with a polyol containing at least two hydroxy groups, wherein at least any two of the hydroxy groups are separated by no more than two intervening atoms. Water-stabilized organosilane compounds. A water stable composition made from the polyol and organosilane or compound and water. A method of treating a substrate by mixing or contacting the substrate with the product, compound, or composition of this invention for a period of time sufficient for treatment of the substrate. A treated substrate having adhered thereto the product, compound, or composition of this invention. A method of dyeing and treating a substrate. A method of antimicrobially treating a food article. A
method of antimicrobially coating a fluid container. A method of antimicrobiallycoating a latex medical article. A method of making a siloxane in the presence of a stabilizer.

Description

,OESCRIPTION

WATER-STAB~T ~7Fr~ ORGANOS~T.~NE COMPOUNDS AND
MFTHODS FOR USING TH~ SAME

~ aclc~rolln~ of the Invention Field o~the Invention:
The invention relates to organ~-sil~n~ compounds, products and methods for their use. In particular, this invention provides water-stable organosilane compounds, 10 products, and compositions for treating various substrates, articles treated with the compounds, products and compositions, and m~tho~s of tre~tm~nt using the compounds, products and compositions.

Back~round:
Org~nosil~n~s of the general formula RnSiX4 n where n is an integer of from 0 to3, but more generally from 0 to 2 (where when n is 3 the organosilanes may only dimerize); R is a nonhydrolizable organic group, such as, but not limited to, alkyl, aromatic, organofimrtion~l, or a combiDation thereof, and X is alkoxy, such as methoxy or ethoxy, are prone to self-con~enc~tion rendering such organosil~nç~
unstable in water over commercially relevant periods of time. Additionally, X can be a halogen, such as Cl, Br, or I, and is similarly liberated as HCI, HBr, or HI. For such org~nosil~n~s, the X moiety reacts with various hydroxyl cont~ining molecules inaqueous media to liberate m~th~nol, ethanol, HCl, HBr, HI, H2O, acetic acid, or an unsubstituted or substituted carboxylic acid and to form the hydroxylated, but con~enc~tion-prone compound.
For organosil~n~s RnSiX4 n, where n is an integer from 0 to 2, hydrolysis of thefirst two X groups with water produces a species bearing -Si(OH)2- units which can self-condense through the hydroxyl moieties to linear and/or cyclic oligomers possessing the partial structure HO-Si-(O-Si)l",n-O-Si-O-Si-O-Si-OH, where mm is an A:\BSTI~lAPP~NB/~HB/Mayl,1997 integer such that an oligomer is formed. For those cases, RSiX3, hydrolysis of the third X group generates a silanetriol (RSi(OH)3) which produces insoluble organosilicon polymers through linear and/or cyclic self-con-l~n~tion of the Si(OH) units. This water inrl~lced self-con~e~tion generally precludes storage of most organosilanes RnSiX~n, where n ranges from 0 to 2, inclusive, in water. Except for some organrsil~nPs 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.
One col~ cLcially relevant example of an organosilane ~ufr~ g from such undesirable self-condensation is the anfimi~robial Dow Corning 5700 (Dow CorningCorporation, Midland, MI). The lileralule describes the active ingredient of DowCorning 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. Nonçtheless, 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride is a water activated ~ntimicrobial 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 isprepared by quatellli2ation of dimethyloct~lecylamine with 3-chloloplo~yl trimethoxysilane.
The C~8 hydrocarbon chain qU~tp-rn~ry ammonium portion of the molecule pQSSesCeS long-acting ~ntimirrobial plopc.Lies and provides initial association with the surface of the substrate through ionic bonds and/or ele~;LIu~ ic interaction.
Preferably, the treated surface becomes perrn~n~ntly coated with a covalently bound octadecyl~mmnnil~m ion, providing a durable, long-acting ~ntimirrobial coating that is able to destroy microbes that come into contact with the surface.
Unfortunately, as noted above, or~nosil~nPs in water, such as the activated mixture of 3-(trimethoxysilyl)propyl~illl. lhyloctadecyl ammonium chloride and water, are generally unstable and prone to self-co~1enc~ion. For in.ct~nre, the mixture of 3-A:lBST~ APP/DNB/GHB/Mayl,1997 CA 02236893 1998-0~-04 ~trimethoxysilyl)propyl-dimethyloctadecyl ammonium 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 even shorter times. The limit~ti~ns of such org~nosil~n~s in aqueous media are further described in United States Patent No.5,411,585, the contents of which are hereby incorporated by this reference. Moreover, such products are notorious for ~git~tion ~lifficl-lty during the addition of the silane to water. ' Nevertheless, according to the present invention, clear aqueous gels are considered to be useful compositions.
The use of quaternary arnmoniurn 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 co~ of which are hereby incorporated by this reference. It is also taught that these compounds possess certain antimirrobial plopc.Lies 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 ~mmnnium silicon compounds have been employedto sterilize or disinfect many surfaces, their employment is still limited because of their toxicity often as a result of the solvent system used to deliver the compound, the necessity for a solvent solution (for in~t~nre, Dow Corning ~ntimirrobial agents contain 50 % m~th~nol), short term stability (stability of aqueous silane solutions varies from hours to several weeks only) and poor water solubilit.,v. For in~t~n~e~ while 3-(trimethoxysilyl)propyl-dimethyloct~ecyl ~mmnr~ m chloride does not suffer from water insolubility, it is unstable in water and also, because it is shipped in 50%
mPth~nnl, it is overly toxic. Many other antimirrobial organo.cil~nrs, especially quaternary ammonium silicon compounds, also suffer from problems associated withphysical health hazards, e.g., prec~ntion.~ must be taken to avoid contact with both skin md eyes, accid~nt~l spills to the ~ull~unding area, fl~mm~hility, and the added A:\BST~ PP/DNB/GHB/Mayl,1997 CA 02236893 1998-0~-04 m~mlf~ctllring steps needed in order to incorporate the such antimicrobial agents into other articles and surfaces, res~llting in much higher m~n~lfactl1ring costs.
The,efole, there exists a need for ex~en~e~l shelf-life, water-stable organosilane compounds, products and compositions whereby, upon application, the active portion S of the or~nosil~n~ is operative for the selecte~l application. Moreover, there exists a need for water-stable, organosilane compounds, products and compositions which are e~sçntiAlly non-toxic, non-fl~mm~hle, uniformly dispersable, and simple and eConomiral to use.
In Provisional Application Serial No. 60/016985, a method for producing water stable organosilane solutions and compositions is r~icrlosecl. According to thatinvention, stabilization is achieved by reacting the organosilane with a polyol cont~inin~ at leact three hydroxy groups, wherein any two hydroxy groups are separated by at least three iule~ nillg atoms. The archetypal example of such a polyol disclosed in that application being pentaerythrytol.
In the instant application, we disclose the finding that compounds having at least two hydroxy groups stabilize aqueous organosilane solutions, even though there are less than three atoms se~alaling at least two of the hydroxyl groups that are present in the polyol. The archetypal example of polyols of the instant invention being glucose, wherein there are several hydroxy groups, several of which are separated by no more than two intervening atoms. According, this invention provides for a much exran~ecl scope of hydroxy cont~inin~ compounds useful in the stabilization of organosil~ne compounds.

Brief Su",l~ 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, m~tho~c for their use, and articles pr~a~ed using the compounds, products, and compositions. The compounds, products, and compositic)rL; of the present invention are non-toxic, non-fl~mm~ble, simple, and A:lBST-l~)APP/DNBlGHBlM~yl,1997 CA 02236893 1998-0~-04 economical.
In particular, the present invention provides the product formed from mixing an organosilane of the formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, S independently, a hydrolyzable group; with a polyol cont~ining at least two hydroxy groups wherein any two hydroxy groups of the at least two hydroxy groups present are separa~ed by less than three intervening atoms. Accordingly, alcohols having at least two hydroxyls, carbohydrates, inc~ ng monosaccharides, ~lie~rch~rides~
oligosaccharides, polysaccharides, m- tlifi~d carbohydrates, including graft and block co-polymers, partially alkylated, partially acylated or partially acetylated carbohydrates, carbohydrate oxitl~tion products (e.g. glucuronic acid, mucic acid), reduced carbohydrates and substit~-ted carbohydrates (e.g. m-cleQsi~les, nucleotides, nucleic acids), are all polyols which are useful according to the instant invention.
Accordingly, in one embo-lim~nt this invention provides a water-stable composition, comprising the product or composition of the invention and water.
In a further embodim~nt, 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, co.l.~lising mixing the substrate with a sumrient amount of the product, compound or composition of the invention for a period of time suffirient for treiqtm~r~t of the substrate.
In a further embodim~nt, the present invention provides a treated substrate having adhered thereto the product, compound or composition of the invention.
2~ In addition, the present invention provides a method of dyeing and treating a substrate, COlll~liSillg cont~rtin~ the substrate with an aqueous composition colllplisil~g an aqueous soluble dye suitable for dyeing a substrate and the product formed from mixing an organosilane of the formula RnSiX4.n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, indepen~ently, a nonhydrolizable organic group; and each A:~0~-laOAPP/DNP/GHP/M;Iyl.1~7 CA 02236893 1998-0~-04 X is, independently, a hydrolyzable group; with a polyol cont~ining at least twohydroxyls which are separated by less than three intervening atoms, for a period of tirne sufficient to dye and treat the substrate.
In a further embo-limPnt the present invention provides a method of antimicrobially treating a food article, co~ isil,g cont~rtin~ or mixing the food article with an effective amount of the product formed from mixing an ~ntimicrobial organc~ilane of the formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; each R~ is, in~epenAently, a nonhydrolizable organic group; and each X is,independently, a hydrolyzable group; with a polyol co.~la~ at least two hydroxyls which are separated by less than three intervening atoms, for a period of time sufficient to ~ntimirrobially treat the food article.
In yet another embo-lim~t the present invention provides a method of ~ntimicrobially coating a fluid conhiner used for cont~inin~ a human or animal consuma~le product, comprising collt~rtin~ the cont~inPr with an effective amount of the product formed from mixing an :~ntimirrobial organosilane of the formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group;
with a polyol cont~ininP at least two hydroxyls which are separated by less than three intervening atoms, for a period of tirne sufflcient to ~ c.obially coat the container.
In yet another embo-limPnt the present invention provides a method of ~ntimicrobially coating a latex mPrlir~l article for use in a human or anirnal mP-ljc~l procedure, comprising cont~rting the article with an effective arnount of the product formed from mixing an ~ntimirrobial organosilane of the formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, inllepenAçntly, a nonhydrolizable organic group; and each X is, inAepenllçntly, a hydrolyzable group;
with a polyol cc~ g at least two hydroxyls which are sepaldted by less than three intervening atoms, for a period of time suffirient to ~ntimirrobially coat the article.
A filrther embodiment of the present invention provides a method of ~ntimirrobially treating a substrate selected the group consisting of a concrete pipe, a A:\B~ APP/DNB/GHBlM~yl.1997 CA 02236893 1998-0~-04 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, an HDP plastic cover, a silicone or TEFLON~ coated fiberglass article, a Dryvitt finish, a stucco finish, blended cotton, a bio-film, a bio-S adhesive, a single ply roofing, a roofing shingle, and a fiberglass leinfoicement product, comprising cl~nt~rting the substrate with an effective amount of the product formed~ from. mixing an ~ntimirrobial org~nosil~ne of the formula RnSiX4n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, inf~epen-1çntly, a nonhydrolizable organic group; and each X is, indep~nf1~ntly, a hydrolyzable group;
with a polyol cont~ining at least two hydroxyls which are separated by less than three intervening atoms, for a period of time suffici~nt to antimirrobially treat the substrate.
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 a~lmixing with the product an effective amount of the product 1~ formed from mixing an ~ntimirrobial organosil~nP of the forrnula RnSiX4.n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, in~epenrl~ntly, a hydrolyzable group;
with a polyo:l cont~ining at least two hydroxyls which are s~alaled by less than three intervening atoms, for a period of tirne sufficient to ~ntimicrobially enh~nre the product.
A further embodiment of this invention is a method for m~king an org~n- sil~nç
of the formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; each R
is, indepen~ently, a non_ydrolizable organic group; and each X is, int1~penrlrntly, a hydrolyzable group; from starting materials in an aqueous solution in the presence of a polyol cont~ining at least two hydroxyls which are separated by less than three intervening atoms, in an effective amount of the polyol s~lffirient to stabilize the organosilane as it is formed from the re~ct~nt~.
Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the descliplion, or may be learned by A:\B~-I~APP/DNBJGH8/M~~/1.1997 CA 02236893 1998-0~-04 routine practice of the invention as disclosed herein. The advantages of the invention will be realized and ~tt~ined by means of the elem~nts and colllbi~lions particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following det~ile l descl i~Lion are exemplary and explanatory only and are not restrictive of the invention, as cl~imr~l.

Detailed Disclosure of th~ Invrn~ion The present invention may be understood more readily by lef~lence to the following detailed description of pr,~led embodiments of the invention.
Before the present compounds, products and compositions and methods are disclosed- and described, it is to be understood that the terminology used herein is for the purpose of describing particular embo lim~nts only and is not intended to belimiting. It must be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural rereienl~ unless the context clearly ~iirt~te~ otherwise.
Throughout this ~pplication, where publications are referenced, the disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.
The l:erm "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. Flefell.,d alkyl groups herein contain from 1 to 12 carbon atoms. The term '~lower alkyl" intends an alkyl group of from one to six carbon atoms, preferably from one to four carbon atoms. The term ~cycloalkyl"
intends a cyclic alkyl group of from three to eight, prefe~ably five or six carbon atoms.
"Lower alkyl alcohol" refers to lower alkyl having ~tt~rh~d thereto one or more hydroxy moieties, such as, but not limited to, -CH2CH2OH, CH2CH(OH)CH3, CH2OH, A:lBST~ APP/DNBlGHB/M2.yl,1997 CH2CH2CH2OH. CH2CH2CH(OH)CH3, CH2CH2CH(OH)CH2OH, OR
CH2CH(OH)CH(OH)CH3 .
The term "alkoxy" as used herein intends an alkyl group bound through a single terminal ether linkage; that is, an Ualkoxy" group may be defined as -OR where R is alkyl as defined above. A Ulower alkoxy" group intends an alkoxy group cont7.ining from one to six, more preferably from one to four, carbon atonLC. "Polyether~ refers to a compound or moiety poC.cessing multiple ether linkages, such as, but not limited to, po~yethylene glycols or polypropylene glycols. "Polyalkylethers" refers to alkyls interconn~cle(l by or otherwise possçssing multiple ether linkages.
As used herein, "optional" or "optionally" means that the subsequently described event or cir~;ulllsl~ce may or may not occur, and that the descriptionincludes instances where said event or ci~--u~ re occurs and in.ct~n~es where it does not. For example, the phrase "optionally s~-bstituted lower alkyl" means that the lower alkyl group may- or may not be substituted and that the description in~.ludec both unsubstituted lower alkyl and lower alkyl where there is substitl~tion.
By the term "effective amount" of a compound, product, or composition as provided herein is meant a sufflcient 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 a-1minic~ration, and the like. Thus, it is not always possible to specify an exact "erreclive amount." However, an apl.ro~liate effective amount may be det~l,l",led by one of ordi~, y skill in the art informed by the instant disclosure using only routine expe~ P~ inn.
The l:erm "aryl" as used herein refers to a compound or moiety whose molecules have a ring or multiple ring structure characteristic of benzene, n~phth~len~, phena,lll"cne, anthracene, etc., i.e., either the six-carbon ring of benzene or t_e con~n.ce~ six-carbon rings of the other aromatic derivatives, including, but not limited to phenyl, benzyl, naphthyl, benzylidine, xylyl, styrene, styryl, phenethyl, phenylene, bem~n~triyl, etc. As used herein, the term "aromatic" refers to the group of A:\PST~ APP/DNB/GHB/Mayl.1997 CA 02236893 1998-0~-04 unsatuLrated cyclic hydrocarbons, typified by benzene, having a 6-carbon ring cont~inin!J three double bonds or multiple att~rhe(l benzene rings. Moreover, certain five membered cyclic compounds, such as furan (heterocyclic), are analogous to aromatic compounds. Aromatics include the cyclic compounds based upon a benzene functionality, as specified for "aryl" above. Moreover, the term "cyclic~ is used to refer to all aliphatic or aromatic hLydloc~,l,ons having one or more closed rings, whether unsaturated or saturated. Preferably, cyclic compounds possess rings of from 5 to 7 carbon atoms, preferably 6 carbon atoms. Such rings fall into three classes:
alicyclic, aromatic ("arene"), and heterocyclic. Moreover, when used with respect to cyclic cornpounds or moieties, the terrcL "unsaturated" refers to such compound or moiety possessing at least one double or triple bond or ot}l~l~ise COl~. IiL~ .g an aromatic c ompound or moiety. Moreover, thLe term "saturated~ refers to compounds or moieties possessing no double or triple bonds, i. e., where all available valence bonds of an atom, I specially carbon, are ~tt~c~d to othLer atoms.
The term "heteroaryl~ refers to an aryl where one or more of the carbon atoms of a ring have been substituted with a heteroatom, includinLg, but not limited to, O, N, or S. Similarly, the term "heterocyclicn refers to a cyclic compound or moiety where one or more of the carbon atoms of thLe ring has been substituted with a heteroatom, including, but not limited to O, N, or S.
As used herein, especially in lefe.enLce to alkyl and aLkoxy, the term "lower"
refers to aL moiety having from 1 to 6 carbon atorns, 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 rl~t~ i.lPd by one of OrdLL~L1Y
skill in the art using only routine eA~cl;~"~ tion.
As used herein, "substituted~ is used to refer, generally, to a carbon or suitable heteroatorn having a hydrogen or other atom removed and replaced with a further moiety. In one embo~limPnt halogen, hydroxy, and nitrogen based substitutions ofhydrocarbon hydrogens are contemplated as withLin the scope of the present invention A:~8Sl'-lOOAPPlDNB/GHBlMay 1, 1997 CA 02236893 1998-0~-04 for the cl~irn~d structures . Moreover, it is intPn~ed that ''~ S~ iluled " refer to substinltionli which do not change the basic and novel utility of the underlyingcompounds, products or compositiorls of the present invention. "Unsubstituted" refers to a structure wherein the reference atom does not have any further moieties ~tt~ehed thereto or Slll~S~ Pd therefor.
As used herein, ~branchedn is used to refer, generally, to a moiety having a carbor~chain backbone, e.g., alkyl or alkoxy, wherein the backbone may contain one or more suboldinate carbon chain ~lanches. For example, isobutyl, t-butyl, isopropyl, CH2CH2C(('H3)(H)CH2CH3, CH2C(CH2CH3)(H)CH2CH3, CH2CH2C(CH3)CH3, and CH2CH2C(('H3)3 would all be considered branched moieties. Moreover, it is intentled 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. "Unbranchedn 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 "acyln refers to organic acid derived moieties of the formula RCOX where R is an organic molecule and X, instead of being hydroxy, is replaced with another su~stih~ent~ preferably, a suitable anion.
As used herein, the term Uperfluoron or "perfluoro- analog" refers to a hydrocarbon where the hydrogen atoms att~('h~d to carbons have been replaced with F
atoms. Preferably, but not nPcesc~rily, in perfluoro- analogs, most if not all of the H
atoms are replaced with F atoms. A "fluoro-" analog is contemplated to intiir~e a hydrocarbo;n where at least one hydrogen atom ~ rll~d to a carbon is replaced with an F atom.
As used herein, "~ubslraten refers to any article, product, or other surface that can be treated with the inventive compounds, preferably as e~lull~e,ated herein below under the he~line Uses, as described in the Examples hereto, and as specified in the relevant claims appended hereto. Suitable substrates are generally cha acl. .,zed in preferably having a negatively charged surface of oxygen atoms, or any surface capable A:lBST-lOOAPP/DNBlaHB/1Ul~y 1, 1997 CA 02236893 1998-0~-04 of electrostatically, ionically 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 org~nrlsil~nç portion of the conl~cJullds, products, or compositions of the present invention, but such binding is not a requirement.
Therefore, clS used herein, the term "adhere" is meant to refer to ionic, covalent, electrostatic, or other cll~m~ attachm~nt of a compound, product or composition to a substr~te.
As used herein, the term "antirnicrobially enhancing" refers to the use of the compounds, products, or compositions of the present invention, preferably those wherein the organosilane has ~ntimitrobial activity, along with other ingredients, surfact~nts, fillers, wetting agents, pigrn~nte, dyes, ~ntimigrants~ etc., to create a composition or solution capable of fillfilling its original purpose, based upon the other ingredients, and also of providing ~ntimirrobial protection during the particular application. The term ~enhance" re~ers to the addition of antimicrobial activity to such compositions or solutions where no such activity previously existed, or to the increase of ~ntimicrc,bial activity wherein the starting compositions or solutions inherently possessed alltimirrobial 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, Unonhydroli7ablen 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, Uanionic" is used to refer to any compound, ion or moiety possessing a negative charge. Furthermore, Umonovalent'' and "divalent" are used to refer to moieties having valances of one and two, respectively.
Moreover, as used herein, the term "salt" is meant to apply in its generally defined sense as "cc)mpound formed by replacing all or part of the hydrogen ions of an acid with one or more cations of a base." See, e.g., American Heritage Dictionary, A:~BST~ APP/DNB/GHB/M-yl,1997 CA 02236893 1998-0~-04 Definition of "Salt" (1981). Therefore, suitable salts for the present invention may be formed by replacing a hydrogen ion of a moiety with a cation, such as K +, Na+, Ca2+, Mg2+, etc. In addition, other suitable methods of generaling salts are specifiedthroughout this specification and are within the scope of the present de~mition. It is believed tha.t, for the purposes of the present invention, the specific identity of the cation used for forming the salt is of lesser importance than the ch~rni~l structure of the anibn 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 embotlim~nts, the food articles referred to herein are those which are perishable or prone to spoilage upon exposure to microbes or other pathogeris. 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 me2ms into a human or animal.
As used herein, the term "antimirrobial" is used in its general sense to refer to tbe property of the described compound, product, composition or article to prevent or reduce the growth, spread, formation or other livelihood of organicmc such as bacteria, viruses, protozoa, molds, or other org~nicmc likely to cause spoilage or infection.
As wsed herein, the term "mP~lic~l article" is used to refer to any suitable substrate which is or may come into contact with m~dic~l p~tiçntC (human or animal), m~lir~l care givers, bodily fluids, or any other source of con~ tion or infection generally associated with hospitals, I~linics, physician's offices, etc.
As used herein, the term "stabilizer" is used to refer to the class of polyols cont~ining at least two hydroxyls which are separated by less than three intervening atorns. Such compounds have been found to stabilize the org~n- sil~n~s of the invention by preventing self-conflçnc~tion or other inactivation of the resultin~ compounds and products.

A:\BST-I~APP/DNB/GHBM~yl,1997 CA 02236893 1998-0~-04 As used herein, the terms ~polyol" and "stabilizern are used interchangeably to describe a molecule having at least two hydroxyls separated by no more than two atoms.
Finally, the terms ahalogen" are used to refer to Fluorine "F", Chlorine "Cl", 5 Bromine "Br", Iodine "I", and Astatine ~At". Preferably, halogen or halide refers to F, Cl, or Br. The term ~halide" is meant to include these halogens.
~ With these definitions in mind, the present invention provides the product formed from mixing an org~nosil~n~ of the formula RnSiX~n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, indepen-l~ntly, a nonhydrolizable organic 10 group; and each X is, independently, a hydrolyzable group; with a polyol cont~ining at least two hydroxyls which are separated by less than three intervening atoms (i.e.
regardless of the total number of hydroxy groups in the compound, there are at least two which are separated by less than three intervening atoms).
More preferably, in the above product, n is an integer from 0 to 2, preferably 1; each R is, indepenflently, alkyl, preferably of from 1 to 22 carbon atoms branched or unbranched, substituted or unsubstihlted, 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 sirnilar carbon lengths, br~nt~hing and substitution, or arol,-alic, such as benzyl, phenyl, etc.; each X is, independently, hydroxy, alkoxy, halogen (such as, but not limited to, Cl, Br, I, or F), acetyl, acetoxy, acyl, a hydroxylated solid or liquid polymeric moiety, polyether or polyalkylether; and the polyol is an alcohol having at least two hydroxyls, a carbohydrate, including a mon~s~cch~ride, a ~lic~-~rh~ride, an oligos~crh~ride, a polysaccharide, a modified carbohydrate, including a graft or block co-polymers, a partially alkylated, acylated or acetylated carbohydrate, a carbohydrate oxid~tion product (e.g. glucuronic acid, mucic acid), reduced carbohydrates, substituted carbohydrate or sllbstihlted carbohydrate polymers (e.g. nucleosides, nucleotides, nucleic acids). In one emho~im~ont, the polyol is a simple monosaccharide, such as glucose, fucose, fructose. In a further embodimenl:, the polyol is an oligomeric sugar (e.g. a dimer, such as sucrose, a trimer, A:\BST~ APPlDNB/GHBlM~yl,1997 CA 02236893 1998-0~-04 -a tetramer, etc). In another embo~i-n~nt, the polyol is m~nnitol, ascorbic acid, glyoxal or a nucleoside. Where ascorbic acid or like compound is used as the polyol, it is frequently desirable to include an anti-oxidant in the composition, to prevent oxidation of the ascorbic acid. In another emborlim~nt the polyol is an oxidized sugar, such as S glucuronic acid. In another embo~limPnt the polyol is a polymeric carbohydrate, such as cellulose, partially hydrolyzed cellulose, partially hydrolyzed cellulose acetate, starch,~soluble starch, a starch acrylic àcid graft copolymer. As a source of certain of these polyo].s, cost-effective carbohydrate and even complex carbohydrate compositions include corn syrup, honey or like compositions. In order to control bacterial growth, these compositions may optionally include a preservative, such as benzoic acid, which is acceptable for human applications, and which provides an ~ntib~cterial function.
This is particularly important where the org~n--sil~n~ to be stabilized does not itself have antimicrobial activity, and is much less signific~nt where the organosil~n~ itself is antibacterial.
1~ In a further embodiment of the present invention, the invention provides the product described above, wherein the organosilane is of the formula II, III, IV, or V:
(R,)3SiR2N+(R3)(E~4)(R5)Y~
(R,)3SiR2N(R3)(R4) (III) (R,)3SiR2R35 (R,)2Si(R36)(R37) wherein each R, is, indepen-lently, halogen or R60, where R6 is H, alkyl of from 1 to about 22 carbon atoms, acetyl, acetoxy, acyl, propylene glycol, ethylene glycol,polyethylene glycol, polypropylene glycol; block and copolymers of ethylene and propylene glycol, the alkyl monoether of from 1 to 22 carbons of propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; block and copolymers of ethylene and propylene glycol or the monoester of a carbonic acid of from 1 to 22 carbons and propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; bloc:k and copolymers of ethylene and propylene glycol; octyphenol;
nonylphenol; and sorbitan ethers;

A:\BST-lDOAPP/DNB/GHB/M~y 1, 1997 CA 02236893 1998-0~-04 R35 is H, halogen (such as Cl, Br, F, or I), NH2(CH2)2NHR2, NH2R2, C3H5O2R2, C4H5O2R2, NaO(CH3O)P(O)R2, or CICH2C6H4R2; R36 and R3, are, independently, halogen, H, alkyl of from 1 to about 8 carbon atoms, preferably of from 1 to 4 carbon atoms, more preferably of from 1 to 2 carbon atoms, isobutyl, phenyl, or n-octyl; R2 is benzyl, vinyl or alkyl of from 1 to about 3 carbon atoms; R3 and R4 are, independently, lower alkyl alcohol of from 1 to 4 carbon atoms, lower alkoxy of from 1 to 4 carbon atoms, alkyl of from l to about 22 carbon atoms, preferably 1 to about lO carbonatoms, more preferably alkyl of from 1 to 4 carbon atoms, or more preferably of from 1 to 2 carbon atoms; or R3 and R4 can, together, form a morpholine or cyclic or heterocyclic, unsalulat~d or s~lulaL~d~ five to seven-mPmhered ring of the formula VI:
-R3-(R7)k-R~- (Vl) where k is an integer from 0 to 2, preferably 0 to l, most preferably l, R7, where the ring is saturated, is CH2, O, S, NH, NH2+, NCH2CH2NH2, NCH2CH2NH3+, NCH2CH2N(R8)(Rg)~ NCH2CH2N+(R8)(R9)(Rlo), N(alkyl), N(aryl), N(benzyl), where each R8, Rg, and Rlo is, independently, benzyl, polyether, lower alkyl alcohol of from 1 to 4 carbon atorns, lower alkoxy of from l to 4 carbon atoms, or alkyl of from l to about 22 carbon atoms, preferably l to about 10 carbon atoms, and the "alkyl"
specified above is of from 1 to 22 carbon atoms, more prer~lably of from l to lOcarbon atorns, most preferably of from 1 to 3 carbon atoms, the "aryl~ is more preferably phenyl or benzyl, and R~, where the ring is unsalulated is, CH, N, N +H, N+(alkyl), N+(aryl), N+(benzyl), N-CH2-N, N+H-CH2-N, N+(alkyl)-CH2-N, N+(aryl)-CH2-N, or I~+(benzyl)-CH2-N where the alkyl, aryl, or benzyl is as described above;
wherein the ring is unsubstituted or substituted with alkyl of from 1 to 22 carbon atoms, more preferably of from l to lO carbon atoms, most preferably of from 1 to 3 carbon atoms, ester, aldehyde, carboxylate (preferably acetoxy, acetyl, acyl or perfluorocarboxylate~, amide, thionamide, nitro, amine, or halide, most preferably Cl, Br, or I; R5 is lower alkyl alcohol, preferably of from 1 to 6 carbon atoms, more preferably of from l to 4 carbon atoms, CH2C6H5, polyether, such as a A:\BST-1OOAPP/DNB/GHB/May 1, 1997 CA 02236893 1998-0~-04 polyethyleneglycol or a polypropylene glycol, alkyl of from 1 to 22 carbon atoms, more preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms, alkoxy, of from 1 to 22 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 22 5 carbon atoms, more preferably of from 1 to 10 carbon atorns, most preferably of from 1 to 6 carbon atoms, perfluoroalkylsulfonate, of from 1 to 22 carbon atoms, moreplefel~ly of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms, or perfluoroalkylcarboxylate, or is a five to seven-mf ~.~h~.ed ring of formula V~ as described above; and Y~ is a suitable anionic moiety to form the salt of the compound 10 of formula II, III, IV or V.
This invention provides a water stable composition, comprising water and the organosilane, mixed with the polyol.
In addition, the present invention also provides a composition for treating a substrate, comprising a carrier and an effective amount of an organ-)sil~nP and a polyol 15 as described herein. In an alternate embo~imPnt, the present invention provides a composition for treating a substrate, co~ ing a carrier and an effective amount of the compound as described above. ln further embo~ r~".~i, the carrier is other than water.
In a further embo~im~nt, the organosilane is 20 3-(trimethoxysilyl)propyldimPthyloctadecyl ~mm~nillm chloride, 3-(trimethoxysilyl)propylmethyldi(decyl) ~~ oniulll chloride, 3-chloropropyltrimethoxysilane, octadecyltrirnethoxysilane, or perfluorooctyltriethoxysilane and the polyol is an alcohol having at least t vo hydroxyls, carbohydrates, inrl~ ing monos~cch~rides, ~ crh~rides, oligosarch~rides, 2~ polysaccharides, modified carbohydrates, inrluding graft and block co-polymers, partially alkylated, acylated or acetylated carbohydrates, carbohydrate oxidation products (e.g. glucuronic acid, mucic acid), reduced carbohydrates and substit~lted carbohydrates (e.g. nucleosides, nucleotides, nucleic acids).
In yet another embodiment, the organosil~nP is A~ APP/DNB/GHP/Mayl.1997 CA 02236893 1998-0~-04 (CH30)3Si(('H2)3N+(CH3)2C,BH3,CI-, (CH30)3Si(CH2)3Nt(CH3)2C,8H37Br-, (CH30)3Si(CH2)3N+(CloH2l)zcH3cl-~ (CH30)3Si(CH2)3N+(CIOH2~)2CH3Br-, (cH3o)3si(cH2)3N+(cH3)3cl-~ (CH30)3Si(CH2)3N+(CH3)2C8Hl~cl-~
(cH3o)3si((-H2)3N+(cH3)2cloH2lcl~(cH3o)3si(cH2)3N+(cH3)2cl2H25cl-~
(CH30)3si(cH2)3N+(cH3)2c,4H29cl-~ (CH30)3Si(CH2)3N+(CH3)2C,6H33CI-, (CH30)3Si((-H2)3N+(CH3)2C20H4,Cl-, (CH30)3Si(CH2)3N+(C4H9)3CI-, (CH30')3Si((-H2)3N+(C2H5)3CI-, (CH3CH20)3Si(CH2)3N+(CH3)2C,BH2,CI-, (CH3o)3si(cH2)3NHc(o)(cF2)6cF3!~ (CH30)3Si(CH2)3NHC(O)(CF2)BCF3, (CH30)3Si(CH2)3NHC(O)(CF2)l0CF3, (CH30)3Si(CH2)3NHC(O)(CF2)12CF3, (CH30)3Si(CH2)3NHC(O)(CF2),4CF.,. (CH30)3Si(CH2)3NHC(O)(CF2)t6CF3, (CH30)3Si(~-H2)3NHSO2(CF2),CF3, (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHc(o)(cH2)6cH3 (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHc(o)(cH2)8cH3 (cH3o)3si(l-H2)3N+(cH3)2(cH2)3NHc(o)(cH2)locH3 (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHc(o)(cH2)l2cH3~
(CH30)3,Si~ CH2)3N+(CH3)2(CH2)3NHC(O)(CH2)l4CH3, (cH3o)3si('-H2)3N+(cH3)2(cH2)3NHc(o)(cH2)l6cH3 (cH3o)3si('-H2)3N+(cH3)2(cH2)3NHc(o)(cF2)6cF3, (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHc(o)(cF2)BcF3, (CH30)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(cF2)l0cF3, (CH30)3Si(~"H2)3N+(CH3)2(CH2)3NHC(O)(CF2)l2CF3, (CH30)3Si('''H2)3N+(CH3)2(CH2)3NHC(O)(CF2)14CF3, (cH3o)3si(l'-H2)3N+(cH3)2(cH2)3NHc(o)(cF2)l6cF3 (cH3o)3si(lrH2)3N+(cH3)2(cH2)3NHso2(cF2)7cF3 (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHso2(cF2)9cF3 (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHso2(cF2)llcF3 (cH3o)3si(cH2)3N+(cH3h(cH2)3NHso2(cF2)l3cF3 (CH3o)3si(lr'H2)3N+(cH3)2(cH2)3NHso2(cF2)l5cF3~ or (CH30)3Si(lCH2)3N + (cH3)2(cH2)3NHso2(cF2) ~6CF3 A:\BST-lOOAPP/DNB/GHBII~/lay 1, 1997 CA 02236893 1998-0~-04 Moreover, in still another embo~limPnt the organosilane is NH2(CH2)2~H(CH2)3Si(OCH3)3, NH2(CH2)3Si(OCH3)3, NH2(CH2)3Si(OCH2CH3)3, Cl(CH2)3Si(OCH3)3, Cl(CH2)3Si(OCH2CH3)3, CI(CH2)3SiCl3, C3H502(CH2)3Si(OCH3)3, C3H502(CH2)3Si(OCH2CH3)3, C4H502(CH2)3Si(OCH3)3,C4H502(CH2)3Si(OCH2CH3)3, CH3SiHCl2, NaO(CH3O)P(O)(CH2)3Si(OH)3, SiHCI3, n-2-vinylbenzylamino-ethyl-3-aminopropyltrimethoxysilane HCL, H2C = CHSi(OCOCH3)3, H2C = CHSi(OCH3)3, H2C=~HSi(OCH2CH3)3, H2C=CHSiCl3, (CH3)2SiCl2, (CH3)2Si(OCH3)2,(C6H5)2SiCI2, (C2H5)SiCl3, (C2H5)Si(OCH3)3, (C2H5)Si(OCH2CH3)3, isobutyltrimethoxysilane, n-octyltriethoxysilane, CH3(C6H5)SiCl2, CH3SiCl3, CH3Si(OCH3)3, C6H5SiCI3, C6H5Si(OCH3)3, C3H7SiCl3, C3H7Si(OCH3)3, SiCl4, ClCH2C6H4CH2CH2SiCl3n, ClCH2C6H4~H2CH2Si(OCH3)3, ClCH2C6H4CH2CH2Si(OCH2CH3)3, decyltrichlorosilane, dichloromethyl(4-methylrh~n~thyl)silane, diethoxymethylphenylsilane, [3-(diethylarnino)propyl]trimethoxysilane, 3-(dimethoxymethylsilyl)-l-propqnethiol, dimethoxymethylvinylsilane, 3-[tris(trimethylsilyloxy)silyl]propyl n-~h~rrylate, trichloro[4-(chloromethyl)phenyl]silane, methylbis(khlle~ylsilyloxy)vinylsilane, methylkipropoxysilane, or trichlorocyclopentylsilane.

Moreover, the present invention also provides a product from mixing an organosilane of the formula II, III, IV, or V:
(Rl)3SiR2N+(R3)(R4)(R5)Y- (II) (R,)3SiR2N(R3)(R4) (nI) (Rl)3SiR2R35 (Rl)2si(R36)(R37) (V) as s~-bs~nti~lly previously described with rerere~ce to the formula numbers II, III, IV
and V, with alcohols having at least two hydroxyls, carbohydrates, inrlllAing monosacch:~rides, ~ cch~rides, oligos~cch~rides, polysaccharides, mo~ifi~ocl carbohydrates, inrl~ in~ graft and block co-polymers, partially alkylated, acylated or acetylated carbohydrates, carbohydrate oxidation products (e.g. glucuronic acid, mucic A:1135T-I/~OAPP/DNB/GNB/l~l~y 1, 1997 CA 02236893 1998-0~-04 acid), reduced carbohydrates and suhstihlted carbohydrates (e.g. nucleosides, nucleotides, nucleic acids).
In addition, the present invention also provides a method of treating a substrate, comprising ,-ontarting the substrate with a sufficient amount of the composition as described above for a period of time s~lfficient for tl~ lf ~1l of the substrate.
Moreover, in an alternate emboclim~nt~ the present invention provides a method of treating a substrate, comprising cont~cting the substrate with a s--ffirient amount of the compound as described above for a period of time sufficient for treatm~nt of thesubstrate.
In addition, the present invention provides a keated substrate having adhered thereto the product produced by cont~rting the organosilane and the polyol as described above. Alternatively, the present invention provides a treated substrate having adhered thereto a co]npound produced by cont~rting the org~nnsil~n~ and the polyol as described above.
In yet another embo(lime~t, the present invention provides a method of dyeing and treating a substrate, co~ ,ising cont~rting the substrate with an aqueous (i.e., substantially water soluble) composition comprising an aqueous soluble dye suitable for dyeing a substrate and the product formed from mixing an organosilane of the formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, indepen~ently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group; with a polyol cc~l~lising at least two hydroxy groups, wherein at least two sul~h groups are separated by less than three intervening atoms, for a period of time sufficient to dye and treat the substrate.
In a further preferred embo~im~nt the present invention provides a method of antimicrobially treating a food article, comprising cont~cting the food article with an effective amount of the product formed from mixing an ~ntimirrobial organosilane of the formula RnSiX4 ~ where n is an integer of from 0 to 3, prefelably O to 2; each R is, independently, a nonhydrolizable organic group; and each X is, indepen~ently, a hydrolyzable group; with a polyol colllplising at least two hydroxy groups, wherein at A:~OsT-ICOAPP/DNB/GHB/M;Iyl.1997 CA 02236893 1998-0~-04 ..

21 BST-l00 least two such groups are separated by less than three intervening atoms, for a period of time sufficient to ~nt;,,,ic~obially treat the food article.
In yet another embo~im~nt t_e present invention provides a method of antimicrobia]ily coating a fluid container used for cont~inine a human or animalconsulllable product, C(~ iSillg contactine the cont~in~r with an effective amount of the product formed from mixing an ~ntimi~robial organosilane of the formula RnSiX1 n where h is an integer of from 0 to 3, preferably 0 to 2; each R is, in-lepen-lent1y, a nonhydrolizable organic group; and each X is, in~epen-l~ntly, a hydrolyzable group;
with a polyo:l comprising at least two hydroxy groups, wherein at least two such groups are separatecl by less than three intervening atoms, for a period of time sufficient to ~ntimirrobially coat the container.
Moreover, in yet another embotlim~nt, the present invention provides a method of antimicrobially coating a latex m~1ir~1 article for use in a human or anirnal medical procedure, comprising ct)ntarting the article with an effective amount of the product formed from mixing an ~ntimi~robial or~nosil~n~ of the formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, indep~n~çnt1y, a hydrolyzable group;
with a polyol co~ .ishlg at least two hydroxy groups, wherein at least two such groups are separated by less than three intervening atoms, for a period of time sufficient to antirnicrobially coat the article. In a further embodim~nt of this mPthod, the article is a surgical glove.
In yet another embodim~nt, the present invention provides a method of ~ntimi~robia.lly treating a substrate selecte~ from the group con~i.cting of a concrete pipe, 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 e~cposed work of art, an HDP plastic cover, a silicone or TEFLON2 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 lehlforcement product, comprising cont~ctine the su~ ale with an effective amount of the product A:~BST~ APP/DNB/GHB/M:ayl,1997 CA 02236893 1998-0~-04 formed fror~l mixing an Antimirrobial organosil~nP of the formula RnSiX4.n where n is an integer oi from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, indeper~e~tly, a hydrolyzable group;
with a polyol comprising at least two hydroxy groups, wherein at least two such groups S are sepalated by less than three inter~ening atoms, for a period of time sufficient to ~ntimicrobially treat the substrate.
'Moreover, in yet another embo-iimPnt, the present invention provides a method of ~ntimicrobially enhancing a product of rubbing alcohol, a flower preservative, or a waterproofing solution, comprising ~r~mixing with the product an effective amount of the product formed from mixing an ~ntimi~robial organosilane of the formula RnSiX~n where n is an integer of from 0 to 3, preferably 0 to 2; each R is, indepen~ently, a nonhydroliz;able organic group; and each X is, independently a hydrolyzable group;
with a polya,l comprising at least two hydroxy groups, wherein at least two such groups are separated by less than three intervening atoms, for a period of time sufflcient to ~nrimi~robially er~h~n~e the product.
The present invention provides water-stabilized and/or 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 organnsil~n~s of the general formula RnSiX4 n where n is an integer of from 0 to 3, preferably 0 to 2; R is a nonhydrolizable organic group, such as but not limited to, alkyl, aromatic, organofiln~tion~l, or a combination thereof; and X is halogen, such as but not limited to, Cl, Br, or I, or X is hydroxy, alkoxy such as methoxy or ethoxy, acetoxy, or ~mcubstit~lted or s~lkstit~-ted acyl. For such organosilanes, X is prone to react with various hydroxyl cont~ining molecules.
In a further embo~lim~nt, the present invention employs from about 0.001% to about 20% by weight of an organo~ n~ co~ g hydrolyzable groups and from about 0.01 to about 20.0 weight equivalents, preferably from about 0.1 to about 5 weight equivalents of a polyol stabilizer of the invention. This ple~alation is preferable for water soluble stabilizers, such as glucose, sucrose, glucuronic acid, A:~BST-ll)OAPP/DNBlGHBlMiy 1, 1997 CA 02236893 1998-0~-04 23 BST- l00 nucleosides, nucleotides, polynucleotides. Alternatively, where the stabilizers are not sufficiently water-soluble, additional stability is achieved by mixing the organosilane with the stabilizer in a non-aqueous solvent. In such an alternative prepdlation, the rerni~ining solvent (e.g., m~thi~nol) iS liberated via ~ ti11~tion, freeze-drying, evaporation or other methods known in the art for removal or volatile organic solvents.
For polyols within this invention that are thernselves not very soluble in water, an organo'silane stabilizing effect may still be achieved by i~dmixing the orgPnosili~ne with, for example, a carbohydrate in water, followed by filtration. The filtrate may thus be stabilized while still exhibiting a desirable ~ropllly, such as i~ntimi~robial activity.
Where the organosili~n~ is not an i~ntimicrobial agent, spectral evidence of thecompound's presence is useful to dernor..el.ate the compound's presence. These methods provide stable, clear solutions of the organosilane which are capable ofcoating surfaces with the org~n-~si1~n~ upon treatm~nt of the surface with the solution.
The solutions are stable for ext~nAed periods, from several days to several months. It ~will also be recognized that while aqueous siloxane stock solutions of up to 20% siloxane may be stabilized by polyols dieclosed herein, working siloxane concentrations tend to be in the 0.001-5% siloxane range where the stabilization effects of the herein disclosed stabilizers are less ch~ nged by the higher siloxane concentrations required in stock solutions.
The solutions of the present invention are, in certain l)rcÇelled embodiments, useful for tb,e application of various org~nosi1i~n~ coupling agents to surfaces in industrial and household uses without the use of toxic and/or fl~mm~le organic solvents. One of ordinary skill in the art would recognize that the above preparation steps are merely guidelines and such a person would, without undue e~.,~;~"~nti~tion, be able to prel)are the composition by varying the parameters for conti~cting 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.

A:~BST-lOOAPP/DNB/GHB/Milyl,1997 CA 02236893 1998-0~-04 Silanes The present invention is useful for stabilizing organosil~nes of the general formula RnSiX4.n where n is an integer of from 0 to 3, preferably 0 to 2; R is anonhydrolizable organic group (alkyl, arornatic, organofunctional or a combination thereof); and X is hydroxy, alkoxy, preferably methoxy or ethoxy, halogen, preferably Cl, Br, or I, acetoxy, acyl or substit~te(l acyl, or a hydrolyzable polymer or other moiety'prone to hydrolysis and/or environm~nt~l harrnfulness.
The organosil~n~s used in the practice of the present invention need not be, andoften are not, water soluble. By varying the stabilizer and preparation method, the organosil~nf s selected for use in the present invention are solubilized in water by the stabilizer.
Nun~lerous art-known organosil~n~s are suitable for the present stabilization procedures ItO 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 theirentirety herein by this reference for the te~ching~ of suitable org~n- sil~n.os. These organc sil~n~s are suitable for the formation of the water-stabilized organosilane compounds, products and compositions of the present invention. In ad-lition, thedisclosure of U.S. Patent No. 4,390,712 is hereby incorporated by reference for its teaching of siloxane synthesis in an aqueous m~dillm Per the instant disclosure, those skilled in the art will appreciate that the aqueous siloxane synthesis m~othoflc of the 4,390,712 patent are motlifi~d to advantage by pclro~ g the siloxane synthesis in the presence of the polyol stabilizer as defined herein, thereby forming a stabilized siloxane-water composition while still taking advantage of the accclclc.ted kin~tics of siloxane formation in aqueous media noted in the 4,390,712 patent. Accordingly, a fulther embo~lim~ nt of this invention is a method for making an organosilane of the formula RnSiX4.n where n is an integer of from 0 to 3, p~eferably 0 to 2; each R
is, indepenrlently~ a nonhydrolizable organic group; and each X is, inrlepenrlently, a A:~BST-l~APP~DNBlGHB/Mayl,1~7 CA 02236893 1998-0~-04 hydrolyzable group; from starting materials in an aqueous solution in the presence of a polyol cont~i~in~ at least two hydroxyls which are separated by less than three intervening atoms in an effective amount of the polyol sufficient to stabilize the organosilane as it is formed from the re~ct~nt.c.
Pl~fe,fed silanes for use in the compounds, products and composition~ and methods of l:he present invention include silanes of the following formula:
(R,)3SiR2N+(R3)(R4j(R5)Y- or (R,)3SiR2N+CsH5Y-wherein each R~ is, independently, halogen [Cl, Br, I, F] or R6O, where R6 is H, alkyl of from 1 to about 6 carbon atoms, ~ln~ub~ e~ or substituted, prefelably from 1 to about 2 carblon atoms and more preferably I carbon atom, or acetyl- or other acyl, including substituted acyl, or R6O can be derived from any hydroxylated polymer,hydroxylated liquid, or hydroxylated. solid regardless of water solubility, or R6O can be derived from any polyether such as, but not limited to, polyethyleneglycols or polypropyle-neglycols, such as poly(propyleneglycol)triol (glycerol propoxylate); R2 is unsubstituted or s~-bstitl-ted benzyl- or an un~bstinltçd or substituted alkyl of from 1 to about 3 carbon atoms, preferably alkyl of from 1 to 22 carbon atoms; R3 and R4 are, independently, lower alkoxy of from 1 to 4 carbon atoms, preferably of 2 ca~bon atoms, such as CH2CH2OH, CH2CH(OH)CH3, alkyl of from 1 to about 22 carbon atoms, preferably from 1 to about 10 carbon atoms and most preferably from 1 to 2 carbon atomls or R3 and R4 can, together, form a morpholine or other cyclic or heterocyclic, unsa~uiated or saturated, five to seven-membered ring of the formula:
-R3-(R,)k-R4-where k is a.n integer from 0 to 2 and R7, where the ring is saturated, is CH2, O, S, NH, NH2+, NCH2CH2NH2, NCH2CH2NH3+, NCH2CH2N(R8)(Rg), NCH2CH2N+(R8)(Rg)(RIo)~ N(alkyl), N(aryl), N(benzyl), and R7, where the ring is unsaturated is, N, N+H, N+(alkyl), :N+(aryl), N+(benzyl), N-CH2-N, N+H-CH2-N, N+(alkyl)-CH2-N, N+(aryl)-CH2-N, or N+(benzyl)-CH2-N where R8, R9, and Rlo are, independently, benzyl, polyether, 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 A:\BSDl(~APP/DNB/GHB/May 1, 1997 CA 02236893 1998-0~-04 26 BST-lO0 atoms, preferably 1 to about 10 carbon atoms; R5 is CH2C6H5, CH2CH20H, CH2CH(OH)CH3, a polyether such as polyethyleneglycol: -(CH2CH20)aH, polypropyleneglycol: -(CH2CH(CH3'~O)aH, or alkylated polyoxyethylene: -(CH2CH20)jlB where B is alkyl of from 1 to 22 carbon atoms, un~u~ uled or substituted, and where each a is, indepe~ tly, an integer of from 1 to 12, more preferably of from about 1 to about 5, or R5 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, functionaliz~ d carboxylate, such as trifluoro~ret~te and perfluoroalkylcarboxylates, or other alkyl ~md arylsulfonate salts, inrl~-ling trifluoromethylsulfonate and perfluoroalk~lsulfonate salts, phosphate and phosphonate salts, borate and boronate salts or any other suitable anionic moiety.

Plefe,l~d org~nosil ln~s include, but are not limited to:
3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, 3-(trimethoxysilyl)propylmethyldi(decyl) ammonium chloride, 3-chloro~ropyl~ hoxylsilane, octadecyltrimethoxysilane, perfluorooctyltriethoxysilane, (CH30)3Si(CH2)3N+(CH3)2cl8H37cl-~
(CH30)3Si(('H2)3N+(CH3)2C,8H3,Br~"
(cH3o)3si(('H2)3N+(cloH2l)2cH3cl, (CH30)3Si(('H2)3N+(C~OEI2~)2CH3Br ., (CH30)3Si(CH2)3N + (CH3)3Cl-, (cH3o)3si(~-H2)3N+(cH3)2c8Hl7 (CH30)3Si(CH2)3N+(CH3)2CloH2lcl~ ~
(CH30)3Si(CH2)3N+(CH3)2C,2H25Cl-!, (CH30)3Si(CH2)3N+(CH3)2cl4H29cl-A:\BST-8)0APP/DN8/GH8/May 1, 1997 CA 02236893 1998-0~-04 (CH30)3Si(CH2)3N + (CH3)2C ~6H33Cl- .
(cH3o)3si(cH2)3N+(cH3)2c2oH4lcl-~
(CH30)3Si(CH2)3N +(C4Hg)3Cl-, (CH30)3Si(CH2)3N+(C2H5)3CI-~
(cH3cH2o~l3si(cH2)3N+(cH3)2cl8H2 (CH30)3Si(CH2)3NHC(O)(CF2)6CF3, (CH3C~)3Si('''H2)3NHC(O)(cF2)8cF3 .
(cH3o)3si(cH2)3NHc(o)(cF2)locF3 ~
(cH3o)3si(cH2)3NHc(o)(cF2)l2cF3 .
(cH3o)3si(cH2)3NHc(o)(cF2)l4cF3~
(cH3o)3si(cH2)3NHc(o)(cF2)l6cF3 .
(CH30)3Si('''H2)3NHSO2(CF2)7CF3, (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHc(o)(cH2)6cH3~
(CH30)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CH2)8CH3, (CH30)3Si(CH2)3N + (CH3)2(CH2)3NHC(O)(CH2) ~oCH3, (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHc(o)(cH2)~2cH3~
(CH30)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CH2),4CH3, (cH3o)3si(l-H2)3N+(cH3)2(cH2)3NHc(o)(cH2)l6cH3 (CH30)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2)6CF3, (cH3o)3si(~H2)3N+(cH3)2(cH2)3NHc(o)(cF2)8cF3~
(CH30)3Si('''H2)3N+(CH3)2(CH2)3NHC(O)(CF2),0CF3, (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHc(o)(cF2)ucF3~
(CH30)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2),4CF3, (CH30)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2),6CF3, (cH3o)3si(cH2)3N+(cH3)2(cH2)3NHso2(cF2)~cF3~
(CH30)3Si(lCH2)3N+(CH3)2(CH2)3NHSO2(CF2)9CF3, (CH30)3Si(~CH2)3N+(CH3)2(CH2)3NHS02(CF2)~ ~CF3, (CH30)3Si(CH2)3N+(CH3)2(CH2)3NHSO2(CF2),3CF3, (cH3o)3si(c~H2)3N+(cH3)2(cH2)3NHso2(cF2)~5cF3 A:\BST-~APP/DNB~GHB/~Iayl,1997 (CH30)3Si(C'H2)3N + (CH3)2(CH2)3NHSO2(CF2) ,6CF3 .
aminoethylarninopropyltrimethoxysilane: NH2(CH2)2NH(CH2)3Si(OCH3)3, 3-aminopropyl~ cLhoxysilane: NH2(CH2)3Si(OCH3)3, 3-arninopropyltriethoxysilane: NH2(CH2)3Si(OCH2CH3)3, 5 3-chloroplopyltrimethoxysilane: Cl(CH2)3Si(OCH3)3, 3-chloropropyltriethoxysilane: Cl(CH2)3Si(OCH2CH3)3, 3-chloro~l o~yltrichlorosilane: Cl(CH2)3SiCI3, 3-glycidoxypropyltrimethoxysilane: C3H502(CH2)3Si(OCH3)3, 3-glycidoxy~?-c~yltriethoxysilane: C3H5O2(CH2)3Si(OCH2CH3)3, 3-m~th~crylo~y~lG~yltrimethoxysilane: C4H5O2(CH2)3Si(OCH3)3, 3-met_acryloxypropyltriethoxysilane: C4H5O2(CH2)3Si(OCH2CH3)3, methyldichlorosilane: CH3SiHCl2, silane-modilled m~l~minç: Dow Corning Ql-6106, sodium (trihydroxysilyl)propylmethylphosphonate: NaO(CH30)P(O)(CH2)3Si(OH)3, 1.5 trichlorosilane, SiHCI3, n-2-vinylbenzylarnino-ethyl-3-aminopropyltrirnethoxysilane HCL: Dow Corning Z-6032, vinyltriacetoxysilane: H2C = CHSi(OCOCH3)3, vinyltrirnethoxysilane: H2C = CHSi(OCH3)3, vinyltriethoxysilane: H2C = CHSi(OCH2CH3)3, vinyltrichlorosilane: H2C =CHSiCI3, dirnethyldichlorosilane: (CH3)2SiCI2, dimethyltlinl~thoxysilarle: (cH3)2si(ocH3)2 diphenyldic:hlorosilane: (C6H5)2SiCl2, ethyltrichlorosilane: (C2H5)SiCI3, ethylL.hl.eLlloxysilane: (C2H5)Si(OCH3)3, ethyltriethoxysilane: (C2H5)Si(OCH2CH3)3, isobutyltrimethoxysilane, n-octyltriethoxysilane, A:~ST-I~APPlDNB/GHB/W~yl,1997 CA 02236893 1998-0~-04 29 BST-l00 methyltrichlorosilane: CH3SiCl3, methylLIinl~,Lhoxysilane: CH3Si(OCH3)3, phenyltrichlorosilane: C6H5SiCl3, phenyltrimethoxysilane: C6HsSi(OCH3)3, n-propyltrichlorosilane: C3H,SiCl3, n-propyltrimethoxysilane: C3H7Si(OCH3)3, silicon tetrachloride: SiCl4, ClCH2C6H4CH2CH2SiCl3n ~
ClCH2C6H4CH2CH2Si(OCH3)3, ClCH2C6H4CH2CH2Si(OCH2CH3)3, decyltrichlorosilane, dichloromethyl(4-methylphenethyl)silane, diethoxymethylphenylsilane, [3 -(diethylamino)propyl]trimethoxysilane, 3-(~im~thnxymethylsilyl)-1-propa~ ~iol, dimethoxymethylvinylsilane, 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate, trichloro[4-(chloromethyl)phenyl]silane, methylbis(l~.hl~lhylsilyloxy)vinylsilane, methyllliplopoxysilane, and trichlorocyclopentylsilane .

In one particular embodiment of this invention, namely the use of the organosilane as a W piotect~l, for example in a sun-tan lotion, para-amino benzoic acid is an active co1~on~ . According to this embodiment of the invention, the org~nosil~n~ is selected from:
(CH30)3Si('''H2)3NHC6H4COOH
(CH30)3Si(CH2)3NHC6H4COOCH3 (CH30)3Si(CH2)3NHC6H4COOc2H5 A:~BST-I~APP~NBlGHB~layl. 1~7 CA 02236893 1998-0~-04 (CH30)3Si(CH2)3NHC6H4COOc3H7 (CH30)3Si(CH2)3NHC6H4COOC4Hg (cH3o)3sl(cH2)3NHc6H4coocH2c6H5 (CH30)3Si(CH2)3NHC6H4COOCH2C6H4NH2 (CH3O)3Si(CH2)3NHC6H4COOCH2c6H4N(cH3)2 (CH30)3Si.(CH2)3NHC6H4COOCH2C6H4N(cH2cH3)2 (CH30)3Si.(CH2)3NHC6H4COOCH2C6H4N+(CH3)3 Y-(CH30)3Si(CH2)3NHC6H4COOCH2C6H4N+(CH2CH3)3 Y-(CH30)3Si(CH2)3NCH3C6H4COOH
(CH30)3Si(CH2)3NCH3C6H4COOCH3 (CH30)3Si(CH2)3NCH3C6H4COOC2Hs (CH30)3Si(CH2)3NCH3C6H4COOC3H, (CH30)3Si(CH2)3NCH3C6H4COOC4Hg (CH30)3Si(CH2)3NCH3C6H4COOCH2C6H5 (cH3o)3si(cH2)3NcH3c6H4coocH2c6H4NH2 (CH30)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH3)2 (CH30)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH2CH3)2 (CH3O)3Si(CH2)3NCH3C6H4COOCH2C6H4N + (CH3)3 Y-(CH30)3Si(CH2)3NCH3C6H4COOCH2C6H4N+(CH2CH3)3 Y-(CH3O)3Si(CH2)3N+(CH3)2C6H4COOH Y-(CH30)3SI(CH2)3N+(CH3)2C6H4COOCH3 Y-(cH3o)3sI(cH2)3N+(cH3)2c6H4cooc2H5 y-(CH30)3SI(CH2)3N+(CH3)2C6H4COOC3H, Y-(cH3ohsI(cH2)3N+(cH3)2c6H4cooc4H9 Y-(cH3o)3sI(cH2)3N+(cH3)2c6H4coocH2c6H5 Y-(cH3o)3si(cH2)3N+(cH3)2c6H4coocH2c6H4NH2 Y
(CH30)3Si(CH2)3N+(CH3)2C6H4COOCH2c6H4N(cH3)2 Y-(CH30)3Si~CH2)3N+(CH3)2C6H4COOCH2C6H4N(cH2cH3)2 Y-(cH3o)3si(cH2)3N+(cH3)2c6H4coocH2c6H4N (CH3)3 Y Y

A:~BST-lOOAPPlDNBlGHBlMay 1, 1997 CA 02236893 1998-0~-04 (CH3o)3si(cH2)3N+(cH3)2c6H4coocH2c6H4N (CH,CH3)3 Y Y
(CH30)3Si(CH2)3NC2H5C6H4COOH
(CH30)3Si(CH2)3NC2H5C6H4COOCH3 (CH30)3Si(CH2)3NC2H5C6H4COOC4Hg S (CH30)3Si(CH2)3NC2H5C6H4COOC3H7 (CH30)3Si(CH2)3NC2H5C6H4COOC4H9 (CH30)3Si(CH2)3NC2H5C6H4COOCH2C6Hs (cH3o)3si(cH2)3Nc2H5c6H4coocH2c6H4NH2 (cH3o)3si(cH2)3Nc2H5c6H4coocH2c6H4N(cH3)2 (cH3o)3si(cH2)3Nc2H5c6H4coocH2c6H4N(cH2cH3)2 (cH3o)3si(cH2)3Nc2H5c6H4coocH2c6H4N (CH3)3 Y
(CH30)3Si(CH2)3NC2H5C6H4COOCH2C6H4N+(CH2CH3)3 Y-(CH30)3Si(CH2)3N+(C2H5)2C6H4COOH Y-(CH30)3Si(CH2)3N+(C2H5)2C6H4COOCH3 Y-(CH30)3Si(CH2)3N+(C2H5)2C6H4Cooc2H5 y-(CH30)3S i(CH2)3N + (C2H5)2C6H4COOC3H7 y-(CH30)3Si(CH2)3N+(C2H5)2C6H4COOC4H9 Y-(cH3o)3si(cH2)3N+(c2H5)2c6H4coocH2c6H5 y-(cH3o)3si(cH2)3N+(c2H5)2c6H4coocH2c6H4N2 Y-(cH3o)3si(cH2)3N+(c2H5)2c6H4coocH2c6H4N(cH3)2 Y-(CH30)3Sii(CH2)3N+(C2H5)2C6H4COOCH2C6H4N(CH2cH3)2 Y-(cH3o)3sii(cH2)3N+(c2H5)2c6H4coocH2c6H4N (CH3)3 YY
(cH3o)3sii(cH2)3N+(c2H5)2c6H4coocH2c6H4N+(cH2cH3)3 y y (CH3CH20)3Si(CH2)3NHC6H4COOH
(CH3CH20)3Si(CH2)3NHC6H4COOCH3 (CH3CH20)3Si(CH2)3NHC6H4COOC2H5 (CH3CH20)3Si(CH2)3NHC6H4COOC3H7 (CH3CH20)3Si(CH2)3NHC6H4COOC4H9 (CH3CH2C))3Si(CH2)3NHC6H4COOCH2C6H5 A:\BST-l~APP~NB/GHB,~ayl,1997 CA 02236893 1998-0~-04 (CH3CH20)3Si(CH2)3NHC6H4COOCH2C6H4NH2 (CH3CH20)3Si(CH,)3NHC6H4COOCH.C6H4N(CH3)2 (cH3cH2o)3si(cH2)3NHc6H4coocH2c6H4N(cH~cH3)2 (CH3CH20)3Si(CH2)3NHC6H4COOCH2C6H4N+(CH3)3 Y-(CH3CH2O)3Si(CH2)3NHC6H4COOCH2C6H4N+(CH2CH3)3 Y-(cH3cH2o)3si(cH2)3NcH3c6H4cooH
(cH3cH2o)3si(cH2)3NcH3c6H4coocH3 (CH3CH20)3Si(CH2)3NCH3C6H4COOC2Hs (CH3CH20)3Si(CH2)3NCH3C6H4COOC3H7 (CH3CH20)3Si(CH2)3NCH3C6H4COOC4H9 (cH3cH2o)3si(cH2)3NcH3c6H4co ocH2c6H5 (CH3CH20)3Si(CH2)3NCH3C6H4COOCH2C6H4NH2 (CH3CH20)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH3)2 (CH3CH20)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH2CH3)2 (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H4N+(CH3)3 Y-(CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H4N + (CH~CH3)3 Y-(CH3CH20)3Si(CH2)3N + (CH3)2C6H4COOH Y-(CH3CH20)3Si(CH2)3N+(CH3)2C6H4COOCH3 Y-(CH3CH20)3Si(CH2)3N+(CH3)2C6H4COOC2Hs Y-(cH3cH2O)3si(cH2)3N+(cH3)2c6H4cooc3H~ y-(cH3cH20)3si(cH2)3Nf(cH3)2c6H4cooc4H9 y-(cH3cH2o)3si(cH2)3N+(cH3)2c6H4coocH2c6H5 y-(CH3CH2C))3Si(CH2)3N+(CH3)2C6H4COOcH2c6H4NH2 Y-(CH3CH2C))3Si(CH2)3N+(CH3)2C6H4COOcH2c6H4N(cH3)2 Y-(cH3cH2c))3si(cH2)3N+(cH3)2c6H4coocH2c6H4N(cH2cH3)2 Y-(CH3CH2C))3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N+(CH3)3 Y-Y-(cH3cH2c))3si(cH2)3N+(cH3)2c6H4coocH2c6H4N+(cH2cH3)3 y-y-(cH3cH2o)3si(cH2)3Nc2H5c6H4cooH
(cH3cH2c))3si(cH2)3Nc2H5c6H4coocH3 A:\85T-l~APPlDNB/GHB/Mayl,19~

CA 02236893 1998-0~-04 (CH3CH20)3Si(CH2)3NC2H5C6H4COOCH3 (CH3CH20)3Si(CH2)3NC2H5C6H4COOC2H5 (CH3CH20)3Si(CH2)3NC2H5C6H4COOC3H, (cH3cH2o)3si(cH2)3Nc2H5c6H4cooc4H9 (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H5 (CH3CH20)3,Si(CH2)3NC2H5C6H4COOCH2C6H4NH2 (CH~CH20)3Si(CH2)3NC2H5C6H4COOCH2C6H4N(CH3)2 (CH3CH20)3Si(CH2)3NC2H5C6H4COOCH2C6H4N(CH2CH3)2 (cH3cH2o)3si(cH2)3Nc2H5c6H4coocH2c6H4N+(cH3)3 y-(CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N+(CH2CH3)3 Y-(cH3cH2o)3si(cH2)3N+(c2H5)2c6H4cooH Y-(cH3cH2o)3si(cH2)3N+(c2H5)2c6H4coocH3 y-(CH3CH20)3Si(CH2)3N+(C2H5)2C6H4COOC2H5 Y-(CH3CH20)3'Si(CH2)3N+(C2H5)2C6H4Cooc3H7 y-(CH3CH20)3Si(CH2)3N+(C2H5)2C6H4COOC4H9 Y-(cH3cH2o)3lsi(cH2)3N+(c2H5)2c6H4coocH2c6H5 y-(CH3CH20)3Si(CH2)3N~(C2H5)2C6H4cOOcH2c6H4NH2 Y-(CH3CH20)3Si(CH2)3N+(C2H5)2C6H4COOcH2c6H4N(cH3)2 Y-(CH3CH20)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N(CH2CH3)2 Y-(CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N+(CH3)3 Y~Y~, and (CH3CH20)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N+(CH2CH3)3 y-y-.

Stabili7~rs As described herein, plefell~d stabilizers of the present invention preferably contain at least two hydroxy groups, where at least two of said at least two hydroxy groups are separated by less than three intervening atoms, i.e., (HO-A-B-OH where A
and B are any one or two atoms). Such stabilizers can stabilize aqueous solutions of the above-described organosilanes RnSiX~n and are generally useful for stabilization of all such solutions where n is an integer from 0 to 2 and where water solubility or A:lBST-IOOAPP/DNB/GHB/May 1, 1997 CA 02236893 1998-0~-04 minimi7~tion or prevention of water-in~llce(l, self-con-1enc~tion (and associated polymerization) is desired. In particular, prerelled stabilizers are monosaccharides, including but not limited to glucose, tli~acçharides, including but not limited to sucrose, polysaccharides, polynucleotides, and alcohols, wherein at least two adjacent hydroxyls 5 separated by fewer than three intervening atoms are present in the stabilizer.

Uses The compounds, products and compositions of the present invention are useful for a mllltitllcle of purposes. Such purposes include any known use for the prefelled 10 starting material organosilanes of the above-described general formula. In prerell~d embodim~nts, the presently described, water-stabilized, organosilane compounds, products and compositions are suitable to applications such as: 1) treatment of surfaces, including fillers _nd pigm~nt~, 2) additives to coAtines such as dyes, or 3) as additives to organic monomers (such as acrylics) prior to formation of the respective polymer.
Therefore, in addition to the utility of prior organosilane quaternary ammonium compounds such as 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride as surface bonding antimicrobial agents, numerous other uses of organofunctional silanes are contemplated, such as the use of the compounds, products and compositions of the invention in coating applications which include the l~e~ lrnt of surfaces or particles 2() (pigments or fillers), in primers, in paints, inks, dyes and adhesives, and as reactive interrn~ tes for silicone resin synthesis.
The lpresent invention can be used to prepare, inter alia, agricultural products, cleaning compositions, antimi~robial sponges, antimiçrobial bleaching agents, antimicrobial fillers for paints, plastics, or concrete, and to treat concrete structures 25 such as livestock shelters, where microbial infestation is a problem.
In various embo-lim~nt~, 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, ~l tmina alnminllm chlorohydrate, titanitlm dioxide, A:lBST-l~APP/DNB/GHB/M;~yl,1997 CA 02236893 1998-0~-04 calcium carbonate, wood, glass beads, containers, tiles, floors, curtains, marine products, tents, bac~cl~c, 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 5; are not limited to, air filters and materials used for the m~m-f~c~lre thereof, 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 intim~te apparel; cosmetics, lotions, creams, oi.1~ , disinfectant s~niti7~rs~ wood preservatives, plastics, lO adhesives, paints, pulp, paper, cooling water, and laundry additives and non-food or food cont~tin~ surfaces in general.
For the above described substrates, mixtures and applications, treatment generally involves cont~rting or mixing the article to be treated with a water-stabilized organosilane solution of the present invention, comprising the org~nosi1~n~-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.
Generally, tre~tm~nt begins almost imm~ tely upon contact, but preferably requires from about ] 5 seconds to about 48 hours, more preferably from about l minlltes to about 24 hours, even more preferably from about five minutes to 1 hour, and even20 more preferably for about 30 mim1tes. Further general guidelines for application are as follows: For dipping a large object, it is prer.".ed that 1-2 ...i~ es 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 cont~cting times, for example, fabric may pass through an aqueous bath of the composition at a rate of up to 2'i 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 A:lBST-l~APP/DNBlGHB/M~yl,l997 CA 02236893 1998-0~-04 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) minl~tes. In addition, the solutions can be added to an emulsion or other existing form~ tion prior to use. Also, the solutions can be used in adAitinn 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 appare.ll from the stabilized organosilane compounds, products and compositions of the present invention and would, without undue eXperim~nt~tinn~ be able to cleterrnin~ effective application methods and treating times for any particular substrate, article, or other appliration. In addition, the compositions can be used in padding processes as are known in textile mills.
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, thelefolc, advantageous in treating a variety of substrates without the use of toxic organic solvents, and provide for the safe, long-term storage of activated or~n~ sil~n~ compound which can be used without further pre"alation.
Moreover, the stabilizers described herein do not interfere with the binding of the organosilane to the substrate. In addition, the present invention provides a generally applicable scheme for solvating some water insoluble or~gan-lsil~nes.
Also apparent will be those applications where organosilanes RnSiX4 n are prel)aled, dissolved, stored, applied, and in any way used in water. In addition, also a~ arcnL will be those applic~tion~ of organosilanes RnSiX4 n, in other solvents or mixed in other media (solids, polymer mixes, fillers, pi~ nt~, powders, dyes or emulsions) where exposure to water occurs but could be detrimental due to undesired or untirnely self-con-ien~tion of the silanol.

A:\PST-I~APP/DNB/GHP/Mayl,1997 CA 02236893 1998-0~-04 Moreover, the stabilizing compounds and m~thorls could be used in addition to or in conjunction with various art-known stabilization methods for organosilanes, such as the use of ionic ornon-ionic surf~rt~nts and detergents.
In addition, it is believed that the compounds, products and compositions of thepresent invention lead to improved wetting and/or coating because the partially hydrolyzed stabilizer/org~nnsil~n~ complex is dense in hydroxyl groups, thus providing for inc~eased hydrogen-bonding to surface OH groups.
Moreover, the present compounds, products and compositions can be used in the incorporation of an org~n~sil~n~ ~ntimirrobial 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 m~nufartllring steps or increase m~mlfart~lring cost.
Incorporating the compounds, products and compositions of the present invention during the dye process yields a textile material with a built-in ~ntimiçrobial 1'i agent with the organosilane characteristics, binding and antimicrobial protection. The incorporation process 1) does not add any additional step in the m~nllf~rtllring process and does no~: require any equipment modification; and 2) is believed not to lose its ~ntimicrobial characteristics and its effectiveness during 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 theorganosilane ~ntimirrobial agent remain unaffected by the dying agent, but the end-product textile goods would also exhibit excellent dyeing pro~cl~ies.
The water-stabilized org~nn~ nP compounds, products and compositions of the present invention are useful for a number of applications where the previous instability, 2'j insolubility 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 (pickledlharvested) with the compounds, products and compositions of thepresent invention imparts ~ntimirrobial protection to the outer surface of the food crop.
ABBST-I~APP/DNB/GHB/MIIyl,1997 CA 02236893 1998-0~-04 It is believed that such protection occurs without diffusing, migrating or le~r~ing the ~ntimicrobi~l agent from the bonded antimicrobial coating of the food item, and provides prolonged, safe and non-toxic antimirrobial protection. The method involves treating fruits and vegetables in the rinse cycle, during or after the normal '5 cleaning/water spraying or during or after bl~n~ in~. Thorough cleaning of fruits and vegetables at the processin~ plant is prere.~ed for initially removing microorgani~m~.
As one~of ordinary skill in the art would recognizel m~hine~ are used initially to remove soil~ chemic~l~ used in growing, spoilage bacteria, and other foreign materials.
These m~hin~ also use high velocity water sprays to clean the products. After the 1() cleaning, raw foods or other crop materials are prepared for further processing such as bl~nching (~.e., the food is immersed in water at 190 to 210 degrees F. or exposed to steam).
Microorg~ni.cm~ are controlled by the production plant up until the fruit or vegetable is removed. But once it is removed, org~nismc such as yeast, mold, and1'5 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 microorgani~m~ and delay 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 2() items for extended periods. For in.~t~n~e, 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 Bonles, Nipples, Pacifiers and Toys with the compounds, products and compositions of the present invention in the factory or A:~BST-I~APP/DNB/GHB/Milyl,1997 CA 02236893 1998-0~-04 39 BST-lO0 leac~ling the agent from the bonded surface, can provide prolonged and safe/non-toxic ~ntimicrobial protection. Treating such articles also elimin~tes odors caused bymicrobial co.~ ion. A dipping method as described above may be used to treatthese articles.
'5 To date, parents have used soaps, detergents, and surface cleaners to alleviate the problems of co~ -.in~tion of these articles. However, these and other sirnilar tre~tm~ntc have, for the most part, been inadequate and required repeated tre~tmPnt. In addition, these treatments have been found to be limited in their ability to offer broad spectrum control of microorg~ni~mC. Therefore, the present compounds, products and 1() compositions can be used to treat these articles to prevent microbial growth and cont~min~tion 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 mimltes 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 antirnicrobial agent.Thorough cleaning and sterilization is a plefe.led step in removing the microorg~ni~mc on the surface of the article prior to "coating" the said articles. In addition, preferably concentrations of 10% or more by volume of the compounds, products and compositions of the invention are used for long lasting protection.
Treating surgical gloves with the compounds, products and compositions of the 2() present invention before or during a surgical procedure can kill rnicroor~nicm~ on contact. It is believed that the treated gloves provide prolonged ~ntimirrobial activity with safe and non-toxic antimicrobial protection. Surgical gloves are treated, preferably, by submerging in the solution of Example I, diluted to 1% W/V for at least 30 seconds. This method will permit doctors to use and, if n~cess~ry, re-use the same 2'3 gloves (even without removing them) without undue fear of co~ tion.
Moreover, one of ordinary skill in the art would be able to implement numerous other end uses based upon the disclosure of the conll.oullds, products and compositions of the present invention. For in~t~nre, the following uses, applications and substrates, are contemplated:

A:'.BST-I~APP/DNBlGHB/M~yl,1997 CA 02236893 1998-0~-04 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 -i coating.s;
2. Tooth Brushes, Combs, Hair Brushes, Dentures and Retainers;
~3. Spa and Pool Filters m~etin~ stringent requirements that no other ~ntimicrobial 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, products and compositions of the present invention;
5. Rubbing Alcohol;
6. Statues and exposed art work;
7. HDP, high density polyester fabric plastic covers for dump sites, water reservoirs and generally for soil protection;
8. Liquid Additive (as flower water preservative for potted plants and cut flowers);
9. Silicone and Teflon coated Fiberglass with antirnicrobial protection including acrylic backing wall covering;
2al 10. Dryvitt and Stucco finish;

11. Waterproofing treated with the compounds, products and compositions of the present invention;

12. A method of treating blended cotton before or after picking m~r.hin~
make the cotton into rolls or laps;

13 . Food pae~ging and cont~in~rs;

14. Bio-films and adhesives (tapes and silicone wafers);

15. Single Ply Roofing and Roof shingles;

16. Fiberglass reinforcement product;

17. Antimicrobial tre~tm~nt of a transplant;

A:~BST-l~APP/D~B/GHB/Mayl.1997 CA 02236893 1998-0~-04 18. Antirnicrobial treatment of an organ or cartilage transplant;

19. ~nrimicrobial treatment of an artificial transplant such as a replacement bone;

20. Antimicrobial treatm~nt of a skin transplant, artificial, not artificial or a ;5 mixture of both;

21. Treatment of a transplant to reduce rejection by the receiving org~nicm;
~22. Tre~tm~nt of a skin transplant;
23. Treatment of a transplant to reduce undesired deposits, especially for artificial transplants;
24. Treatment to accelerate the ~tt~ehment of natural bone to non-organ transplants;
25. Preservation of liquids for consumption without pasteurization and nutrient reduction;
26. Skin tre~tm~nt not incorporating any water insoluble materials to stabilize siloxane;
27. Timed drug delivery, based on hydrolysis of siloxane ~tt~che~ to areas of activity;
28. Throat lozenges providing relief and microbial kill;
29. Treatment of contact lenses to prevent or slow down deposit forrnation;
30. Treatment of contact lenses to prevent microbial growth;
31. Incorporation into cornmercial polymers to render them antimicrobially active and/or prevent damage by microbial growth on surface.
Examples of the co~ cial polymers are polyester, polyamide (nylon), polyvinyl chloride, polyethylene, polypropylene, polystyrene, 2:5 polyurethane, plyvinyl alcohol, polyformaldehyde;
32. Incorporation into contact lenses to achieve the results as noted above in items 28 and 29 for the long terrn and without additional surface treatment;

A:lBST-lOOAPP/DNB/GHB/May 1, 1997 CA 02236893 1998-0~-04 42 BST-lOO
33. Incorporation into polyester to provide food containers with antimicrobial properties without separate surface treatment;
34. Incorporation into polypropylene or polyethylene to provide food containers with antimicrobial properties without separate surface S tre~tm~nt;
35. Incorporation of siloxane into CD-Rom to reduce the effect of microbes growing on surface;
36. Tre~tm~nt of paper (newspaper, books, documents) to prevent aging such as yellowing and weakening of material;
1() 37. Effective cleaning and odor prevention in animal cages, i.e. birds, hamster, pigs, guinea pigs, horses, cattle, rats and mice;
38. Disinfecting in spacecrafts, low vapor pressure and no irritation of astronauts by cleaner but high residual activity;
39. Applications in clean rooms, i.e. clean-rooms used in the microprocessor industries, reduction of harmful effects of microbes and uses as a binder for dust, and inhibitor of static charge;
40. Application of a non-conducting layer over circuit boards to prevent damage from dust and other atrnospheric pollutants;
41. Application of a durable, non irritating UV-protector for polymers, skin, 2(l leather, and wood;
42. The W-protector can be form~ te~ for example in a sun tan lotion or for example with lubricants to protect polymers such as dash boards and car tires;
43. Protection of photographic products from microbials, such as lenses, photographs, film and solutions used in film development;
44. Protection of photographic products, such as lenses, photographs, film and solutions used in film development from static and dirt;
45. Protection of photographic products from stains and scratching, such as lenses, photographs, film and solutions used in film development;

A:~BST-I~APP/DNB/GHB/Mayl.~997 CA 02236893 1998-0~-04 46. Protective coating for microchips;
47. Use of self assembled layers in designing and manufacturing microchips;
48. Use of self assembled layers in wiring of microchips;
49. Use of self assembled layers in manllfartllring molecular processors;
50. Additive to dryer sheets to render clothes antimicrobially active;
5~1. Aid in wound closing and healing and prevention of wound infection;
'52. Treatment of nail fungus for example by addition to nail polish.

It will be appreciated by those skilled in the art, in view of what is disclosedherein, that the compositions of this invention are useful, independent of the mech~nism of operation, which may or may not include the hydrolysis of siloxane to silanol and possible reaction of the silanol with the polyol, or alternatively, mere stabilization of the siloxane by interaction with the polyol, for example, by hydrogen bonding. It will also be understood that where a composition is recited as containing 1Ci an organosilane, mixtures of organosilanes is also inten~ed and encompassed thereby.
In particularly plefelled embodim~nt~, the composition according tO this invention is used to treat skin or other tissues (bone, soft tissues) for use in a transplant to reduce microbial cont~mination. The composition is likewise useful in any toothpaste formulation known in the art to enhance the caries-fighting properties of such compositions through anti-microbial treatmPnt of teeth.
In other pleferled embodiments, the composition is used to protect paper products, to produce dural metal finichPc, such as any car wax fomulation known in the art, to prevent paint scratches and as a protectant against the acc--ml-lation of dirt.

The preferred embo~limPntc of the above-described water-stabilized antimicrobial compounds, products, compositions, and methods are set forth in the following examples. Other features of the invention will become apparent from the following examples, which are for illustrative purposes only and are not inten-led as a limitatinn upon the present invention.

A:\BST-I~APP/DNB/GHB/Mayl,1997 CA 02236893 1998-0~-04 Example 1 In one embo~limPn~, the present invention provides a water-stable composition of glucose and a silylated quaternary all~llonium salt. Upon application of the mixture, ~i the glucose is most likely partially liberated and the product is hydrolyzed. However, such liberation is not n~cess~ry for the operability of the present invention. Its occurrence or non-occurrence does not detract from the general efficacy of the compounds, products and compositions of the present invention. Instead, the notion that glucose (or any other of the present stabilizers) is liberated is offered as one possible explanation of the surprising utility and efficacy of the claimed invention. It is not clear that the stabilizer must be liberated when the organosilane bonds to asubstrate.
Glucose stabilized 3-(trimethoxysilyl)propyl~imPthyloctadecyl ammonium chloride is sl:able in water up to concentrations of 10% W/W of the siloxane. One of ordinary skill in the art would recognize that the stability of other organosilanes may vary and depends upon the specific stabilizer used. In any event, the siloxane and the glucose are mixed, optionally at a higher final siloxane concentration than the working concentration, and then diluted to the desired active concentration in water.

Example 2 Compositions wherein the stabilization of the siloxane is achieved through mixing with sucrose is similar to that described in Example 1 for stabilization with glucose.

Example 3 A series of polyols were tested for their ability to stabilize Dow Corning 5772,which is a blend of [3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride], and 3-chloroproyltrimethoxysilane, aqueous solutions and the degree of stabilization over various time periods was monitored. In general, most concentrations of siloxane A:\BST-I~APP/DNB/GHB/Mayl,1~7 CA 02236893 1998-0~-04 become cloudy overnight in the absence of stabilizer. Therefore, when aqueous siloxanes remain stable overnight in the presence of stabilizer, the polyol is considered to have at least minim~l utility according to this invention. However, those skilled in the art will recognize that for pr~cti~lity and commercial applications, the longer the period for which a stable composition can be achieved the better. Accordingly, a stock of solutions of known concentrations of the stabilizer is prepared in deionized water. A
known~amount of the solution, and in some cases additional deionized water and the siloxane were mixed in a vial. The vial was sealed with parafilm to prevent evaporation, and stored at ambient te,l,p~,~lule. The percent ~ntimi~robially active lCI siloxane was calc~ tPd by multiplying the weight of Dow Corning 5772 added by 0.72 and dividing by the sum of all materials added (polyol, Dow Corning 5772, deionized water). We found that for at least 10% or lower siloxane concentrations, about 1-20%
of the polyoL was effective at stabilizing the aqueous solution.

1'; Example 4 A 57~ siloxane solution with 0.94% to 19% sucrose rem~ine~l clear for at least seven weeks. Another sample at approxirnately 5 % active siloxane rem~inPd clear for at least eighl months.

Ex~mple 5 A 57D siloxane solution with 0.94% to 19% m~nnitol remained clear for seven weeks. At the high m~nnitol concentration, the m~nnitol is not completely soluble, but still active as a stabilizer of the siloxane.

2'i Example 6 A 570 siloxane solution with 0.94% to 19% glucose remained clear for at least eight weeks.

A:lBST-l~APP/D~B/GHB/M.Iyl,1997 CA 02236893 1998-0~-04 Example 7 A 10~ siloxane solution with 0.85% to 17% L-ascorbic acid remained clear for at least five weeks; after two days, solutions with as much as 18% siloxane rem~in~d clear with as little as 0.79% L-ascorbic acid.
~j Exarnple 8 'A 95~ siloxane, with4.1% to 18% glyoxal aqueous solutionreln~in~d clear for at least three weeks.

Exam~le 9 In ter.ms of polymeric polyols, we found that a ~% siloxane, 0.097% agar solution was stable for at least one week. As will be appreciated, for agar, it is necessary to warm the stock agar solution to achieve dissolution of the agar, which is then cooled prior to or in the course of ~-lmixtllre with the siloxane. The resulting solution is a viscous liquid or solid when cold.

Example 10 In terms of an oxidized sugar, we found that a 9.7% siloxane, 0.9% D-glucurono-6,3-lactone aqueous solution was stable for at least four weeks.
2~) F~le 11 A tannic acid siloxane solution was not stabilized to any signific~nt degree.
This result nnay in~ te that hl~ulilies, for example oxidation products, in the tannic acid may have inhibited its action as a stabilizer. Alternatively, the limited stabilization 2'i afforded by tannic acid may in~ic~te that at least two adjacent (separated by less than three atoms) hydroxyls of the stabilizer are preferably non-aromatic.

A:lBST-lOOAPP/DNBlGHBJMay 1, 1997 CA 02236893 1998-0~-04 Example 12 According to this invention, a number of compositions comprisin~ mixtures of siloxanes and polyols may be contemplated for a wide variety of applications. Because stabilizers of this invention include such non-toxic, biocompatible substances as simple '5 sugars and more complex carbohydrates, compositions such as shampoos, hand and face creams, and compositions that come in contact with foods are all acceptableapplica~tions. There are many compositions known in the art for these types of applic~tion~, to which those skilled in the art could apply the instant disclosure, and therefore gneat detail on the various components of those compositions is not provided 1() herein. Thus, shampoo, hand-lotion, tooth-paste, and other biological material cont~etin~ compositions known in the art may include the composition according to this invention. ]~Iowever, such biologically cont~tin~ compositions are by no means the only useful compositions. Other compositions known in the art, such as car wax, furniture polish, shoe polish, leather tre~tm~nt compositions, or glass treatment 1~5 compositions are improved by the inclusion of the composition according to this invention.

From the foregoing examples, those skilled in the art will recognize that the stabilizers disclosed herein may be used at any minim~l concentration at which they are found to have a stabilizing effect, and may be used up to any maximum concentration at which they remain soluble. Even where some amount of solid stabilizer is present, this is not expected to have any deleterious effect, (see the above experiment in which a high m~nnitol conc~ntration was used), although it is anticipated that in terms of siloxane stabilization, a point of ~limini~hing returns is reached where increased 2:5 concentrati~ns of stabilizer do not yield comm~r~ . dle enh~n-~ements in siloxane stabilization.

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 A:~BST-I~APP~DNBlGHBlM~yl,1997 spirit of the invention. Other embo~;lllf ,l~i of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the 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 indjc~t~d by the 5 following claims.

A:~BST-lOOAPP/DN8/GHBlMay 1, 1997

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition comprising a mixture of:
a) an organosilane of the formula RnSiX4-n where n is an integer of from 0 to 3; and R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group; with b) a polyol containing at least two hydroxy groups, wherein at least two of the at least two hydroxy groups are separated by less than three intervening atoms.

2. The composition of Claim 1, wherein n is an integer from 0 to 2; each R
is, independently, alkyl, alkyl alcohol, or aromatic; each X is, independently, hydroxy, alkoxy, halogen, acetyl, acetoxy, acyl, a hydroxylated solid or liquid polymericmoiety, polyether or polyalkylether, and the polyol is glucose, sucrose, fructose, mannitol, ascorbic acid and optionally including an anti-oxidant, adenosine, glucuronic acid, glucurone, dextran, aqueous glyoxal, fucose, cellulose, partially hydrolyzed cellulose, soluble starch, a starch-acrylic acid graft copolymer, a nucleoside, a nucleotide, an oligonucleotide, or a polynucleotide.

3. The composition of claim 2 wherein the polyol is a carbohydrate.

4. The composition of claim 3 wherein said carbohydrate is selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides, modified carbohydrates, graft and block carbohydrate co-polymers, partially alkylated, acylated or acetylated carbohydrates, carboydrate oxidationproducts, reduced carbohydrates and substituted carbohydrates.

5. The composition of claim 3 wherein said substituted carbohydrate is selected from the group consisting of nucleosides, nucleotides, and nucleic acids.

6. The composition of claim 3 wherein said carbohydrate is a ketose or an aldose, natural or unnatural, of either the D or L enantiomeric form.

7. The composition of claim 6 wherein said aldose or ketose is glucose, fucose, fructose, a polymer, oxidation product, reduction product, or water soluble substituted derivative thereof.

8. The composition of Claim 1, wherein the organosilane is of the formula II, III, IV, or V:
(R1)3SiR2N+(R3)(R4)(R5)Y- (II) (R1)3SiR2N(R3)(R4) (III) (R1)3SiR2R35 (IV) (R1)2Si(R36)(R37) (V) wherein each R1 is, independently, halogen or R6O, where R6 is H, alkyl of from 1 to about 22 carbon atoms, acetyl, acetoxy, acyl, propylene glycol, ethylene glycol,polyethylene glycol, polypropylene glycol; block and copolymers of ethylene and propylene glycol, the alkyl monoether of from 1 to 22 carbons of propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; block and copolymers of ethylene and propylene glycol or the monoester of a carbonic acid of from 1 to 22 carbons and propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; block and copolymers of ethylene and propylene glycol; octyphenol; nonylphenol; and sorbitan ethers;

R35 is H, halogen, NH2(CH2)2NHR2, NH2R2, C3H5O2R2, C4H5O2R2, NaO(CH3O)P(O)R2, or ClCH2C6H4R2, R36 and R37 are, independently, halogen, H, alkyl of from 1 to about 22 carbon atoms, acrylic, vinyl, acetylenic, benzyl, styryl, propinyl, isobutyl, phenyl, or n-octyl;

R2 is benzyl, vinyl or alkyl of from 1 to about 22 carbon atoms;

R3 and R4 are, independently, lower alkyl alcohol, lower alkoxy of from 1 to 4 carbon atoms, alkyl of from 1 to about 22 carbon atoms; or R3 and R4 can, together, form a morpholine or cyclic or heterocyclic, unsaturated or saturated,five to seven-membered ring of the formula VI:
-R3-(R7)k-R4- (VI) where k is an integer from 0 to 2, R7, where the ring is saturated, is CH2, O, S, NH, NH2+, NCH2CH2NH2, NCH2CH2NH3+, NCH2CH2N(R8)(R9), NCH2CH2N+(R8)(R9)(R10), N(alkyl), N(aryl), N(benzyl), where each R8, R9, and R10 is, independently, benzyl, polyether, 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, and R7, where the ring is unsaturated is, CH, N, N+H, N+(alkyl), N+(aryl), N+(benzyl), N-CH2-N, N+H-CH2-N, N+(alkyl)-CH2-N, N+(aryl)-CH2-N, or N+(benzyl)-CH2-N;
wherein the ring is unsubstituted or substituted with alkyl of from 1 to 22 carbon atoms, ester, aldehyde, carboxylate, amide, thionamide, nitro, amine, or halide R5 is lower alkyl alcohol, CH2C6H5, polyether, alkyl, alkoxy, perfluoroalkyl, pefluoroalkylsulfonate, or perfluoroalkylcarboxylate wherein the alkyl, alkoxy, perfluoroalkyl, perfluoroalkylsulfonate, or perfluoroalkylcarboxylate is of from1 to about 22 carbon atoms, or is a five to seven-membered ring of formula VI
as described above; and Y- is a suitable anionic moiety to form the salt of the compound of formula II, III, IV or V.

9. A water stable composition, comprising the composition of Claim 1 and water.

10. The composition of Claim 1, wherein the organosilane is 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride and the polyol is glucose, sucrose, fructose, mannitol, ascorbic acid and optionally including an anti-oxidant, adenosine, glucuronic acid, glucurone, dextrose, cellulose, partially hydrolyzed cellulose, soluble starch, a starch-acrylic acid graft copolymer, a nucleoside, a nucleotide, an oligonucleotide, or a polynucleotide.

11. A composition for treating a substrate, comprising a carrier and an effective amount of the composition of Claim 1.

12. The composition of Claim 11, wherein the carrier is other than water.

13. The composition of Claim 1, wherein the organosilane is 3-(trirnethoxysilyl)propyldimethyloctadecyl ammonium chloride, 3-(trirnethoxysilyl)propylmethyldi(decyl)ammonium chloride, 3-chloropropyltrimethylsilane, 3-chloroplopyltrimethoxysilane, octadecyltrimethoxysilane, or perfluorooctyltriethoxysilane and the polyol is an aldose, a ketose, a polymer, an oxidation product, a reduction product, a substituted orpolymeric substitution product thereof.

14. The composition of Claim 1, wherein the organosilane is (CH3O)3Si(CH2)3N+(CH3)2C18H37Cl-, (CH3O)3Si(CH2)3N+(CH3)2C18H37Br-.
(CH3O)3Si(CH2)3N+(C10H21)2CH3Cl-, (CH3O)3Si(CH2)3N+(C10H21)2CH3Br-, (CH3O)3Si(CH2)3N+(CH3)3Cl-, (CH3O)3Si(CH2)3N+(CH3)2CgH17Cl-, (CH3O)3Si(CH2)3N+(CH3)2C10H21Cl-, (CH30)3Si(CH2)3N+(CH3)2C12H25Cl-, (CH3O)3Si(CH2)3N+(CH3)2C14H29Cl-, (CH3O)3Si(CH2)3N+(CH3)2C16H33Cl-, (CH3O)3Si(CH2)3N+(CH3)2C20H41Cl-, (CH3O)3Si(CH2)3N+(C4H9)3Cl-, (CH3O)3Si(CH2)3N+(C2H5)3Cl-, (CH3CH2O)3Si(CH2)3N+(CH3)2C18H27Cl-, (CH3O)3Si(CH2)3NHC(O)(CF2)6CF3, (CH3O)3Si(CH2)3NHC(O)(CF2)gCF3, (CH3O)3Si(CH2)3NHC(O)(CF2)10CF3, (CH3O)3Si(CH2)3NHC(O)(CF2)12CF3, (CH3O)Si(CH2)3NHC(O)(CF2)14CF3, (CH3O)3Si(CH2)3NHC(O)(CF2)16CF3, (CH3O)3Si(CH2)3NHSO2(CF2)7CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CH2)6CH3, (CH3O)3Si(CH2)3N+, (CH3)2(CH2)3NHC(O)(CH2)8CH3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CH2)10CH3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CH2)12CH3, CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CH2)14CH3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CH2)16CH3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)(CH2)3NHC(O)(CF2)6CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2)8CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2)10CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2)12CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2)14CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHC(O)(CF2)16CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHSO2(CF2)7CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHSO2(CF2)9CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHSO2(CF2)11CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHSO2(CF2)13CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHSO2(CF2)15CF3, (CH3O)3Si(CH2)3N+(CH3)2(CH2)3NHSO2(CF2)16CF3, (CH3O)3Si(CH2)3NHC6H4COOH, (CH3O)3Si(CH2)3NHC6H4COOCH3, (CH3O)3Si(CH2)3NHC6H4COOC2H5, (CH3O)3Si(CH2)3NHC6H4COOC3H7, (CH3O)3Si(CH2)3NHC6H4COOC4H9, (CH3O)3Si(CH2)3NHC6H4COOCH2C6H5, (CH3O)3Si(CH2)3NHC6H4COOCH2C6H4NH2, (CH3O)3Si(CH2)3NHC6H4COOCH2C6H4N(CH3)2, (CH3O)3Si(CH2)3NHC6H4COOCH2C6H4N(CH2CH3)2, (CH3O)3Si(CH2)3NHC6H4COOCH2C6H4N+(CH3)3 Y-, (CH3O)3Si(CH2)3NHC6H4COOCH2C6H4N+(CH2CH3)3 Y-, (CH3O)3Si(CH2)3NCH3C6H4COOH, (CH3O)3Si(CH2)3NCH3C6H4COOCH3, (CH3O)3Si(CH2)3NCH3C6H4COOC2H5, (CH3O)3Si(CH2)3NCH3C6H4COOC3H7, (CH3O)3Si(CH2)3NCH3C6H4COOC4H9, (CH3O)3Si(CH2)3NCH3C6H4COOCH2C6H5, (CH3O)3Si(CH2)3NCH3C6H4COOCH2C6H4NH2, (CH3O)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH3)2, (CH3O)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH2CH3)2, (CH3O)3Si(CH2)3NCH3C6H4COOCH2C6H4N+(CH3)3 Y-, (CH3O)3Si(CH2)3NCH3C6H4COOCH2C6H4N+(CH2CH3)3 Y-, (CH3O)3Si(CH2)3N+(CH3)2C6H4COOH Y-, (CH3O)3SI(CH2)3N+(CH3)2C6H4COOCH3 Y-, (CH3O)3SI(CH2)3N+(CH3)2C6H4COOC2H5 Y-, (CH3O)3SI(CH2)3N+(CH3)2C6H4COOC3H7 Y-, (CH3O)3SI(CH2)3N+(CH3)2C6H4COOC4H9 Y-, (CH3O)3SI(CH2)3N+(CH3)2C6H4COOCH2C6H5 Y-, (CH3O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4NH2 Y-, (CH3O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N(CH3)2 Y-, (CH3O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N(CH2CH3)2 Y-, (CH3O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N+(CH3)3 Y-Y-, (CH3O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N+(CH2CH3)3 Y-Y-, (CH3O)3Si(CH2)3NC2H5C6H4COOH, (CH3O)3Si(CH2)3NC2H5C6H4COOCH3, (CH3O)3Si(CH2)3NC2H5C6H4COOC4H9, (CH3O)3Si(CH2)3NC2H5C6H4COOC3H7, (CH3O)3Si(CH2)3NC2H5C6H4COOC4H9, (CH3O)3Si(CH2)3NC2H5C6H4COOCH2C6H5, (CH3O)3Si(CH2)3NC2H5C6H4COOCH2C6H4NH2, (CH3O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N(CH3)2, (CH3O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N(CH2CH3)2, (CH3O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N+(CH3)3Y-, (CH3O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N + (CH2CH3)3 Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOH Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOCH3 Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOC2H5 Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOC3H7 y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOC4H9 y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H5 Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N2 Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N(CH3)2 Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N(CH2CH3)2 Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N+(CH3)3 Y- Y-, (CH3O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N+(CH2CH3)3 Y-Y-, (CH3CH2O)3Si(CH2)3NHC6H4COOH, (CH3CH2O)3Si(CH2)3NHC6H4COOCH3, (CH3CH2O)3Si(CH2)3NHC6H4COOC2H5, (CH3CH2O)3Si(CH2)3NHC6H4COOC3H7, (CH3CH2O)3Si(CH2)3NHC6H4COOC4H9, (CH3CH2O)3Si(CH2)3NHC6H4COOCH2C6H5, (CH3CH2O)3Si(CH2)3NHC6H4COOCH2C6H4NH2, (CH3CH2O)3Si(CH2)3NHC6H4COOCH2C6H4N(CH3)2, (CH3CH2O)3Si(CH2)3NHC6H4COOCH2C6H4N(CH2CH3)2, (CH3CH2O)3Si(CH2)3NHC6H4COOCH2C6H4N+(CH3)3 Y-, (CH3CH2O)3Si(CH2)3NHC6H4COOCH2C6H4N+(CH2CH3)3 Y-, (CH3CH2O)3Si(CH2)3NCH3C6H4COOH, (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH3, (CH3CH2O)3Si(CH2)3NCH3C6H4COOC2H5, (CH3CH2O)3Si(CH2)3NCH3C6H4COOC3H7, (CH3CH2O)3Si(CH2)3NCH3C6H4COOC4H9, (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H5, (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H4NH2, (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH3)2, (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H4N(CH2CH3)2, (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H4N+(CH3)3 Y-, (CH3CH2O)3Si(CH2)3NCH3C6H4COOCH2C6H4N+(CH2CH3)3 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOH Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOCH3 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOC2H5 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOC3H7 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOC4H9 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H5 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4NH2 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N(CH3)2 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N(CH2CH3)2 Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N+(CH3)3 Y-Y-, (CH3CH2O)3Si(CH2)3N+(CH3)2C6H4COOCH2C6H4N+(CH2CH3)3 Y-Y-, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOH, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH3, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOC2H5, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOC3H7, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOC4H9, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H5, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H4NH2, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N(CH3)2, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N(CH2CH3)2, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N+(CH3)3 Y-, (CH3CH2O)3Si(CH2)3NC2H5C6H4COOCH2C6H4N+(CH2CH3)3 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOH Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH3 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOC2H5 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOC3H7 Y-, CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOC4H9 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H5 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4NH2 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N(CH3)2 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N(CH2CH3)2 Y-, (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N+(CH3)3 Y-Y-, or (CH3CH2O)3Si(CH2)3N+(C2H5)2C6H4COOCH2C6H4N+(CH2CH3)3 Y-Y-.

15. The composition of Claim 1, wherein the organosilane is NH2(CH2)2NH(CH2)3Si(OCH3)3,NH2(CH2)3Si(OCH3)3, NH2(CH2)3Si(OCH2CH3)3,Cl(CH2)3Si(OCH3)3, Cl(CH2)3Si(OCH2CH3)3, Cl(CH2)3SiCl3,C3H5O2(CH2)3Si(OCH3)3, C3H5O2(CH2)3Si(OCH2CH3)3, C4H5O2(CH2)3Si(OCH3)3, C4H5O2(CH2)3Si(OCH2CH3)3,CH3SiHCl2, NaO(CH3O)P(O)(CH2)3Si(OH)3,SiHCl3,n-2-vinylbenzylamino-ethyl-3-aminopropyltrimethoxysilane HCL,H2C = CHSi(OCOCH3)3,H2C=CHSi(OCH3)3, H2C=CHSi(OCH2CH3)3, H2C=CHSiCl3,(CH3)2SiCl2,(CH3)2Si(OCH3)2, (C6H5)2SiCl2,(C2H5)SiCl3,(C2H5)Si(OCH3)3,(C2H5)Si(OCH2CH3)3, isobutyltrimethoxysilane,n-octyltriethoxysilane,CH3(C6H5)SiCl2,CH3SiCl3, CH3Si(OCH3)3,C6H5SiCl3,C6H5Si(OCH3)3,C3H7SiCl3,C3H7Si(OCH3)3,SiCl4, ClCH2C6H4CH2CH2SiCl3n, ClCH2C6H4CH2CH2Si(OCH3)3, ClCH2C6H4CH2CH2Si(OCH2CH3)3,decyltrichlorosilane,dichloromethyl(4-methylphenethyl)silane,diethoxymethylphenylsilane, [3-(diethylamino)propyl]trimethoxysilane,3-(dimethoxymethylsilyl)-1-propanethiol, dimethoxymethylvinylsilane,3-[tris(trimethylsilyloxy)silyl]propyl methacrylate, trichloro[4-(chloromethyl)phenyl]silane, methylbis(trimethylsilyloxy)vinylsilane, methyltripropoxysilane, or trichlorocyclopentysilane.

16. A compound having the formula (R)nSi(X)4-n-y(R41)y wherein n is an integer of from 0 to 3; y is an integer of from 1 to 4; each R is, independently, a nonhydrolizable organic group; each X is, independently, a hydrolyzable group; and each R41 is a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms and wherein the R41 is bonded to the Si by removal of the hydrogen from at least one of the at least two hydroxy groups such that at least one of the oxygens of the at least two hydroxy groups is bonded to Si.

17. The composition of claim 1 formed from mixing an organosilane of the formula II, III, IV, or V:
(R1)3SiR2N+(R3)(R4)(R5)Y- (II) (R1)3SiR2N(R3)(R4) (III) (R1)3SiR2R35 (IV) (R1)2Si(R36)(R37) (V) wherein each R1, is, independently, halogen or R6O, where R6 is H, alkyl of from 1 to about 22 carbon atoms, acetyl, acetoxy, acyl, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; block and copolymers of ethylene and propylene glycol, the alkyl monoether of from 1 to 22 carbons of proplylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol;
block and copolymers of ethylene and propylene glycol or the monoester of a carbonic acid of from 1 to 22 carbons and propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol; block and copolymers of ethylene and propylene glycol; octyphenol; nonylphenol; and sorbitan ethers;

R35 is H, halogen, NH2(CH2)2NHR2, NH2R2, C3H5O2R2, C4H5O2R2, NaO(CH3O)P(O)R2, or C1CH2C6H4R2;

R36 and R37 are, independently, halogen, H, alkyl of from 1 to about 8 carbon atoms, acrylic, vinyl, acetylenic, benzyl, styryl, propinyl, isobutyl, phenyl, or n-octyl;

R2 is benzyl, vinyl or alkyl of from 1 to about 22 carbon atoms;

R3 and R4 are, independently, lower alkyl alcohol, lower alkoxy of from 1 to 4 carbon atoms, alkyl of from 1 to about 22 carbon atoms; or R3 and R4 can, together, form a morpholine or cyclic or heterocyclic, unsaturated or saturated, five to seven-membered ring of the formula VI:

-R3-(R7)k-R4- (VI) where k is an integer from O to 2, R7, where the ring is saturated, is CH2, O, S, NH, NH2+, NCH2CH2NH2, NCH2CH2NH3+, NCH2CH2N(R8)(R9),NCH2CH2N+(R8)(R9)(R10), N(alkyl), N(aryl), N(benzyl), where each R8, R9, and R10 is, independently, benzyl, polyether, 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, and R7, where the ring is unsaturated is, CH, N, N+H, N+(alkyl), N+(aryl), N+(benzyl), N-CH2-N, N+H-CH2-N, N+(alkyl)-CH2-N, N+(aryl)-CH2-N, or N+(benzyl)-CH2-N;
wherein the ring is unsubstituted or substituted with alkyl of from 1 to 22 carbon atoms, ester, aldehyde, carboxylate, amide, thionamide, nitro, amine, or halide R5 is lower alkyl alcohol, CH2C6H5, polyether, alkyl, alkoxy, perfluoroalkyl, pefluoroalkylsulfonate, or perfluoroalkylcarboxylate wherein the alkyl, alkoxy, perfluoroalkyl, pefluoroalkylsulfonate, or perfluoroalkylcarboxylate is from 1 to about 22 carbon atoms or is a five to seven-membered ring according to formula VI as described above; and Y- is a suitable anionic moiety to form the salt of the compound of formula II, III, IV or V-, with a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms.

18. The composition of claim 17 which is an aqueous composition.

19. A method of treating a substrate, comprising contacting the substrate with a sufficient amount of the composition of Claim 1 for a period of time sufficient for treatment of the substrate.

20. A method of dyeing and treating a substrate, comprising contacting the substrate with an aqueous composition comprising an aqueous soluble dye suitable for dyeing a substrate and the composition formed from mixing:

a) an organosilane of the formula RnSiX4-n where n is an integer of from 0 to 3; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group; with b) a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms, for a period of time sufficient to dye and treat the substrate.

21. A method of antimicrobially treating a food article, comprising contacting the food article with an effective amount of the product formed from mixing:

a) an antimicrobial organosilane of the formula RnSiX4-n where n is an integer of from 0 to 3; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group; with b) a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms, for a period of time sufficient to antimicrobially treat the food article.

22. A method of antimicrobially coating a fluid container used for containing a human or animal consumable product, comprising contacting the container with an effective amount of the product formed from mixing:

a) an antimicrobial organosilane of the formula RnSiX4-n where n is an integer of from 0 to 3; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group; with b) a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms, for a period of time sufficient to antimicrobially coat the container.

23. A method of antimicrobially coating a latex medical article for use in a human or animal medical procedure, comprising contacting the article with an effective amount of the product formed from mixing:

a) an antimicrobial organosilane of the formula RnSiX4-n where n is an integer of from 0 to 3; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group; with b) a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms, for a period of time sufficient to antimicrobially coat the article.

24. The method of Claim 22, wherein the article is a surgical glove.

25. A method of antimicrobially treating a substrate selected from the group consisting of a concrete pipe, 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, an HDP plastic cover, a silicone or TEFLON~ coated fiberglass article, a Dryvitt finish, a stucco finish, blended cotton, a bio-film, a bio-adhesive, single ply roofing, a roofing shingle, a paper product, teeth, skin, bone, cartilage, a metal finish, a car finish, and a fiberglass reinforcement product, comprising contacting the substrate with an effective amount of the composition formed from mixing:

a) an antimicrobial organosilane of the formula RnSiX4-n where n is an integer of from 0 to 3; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with b) a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms, for a period of time sufficient to antimicrobially treat the substrate.

26. 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 composition formed from mixing:

a) an antimicrobial organosilane of the formula RnSiX4-n where n is an integer of from 0 to 3; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hysrolyzable group; with b) a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms, for a period of time sufficient to antimicrobially enhance the product.

27. A stable composition comprising between about 0.001-20% of a siloxane and between about 0.01-20% of a polyol containing at least two hydroxy groups, wherein any two of the at least two hydroxy groups are separated by no more than two intervening atoms.

28. The composition of claim 27 comprising 0.1-10% siloxane and a polyol selected from the group consisting of: 0.1% to about 5 % of a monosaccharide, a disaccharide, L-ascorbic acid, aqueous glyoxal, D-glucurono-6,3-lactone; or 0.001%
up to its gelation limit, agar.

29. The composition of claim 27 wherein the polyol is glucose, sucrose, fructose, or mannitol.

30. The composition of claim 27 wherein the source of the polyol is corn syrup, maple syrup, or honey.

31. A shampoo, hand-lotion, sun-tan lotion, tooth-paste, car wax, furniture polish, shoe polish, leather treatment composition, or glass treatment composition comprising the composition of claim 27.

32. A method for making an organosilane of the formula RnSiX4-n where n is an integer of from 0-3, preferably 0-2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group; which comprises mixing the organosilane synthesis starting materials in an aqueous solution in the presence of a polyol containing at least two hydroxyls which are separated by less than three intervening atoms wherein said polyol is present in an effective amount sufficient to stabilize the organosilane as it is formed from said starting materials.