ZA200500364B - N-halamine siloxanes for use in biocidal coatings and materials - Google Patents

Description

N-HALAMINE SILOXANES FOR USE IN BIOCIDAL COATINGS AND

MATERIALS

CROSS-REFERENCE TO RELATED APPLICATION

This applicatiora claims the benefit of pending U.S. Provisional Applicat ion

No. 60/388,968, filed on June 14, 2002, and is a continuation-in-part of U.S. Applicat jon

No. 10/400,165, filed March 24, 2003, both incorporated herein expressly by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to the synthesis and use of silane and siloxane compounds for the purp ose of constructing coatings and materials which can be rendered biocidal by exposure to halogen solutions either before or after curing the coating or material. The biocidal coatings and materials can then be used to inactivate pathogemic microorganisms such as bacteria, fungi, and yeasts, as well as virus particles, that can cause infectious diseases, and those microorganisms that cause noxious odors and unpleasant coloring such as mildew. The coatings are compatible with a wide variety of substrates including cellulose, chitin, chitosan, synthetic fibers, glass, ceramics, plastics, : rubber, cement grout, latex caulk, porcelain, acrylic films, vinyl, polyurethanes, silicon tubing, marble, metals, metal oxides, and silica.

BACKGROUND OF THE INVENTION

Previous attempts to incorporate biocidal activity into materials and coatings have primarily involved two methods: (1) physical mixing (blending) of biocides into -the materials and coatings, and (2) chemical binding of biocidal functional groups to -the polymers or copolymers comprising the materials and coatings. Chemical binding showld be preferable for long-term biocidal activity if the bound biocidal functionality does mot adversely affect the other desired properties such as strength, appearance, and chemi cal resistance of the material or coating. For example, a significant amount of work has been performed concerning rendering sponges biocidally active. This involves encapsulation of a variety of weak biocides into the porous structure of the sponge, either throuagh physical blending or chemical bonding to the surface. The sponges modified in t his manner can exhibit biocidal activity, but the contact times necessary for action zare generally long, and somae pathogens are not inactivated even at contact times of seve=ral hours. Anti-fouling polyurethanes have been prepared by chemical incorporation of tributyl tin as described in U.S. Patent No. 5,194,504 and quaternary zammonium salts (see, for example, J _Appl. Polym. Sci. 50.663 (1993) and J. Appl. PoZym. Sci. 50.671 (1993)). Coatings comtaining organo tin compounds are being discredited as threats to the environment, and poly/-quats are weak biocides that are non-regenerable. Thus, there is a definite need for more effective biocidal coatings and materials.

A new class o f biocidal monomers and polymers known as N-h alamines, which could be useful in producing biocidal coatings, has recently been developed. A non- toxic, non-irritating, and cost effective material, poly-1,3-dichloro-5-methyl-5-(4'- vinylphenyl) hydantoin, is an inexpensive derivative of polystyrene_ that was first described in U.S. Patent No. 5,490,983. Subsequent disclosures of its biocidal properties for use in disinfecting applications for water filters have recently oc curred (see, for example, find. Eng. Clem. Res. 33:168 (1994), Water Res. Bull. 32:793 ( 1996); Ind. Eng.

Chem. Res. 34:4106 (1995); J. Virolog. Meth. 66:263 (1997); Trends in Polym. Sci. 4:364 (1996); Water Cond. & Pur. 39:96 (1997)). The polymer is effective against a broad spectrum of pathogens including Staphylococcus aureus, Pseudomorias aeruginosa,

Escherichia coli, Candida albicans, Klebsiella terrigena, poliovirus, and rotavirus, among others, causing large log reductions in contact times of the order of a few seconds in water disinfection applications.

N-halamine Functional groups such as hydantoins, oxazolidinones, and imidazolidinones have also been employed recently in producing biocidal cellulose (U.S.

Patent No. 5,882,357), biocidal films on surfaces (U.S. Patent No. 5,902,818), biocidal

Nylon (U.S. Patent Application No. 09/615,184), and biocidal polyester (U.S. Patent

Application No. 09/866,535); these patents and patent applications are Therein expressly incorporated by reference in their entirety.

U.S. Patent No.4,412,078 to Berger describes alkyl and alkoxy silylpropylhydantoin derivatives. Also, silylpropylisocyanurates have b-een reported for use as adhesive sealants (U.S. Patent No. 3,821,218.) Moreover, much work has been done concerning attaching quaternary ammonium functional groups which are weak, non- : regenerable biocides to various silicon compounds which can then be bonded to surfaces to render them weakly biocidal (see, for example, U.S. Patent Nos. 3,560,385; 3,730,701; : 3,794,736; 3,814,7394; 3,860,709; 411,928; 4,282,366; 4,504,541; 4,615,937; 4,692,374; 4,408,996; 4,414,268 ; and 5,954,869). The N-halamine derivatives of the invention rexpresent a significant improvement in biocidal efficacy over perior art in terms of both the rexquired contact times and increased spectrum of activity.

SUMMARY OF THE INVENTION

Compounds according te the present invention have thes following structures: (R-L)n —Si—(R4)4-n (M i . 2

R— L —S—R; @

Ra (R)n——Si——(R)4.n (3)

Ti

R —y Re 4)

Rs

R s

Hogi 5)

R1

I

TOTP (6)

Ry > (R-LDn(R)y—S i—(0);— (7 (R)n(R1)m——Si— (O)— (8)

THOS | ©

I

R

TOTS oO (10)

For structures (1)-(8) above, R1, R2, and R3 are independently selected from a :

C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least ome of R1, R2, or R3 group is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; m

A

=0,1,0r2;n=1,2, or 3 for structures (1), (3), (7), an«d (8); p= 1, 2, or 3; m+n+p = 4; and R is defined below.

L is a linker group that attaches R to the Si moiety. L is a linker alkylene, amine, or ether group, comprised of 1-13 carbons, 0-3 nitrogen «or oxygen atoms, or L is a linker alkylene group of 1-13 carbons and a carbamate, thiocarlbbamate, or urea functional group.

R groups suitable for structures (1), (2). (5), (7), and (9) above are groups (11)- (21).

Imide-Linked Hydantoin

O

Ry

N——

N (a1) ~~

X

O

ER) wherein R4 and R5 are independently selected fiom a Cl1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of clalorine or bromine.

Amide-linked Hydantoin

O

Rs

Rg

N—X

N (12)

Oo wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hy~drogen, chlorine or bromine.

Representative compounds having group (11) or (12) are those wherein R1, R2,

R3 are independently selected from a methyl, ethyl, phen yl, methoxy, ethoxy, or hydroxy group; wherein at least one of R1, R2, or R3 is a methoxy, ethoxy, or hydroxy group; and wherein R4 and RS are independently selected from a methyl, ethyl, hydroxymethyl or phenyl group.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are a methoxy or ethoxy group; R4 and RS are a methyl group, and L is a linker alkylene, amine, or ether group, comprised of 1-7 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-7 carbons and a carbamate, thiocarbamate, or urea functional group.

Representative compounds having geroup (11) or (12) are those wherein RI, R2,

R3 are a methoxy group; X is chlorine; and I is a linker alkylene comprised of 3 carbons.

Representative compounds having group (11) or (12) are those wherein R1, R2,

R3 are a methoxy group; X is bromine; and E. is a linker alkylene comprised of 3 carbons.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are an ethoxy group; X is chlorine ; and L is a linker alkylene comprised of 3 carbons.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are an ethoxy group; X is bromine; and L is a linker alkylene comprised of 3 carbons.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are a methoxy group; X is chloriree; and L is a linker amine or ether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are a methoxy group; X is bromine; and L is a linker amine or ether group comprised of 4 carbons, and 1 nitrogen or oxy/gen atom.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are an ethoxy group; X is chlorine; and L is a linker amine or ether group comprised of 4 carbons, and 1 nitrogen or oxy gen atom.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are an ethoxy group; X is bromine; and L is a linker amine or ether group comprised of 4 carbons, and 1 nitrogen or oxy gen atom.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are a methoxy group; X is chlorine; arad L is a linker alkylene group comprised of 4 carbons and a carbamate, thiocarbarnate, or warea functional group.

Representative compounds having groeup (11) or (12) are those wherein R1, R2, and R3 are a methoxy group; X is bromine; armed L is a linker alkylene group comprised of 4 carbons and a carbamate, thiocarbamate, or virea functional group.

Representative compounds havin g group (11) or (12) are those wherein R1, R2, and R3 are an ethoxy group; X is chlorine; and L is a linker alkylene group comprised of 4 carbons and a carbamate, thiocarbamate, or urea functional group.

Representative compounds having group (11) or (12) are those wherein R1, R2, and R3 are an ethoxy group; X is bromin¢; and L is a linker alkylene group comprised of 4 carbons and a carbamate, thiocarbamate=, or urea functional group.

Imidazolidinone h © N (13)

Rg N Rs

R; \ on J

Re (14)

R

Re N °

R7 \

X

@]

X

AN

N (15)

N——

Ry " 6

Rs R4 wherein R4, R5, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

Representative compounds having garoup (13), (14), or (15), are those wherein R1,

R2, and R3 are a methoxy, ethoxy, or hydroxy group; R4, RS, R6, and R7 are a methy) =.

group; and L is a liraker alkylene, amine, or ether group, comprised of 1-4 carbons, and 0- 1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thi ocarbamate, or urea functional group.

Oxazolidinome ~~

O

O

R, (16)

N

Oo

X wherein R4 is at leas€ one of a C1-C4 alkyl, aryl, or hydroxymethyl group; anc wherein X is at least one of hydrogen, chlorine, or bromine.

Representative compounds having group (16) are those wherein R1, R2, and R3 are a methoxy, ethoxy, or hydroxy group; R4 is a methyl, ethyl, or hydroxymethyl group; and L is a linker alkylene group, comprised of 1-3 carbons, or L is a linker alkylene group, comprised of 1-3 carbons, and a carbamate, thiocarbomate, or urea functional group.

Glycoluril

X

\ Rs

N N

N N an [Lo

X 4X wherein R4 and RS5 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is independently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

Representative compounds having group (17) are those wherein R1, IR2, and R3 are a methoxy, ethoxy, or hydroxy group: R4 and RS are a methyl group; and L. is a linker alkylene, amine, or ether group, comprised of 1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbomate, or urea functional group.

Isocyanurate

O O

~~ ~~

N N N NT

; A PY PY PY er

O | O oO N O

X wherein X is independently selected from at least one of hydrogen, chlorine, brromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

Representative compounds having group (18) or (19) are those whereim RI, R2, and R3 are a methoxy, ethoxy, or hydroxy group; and L is a linker alkylene, amine, or ether group, comprised of 1-4 carbons and 0-1 nitrogen or oxygen atoms, or L as a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbomate , or urea functional group.

Tnazinedione

O

N N

” PY pu 0” ON Ra

Rs

X wherein R4 and R5 are independently selected from a (C1-C4 alkyl, aryl, or hydroxyrnethyl group; and wherein X is independently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

R_epresentative compounds having group (20) are those wherein R1, R2, and R3 are a met hoxy. ethoxy, or hydroxy group; R4 and RS are a methyl group; and L is a linker alkylene, amine, or ether group, comprised of 1-4 carbons and 0 -1 nitrogen or oxygen atoms, ox L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbo mate, or urea functional group.

Pi peridine

Rs N R,

Ra Re 21) wherein R 4, RS, R6, and R7 are independently selected from a €1-C4 alkyl, aryl, or hydroxymethy! group; and wherein X is chlorine or bromine when o»n structure (1) or (2), but X is hydrogen, chlorine, or bromine when on structures (5), (7), or (9).

Representative compounds having group (21) are those whesrein R1, R2, and R3 are a methoxy, ethoxy, or hydroxy group; R4, RS, R6, and R7 are a methyl group; and L 1s a linker alkylene, amine, or ether group, comprised of 1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbomate, or urea functional group.

R gwoups suitable for structures (3) (4) (6) (8) and (10) are an. amino alkylene or a polyamino alkylene group comprising at least one N-chloro or N-bromo group. A representative group for structures (3) (4) (6) (8) and (10) is an amino- propyl group.

For groups (5) (6) (9) and (10), n, is the number of repeating units, not to be confused with n of structures (1) (3) (6) and (7) where, n, is the number of R moieties on

Si. The repeating number of units, n, is greater than or equal to 2. However, n, can be ag much as 500), or greater.

A method for mak ing a modified substrate, comprises applying a solution of a compound of structure (1). and water, to a substrate; drying the solution and. curing the substrate at an elevated temperature to provide a modified substrate, wherein R in structure (1) is a heterocyclic N-Halamine. The solution can further comprise an alcohol.

Alternatively, the solution can be an alkaline solution.

A method for makiang a modified substrate, comprises applying a so lution of a compound of structure (1), and water, to a substrate; drying the solution; and curing the substrate at an elevated temperature to provide a modified substrate, wherein R in structure (1) is a heterocyclic amine from at least an amide-linked hydantoin, imidazolidinone, oxazolidinone, isocyanulate, glycoluril, and triazinedione.

A method for making a modified substrate, comprises applying a sol ution of a silane having a pendant heterocyclic amine, and water, to a substrate; drying th € solution; curing the substrate at an elevated temperature; and halogenating the heterocy«clic amine with an oxidative halogen compound to provide a modified substrate.

A method for making a modified substrate, comprises applying a solution of a compound of structure (3), and water, to a substrate; drying the solution; and «uring the substrate at an elevated temperature to provide a modified substrate.

A method for making a modified substrate, comprises applying a solution of a silane having a pendant aminoalkylene or polyamino alkylene group, and wrater, to a substrate; drying the solution; curing the substrate at an elevated temperature; and halogenating the amino grovap with an oxidative halogen compound to provide a modified substrate.

A method for makirag a modified substrate, comprises applying a solution of a compound of structure (5), and water, 10 a substrate; drying the solution; and curing the substrate at an elevated temuperature to provide a modified substrate, wherein R in the structure (5) is a heterocyclic N-halamine.

A method for making a modified substrate, comprises applying a solu tion of a siloxane of structure (5), and water, to a substrate; drying the solution; and curing the substrate at an elevated temperature to provide a modified substrate, wherein R in the structure (5) is a heterocyclic amine from at least an amide-linked h/dantoin, imidazolidinone, oxazolidinone, isocyanurate, glycoluril, triazinedione, and piperidine.

A method for makin g a modified substrate comprises applying a solution of a siloxane having a pendant heterocyclic amine, and water, to a substrate; drying the solution; curing the substrate at an elevated temperature; and halogenating the heterocyclic amine with an oxidative halogen compound to provicie a modified substrate.

A method for making a modified substrate, comprises applying a solution of a . siloxame of structure (6), and water, to a substrate; drying the solution; and curing the surface at an elevated temperature to provide a modified substrate=.

A method for making a modified substrate, comprises applying a solution of a siloxane having a pendant amino alkylene or polyamino alkylene group, and water, to a substrate; drying the solution; curing the substrate at an elevated temperature; and haloge=nating the amino group with an oxidative halogen compound.

The present invention provides numerous advantages, mncluding the ability of rendering surfaces and materials biocidal when the compounds of” the invention are bound thereto, and the amine moiety has an N-chloro or an N-bromo group.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing aspects and many of the attendant advantag=es of this invention will becom e more readily appreciated by reference to the following de=tailed description, when taken 1 n conjunction with the accompanying drawings, wherein:

The sole figure is an illustration of one embodiment of a reaction mechanism for modifying a substrate according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention may be understood more readilly by reference to the follow3ng detailed description of specific embodiments and the examples included therein.

A silane or silane compound can be a monomer to produce polymers or siloxanes.

The sil anes and siloxanes have heterocyclic and acyclic amine mo ieties. The heterocyclic amine moieties are bound by a linker group. The heterocy«clic and acyclic amine moieties can impart biocidal functionality when the moieties hav-e an N-chloro or an N- bromo group. The silanes and siloxanes can be bound to substrates, and the substrates rendered biocidal. A siloxane compound can be an oligomer or polymer. :

As used herein, "the modified substrate” refers to a surface or material to which a silane or siloxane compound having the structure (1), (2), (3), (4), (5), or (6) has been attache=d through one or more of the moieties R1, Rp, and R3. If ZX in the amine group is

Cl or B3r or combinations thereof, the surface or material will toe biocidal; if X in the amine group is H, the surface or material will not be biocidal, but: the surface or material can be rendered biocidal by exposing it to a source of oxidative chlorine or bromine. The substrates are represented by structures (7), (8), (9), and (103).

The unhalogenated silane compound of the invention can be synthesized by reacting a heterocyclic amine with a base in a solvent, such as ethanol, followed by reaction of the resulting alkali metal salt with a haloalk ylsilane in a solvent such as anhydrous dimethylformamide (DMF) such that the linlser L constitutes an alkylene group.

Alternatively, an unhalogenated silane compound of” the invention can be prepared by reacting a heterocyclic amine containing a hydroxymethyl substituent with an aminoallkylsilane, a haloalkylsilane, an 1socyanatoalkylsilane, an isothiocy’anatoalkylsilane, or a silyl urea in a solvent such as anhydrous dimethyl formamide such that the linker L constitutes an zmine or an ether moiety, an alkylene carbamate, an alkylene thiocarbamate, or an alkylene urea, respectively.

Alternati vely, the unhalogenated silane compound of the invention can be an alkyleneamino or alkylene-poly-amino silane itself to wh ich no heterocyclic amine is attached. In general, the raw materials used in the synthesis of the silane compounds of the invention are inexpensive and available commercially from vendors such as Aldrich

Chemical Company (Milwaukee, WI), Fisher Scientific (Pittsburgh, PA), Gelest Inc. (Tullytovwn, PA), Acros, Inc. (Pittsburgh, PA), and TCI America (Portland, OR).

For group 11, for example, 5,5-dimethylhydantoin can first be reacted with potassiurm hydroxide in ethanol, followed by reaction o-f the potassium salt of the hydantoim with chloropropyltrimethoxysilane in anhydmous dimethylformamide to produce 5,5-dimethyl-3-trimethoxysilylpropylhydantoin according to the method of

Berger ira U.S. Patent No. 4,412,078. All of the starting reagents necessary to make this monomer are available commercially.

For group 13, for example, 2,2,5,5-tetramethyl-1,3- imidazolidin-4-one, prepared according to U.S. No. Patent 5,057,612, can be treated with the mild base sodium carbonate to neutralize the hydrochloric acid proeduced upon reaction of chloropropyltrimethoxysilane at the amine position on the inaidazolidinone ring.

For group 14, the strong base, potassium hydroxicle can be used to form the potassium salt at the amide nitrogen of the imidazolidinone xing in xylene as a solvent as in U.S. Patent No. 4,448,969, followed by” reaction with the chloroproaspyltrimethoxysilane.

For group 16, 4-ethyl-4-hydroxymethyloxazeolidinone, prepared according to U.S.

Patent No. 5,902,818, can be reacted with sodium metal to produce the sodium salt at the oxygen bonded to the exocyclic methylene group, followed by a nucleophilic substitution reaction with chloropropyltrimethoxysilane.

For groups 15 and 17, each possessing am#de nitrogens, representatives can be produced by reacting 4,4,5,5-tetramethyl-1,3-imida=zolidin-2-one, prepared according to

U.S. Patent No. 4,681,948, and dimethylglycoluril, zavailable commercially, respectively, with potassium hydroxide, followed by reaction with chloropropyltrimethoxysilane as for the group 14 case.

For groups 18, 19 and 20, possessing reactive imide nitrogen moieties, the unhalogenated silane compounds can be made, for example, in a procedure analogous to that for the silylhydantoin in group 11 by reacting- a sodium or potassium salt of the isocyanurate (available commercially) or a triazined ione (prepared in analogous manner to a derivative described in U.S. Patent Mo. 5,490,983), respectively, with chloropropyltrimethoxysilane. In the case of tlie isocyanurate of group 18, two equivalents of chloropropyltrimethoxysilane ean be used to bond the trimethoxysilylpropyl moiety to two of the nitrogems of the triazine ring, leaving one nitrogen free for reaction with halogen.

For group 12, two equivalents of a strong ba se, such as sodium hydride, can be employed to produce the disodium salt of the hydan toin, followed by reaction with one equivalent of chloropropyltrimethoxysilane, to produice a mixture of the compounds of groups 11 and 12.

For group 21, the general procedure described in U.S. Patent No. 4,684,726 can be followed to produce, for example, 3-(2,2,6,6-tetramethylpiperidine-4- oxy)propyltriethoxysilane.

The silane compounds can be rendered bioc-idal by reacting the corresponding unhalogenated silane compounds, dissolved in water, at ambient temperature with free chlorine from such sources as gaseous chlorine, socdium hypochlorite bleach, calcium hypochlorite, chloroisocyanurates, and dichlorohy dantoins. In the case of the dichlorohydantoins, the chlorine moiety on the imide mitrogen should transfer to the more stable amide nitrogen, if available. Likewise, the brominated silane compounds can be prepared by exposing them in aqueous solution at ambient temperature to free bromine from such sources as molecular bromine liquid, sodium bromide in the presence of an oxidizer such as potassium peroxy monosulfate, and brominated hydantoins.

Halogenation can also be effected in organic solvents employing free radical halogenating agents such as t-butyl hypochlorite.

The unhalogenated or halogenated silane compounds can be bound or immobilized to a surface or material through either covalent bonding or an adhesive interaction depending on the nature of the surface or material to provide a surface modified with the unhalogenated or halogenated silane compounds. This can be accomplished by exposing the surface or material to a solution of the unhalogenated silane compound at temperatures in the range of 0 to 300°C, more preferably 20 to 150°C, depending upon the nature of the surface or material. Immobilization of the halogenated silane compounds can be accomplished by exposing the surface or material to a solution of the compound at temperatures in the range of 0 to 60°C, more preferably, 20 to 40°C, depending upon the nature of the surface or material. The solvent for the silane compounds should contain at least 50% water to be used in the conversion of any alkoxy groups (comprising the Ry, Ro. and R3 groups in structure II) to hydroxyl groups so as to provide binding sites to the surface or material. Organic solvents such as dimethylsulfoxide, tetrahydrofuran, dimethylformamide, alcohols, acetone, ethyl acetate, and methylene chloride can also be used in conjunction with water for the silane compounds, although alcohols are less useful for the halogenated silane compounds because they partially protonate the nitrogen of the heterocyclic ring or alkyleneamino group liberating halogen. Base can also be added to the aqueous solutions to enhance the solubility of the silane compounds. If water is the only solvent used, the pH should be adjusted to greater than 12. Other additives can be introduced to the solutions of the silane compounds to enhance binding to the surface or materials, e.g., potassium thiocyanate for binding to cellulose. The solutions containing the silane compounds can k be exposed to the surfaces or materials by soaking, spraying, spreading, and the like.

Following drying of the solution on the surface, curing at some temperature (which depends upon the surface or material composition, e.g., 25°C for paper, 95°C for cotton fibers and glass) for 15 to 30 minutes, should be performed.

The unhalogenated or halogenated silane compounds can also be polymerized to form siloxane compounds before attaching them to surfaces by exposing them to an acid such as hydrochloric acid in mixtures of ethanol and water, or water alone. The reaction is illustrated in the FIGURE. The heterocyclic moieties can be introduced before or after the polymerization.

The surface or material can be rendered biocidal if the unhalogenated silane or - siloxane compounds are immobilized on the surface by exposure to a source of oxidative halogen, such as an aqueous solution of sodium hypochlorite bleach, calcium hypochlorite, chloroisocyanurates, and dichlorohydantoins; or an organic solution of t- butyl hypochlorite, for chlorination, or am aqueous solution of molecular bromine liquid, sodium bromide in the presence of an oxidizer such as potassium peroxy monosulfate, and brominated hydantoins for brominat jon. For example, an aqueous solution of 10%

CLOROX can be used for efficient chlorination which can be accomplished at ambient temperature by spraying or soaking the surface or material with same. After halogenation, the surface or material shotald be allowed to dry in air at temperatures up to 40°C (ambient temperature is preferable if time permits) and rinsed with water. The modified surface or material will then exhibit biocidal properties for various time periods dependent upon the composition of the surface or material, the use pattern (contact with organisms and halogen demand), and the storage temperature. When the bound halogen content becomes too low for efficient biocidal activity, the modified surface or material can be recharged with halogen in the same manner as for the original charging noted above.

An alternate embodiment of attaching the biocidal moieties to surfaces is to first bond a silane or a siloxane compound containing a substituted nucleophilic alkyl functional group to the surface, and seceond, bonding the heterocyclic N-halamine or heterocyclic amine group to the tethere=d silane or siloxane through a nucleophilic substitution reaction. For example, ammnopropyltriethoxysilane can be bonded to a surface, and then the amino functionality can be reacted with 3-hydroxymethylhydantoin to produce an anchored hydantoin that can then be halogenated in situ as described above to render the surface biocidal. Alternatively, the tethered aminopropyltriethoxysilane could be directly halogenated in situ as described above to achieve a biocidal surface. In general, the halogen will be stabilized to a greater extent when bonded to nitrogen on a heterocyclic moiety as opposed to an acycli ¢ moiety.

The mechanism of action of the “biocidal surfaces and materials produced as described herein is believed to be a result off surface contact of the organism with chlorine or bromine covalently bound to the heterocyclic functional groups on the bound silane,

The chlorine or bromine atoms are transferred to the cells of the microorganisms “where they cause inactivation through a mechanism not completely understood, but prosbably involving oxidation of essential groups contained within the enzymes comprisirmg the organisms.

A marked advantage of the biocidal surfaces and materials of this inventiora over prior technology is that the surfaces and materials are much more effective bioc idally against pathogenic microorganisms, such as Staphylococcus aureus and PseudorPionas aeruginosa, encountered in medical applications than are commercial biocides such zs the quaternary ammonium salts. T he biocidal surfaces and materials serve a dual function: (1) inactivation of disease-causing pathogens, and (2) inactivation of odor-ca using microorganisms. For this reason, the invention will have widespread use in medical settings such as hospitals, nursing facilities, and research laboratories. It should al so be useful for biocidal applications in a variety of other industrial settings, as well as £n the home.

Representative surfaces and materials that can be made biocidal with. this invention include envelopes, surgical gowns, masks, and gloves, sheets, bandhages, sponges, table and counter tops, glassware, as well as articles made from pl astic, synthetic fibers, wood, chitin, chitosan, cement grout, latex caulk, porcelain, acrylic films, vinyl, polyurethanes, silic on tubing, marble, and metals.

EXAMPLES

EXAMPLE 1

PREPARATION OF A REPRESENTATIVE UNHALOGENATED SILANE

COMPOUND

Two trialkoxysilylpropy’thydantoin derivatives were prepared according to a procedure similar to that outlined in U.S. Patent No. 4,412,078.

A one-liter, three-neck-mxound-bottom flask was fit with a condenser, dropping funnel, and thermometer. To the flask was added a mixture of 500 mL of ethanol, 6 4.0 g (0.5 mol) of 5,5-dimethylhydartoin (Acros, Inc.), and 28.0 g (0.5 mol) of potassium hydroxide. The mixture was hesated to the boiling point until the solution became clear.

Then the solid potassium salt of the 5,5-dimethylhydantoin was isolated by evaporation of the ethanol solvent and the water produced in the reaction under reduced pres sure.

This salt was dried under vacuum at 60°C for four days to form the anhydrous potassium salt. The dry salt was then placed back in the one liter flask where it was mixed with

500 mL of anhydrous N,N -dimethylformamide (DMF), and the mixture was heated at 60°C until. a clear solution formed. Then 1204¢g (0.5mol) of 3- chloropropyltriethoxysilane (Aldrich Chemical Company) were added dropwise: over a one-hour period with stirritag at ambient temperature. The mixture was then heated at 95°C for 4 hours, cooled, and the potassium chloride produced in the reacti on was removed by filtration. The DMF solvent was removed by distillation to produce 150.0 g of a brown, viscous oil identified as 3-triethoxysilylpropyl-5,5-dimethythydantoin, the yield being 90.3% of theoretical. The product was further purified by distillatiom under reduced pressure (16 mmr Hg, fraction collected 235-238°C) for elemental and spectroscopic characterization. Anal. Caled. for C14HpgSiN2O5: C, 50.6; H, 84; N, 8.4. Found: C, 50.3; H, 8 4; N, 9.0. IH NMR (CDCl3) 8 0.61 (2H), 1.22 (9H), 1.43 (6H), 1.73 (2H), 3.48 (2H), 3.82 (6H), 7.17 (1H). IR (KBr) 740, 813, 1081, 1104, 1713, 1774, 2879, 2989, 3279, 3485 cm-l. MS (C/CHy) m+1, 333.

A procedure analogous to that described above utilizing 3-chloropropyltrimethoxysil ane (Aldrich Chemical Company) provided 3-trimethoxysilylpropyl-5,5—dimethylhydantoin as a brown oil (8 mm Hg, fiaction collected 194-195°C), the y-ield being 92.0% of theoretical. 'H NMR (CDCl3) 4 0.62 (2H), 1.43 (6H), 1.71 (2H), 3.53 (11H). 7.07 (1H). IR (KBr) 740, 812, 1091, 1450, 1712, 1773, 2835, 2959, 3000-34040 cm.

EXAMPLE 2

PREPARATION AND BIOCIDAL EFFICACY OF A REPRESENTATIVE

CHIL_ORINATED SILANE COMPOUND

A portion (6.11 g, 0.021 mol) of 3-trimethoxysilylpropylhydantoin, prepared as described in Example 1, was dissolved in 30 mL of methylene chloride in a 1 25 mL

Erlenmeyer flask. Then 2.30 g (0.021 mol) of tert-butyl hypochlorite, prepared acc ording to the method of Mintz, et al. (Org. Syn. 1969, 49:9-12), were added at room temperature, and the flask was stoppered., and the mixture was allowed to stand at room temperature for 3 hours with all light ex cluded. Vacuum evaporation was employed to remo-ve the tert-butyl alcohol produced in the reaction. The product, 1-chloro-3- trimethoxysilylpropyl-5,5-dirnethylhydantoin, was produced as a yellow oil in 89.7% yield. It was stored at 4°C in the absence of light until use. The total chlorine content was determined to be 10.36% by iodometric/thiosulfate titration as compared to the theoretically possible value of 10.94%. The 'H NMR signal at 87.07 for 3-

trimethoxy’silylpropylhydantoin vanished upon chlorination indicating the presence of chlorine at the 1 position of the hydantoin moiety.

A 200.8 mg/L solution of the chlorinated silane compound, prepared as described above, cortaining 11.02 mg/L total chlorine content in chlorime-demand-free water at pH 7 was challenged with S. aureus bacteria (ATCC 6538) for ceontact times of 5, 10, 30, and 60 mira at ambient temperature. Following the contact with the bacteria, further disinfectant action was quenched by adding 0.02 N sodium thiowsulfate. Serial dilutions were then plated onto irypticase soy agar, and colony counts wer-e made after 48 hours of incubation at 37°C. No growth was detected on the plates indicating a complete inactivation (>4.9 logs) at all of the contact times. Thus the chloarinated silane compound is biocidal under the conditions tested. Neither lower contact times, nor lower concentrations, were evaluated.

EXAMPLE 3

PREPARATION OF BIOCIDAL PAPER_

Sma ll pieces of white and brown commercial office envelopes were cut into small squares. A 2% aqueous alkaline solution (pH3 from NaOH addition) of 3-triethoxys 1lylpropyl-5,5-dimethylhydantoin, prepared as described in Example 1, was sprayed frorn an atomizer bottle onto both sides of the paper samples until they became saturated. T hen the wet samples were cured until dry at 60°C for 15 minutes. The cured + 20 samples wexe then sprayed on both sides with 10% CLOROX bleach until saturated, allowed to stand at ambient temperature for 10 minutes, rinse d 5 times with 50 mL portions of chlorine-demand-free water, and dried at ambient tem perature. The samples were stored In a vacuum desiccator until use for analytical and microbiological characterization.

An iodometric/thiosulfate titration procedure was used to determine the chlorine loadings on the squares of the two kinds of paper as a function of ®ime after chlorination.

The data are shown in Table 1. .

TABLE 1. STABILITY OF CHLORINE ON PAPER SAMPLES

Sample Type Time Since % Cl Loading mg/cm? Cl Loading

Chlorination (d)

White 0 0.823 0.055 ‘White 14 0.82 0.049

Sample T ype Time Since % Cl Loading mg/cm? Cl Loading

Chlorination (d)

White 21 0.79 0.047

White 28 0.79 0.0454

White 36 0.781 0.0448

Brown 0 0.51 0.0344

Brown 14 0.50 0.032

Brown 21 0.499 0.034

Brown 28 0.488 0.033

Brown 36 0.464 0.032

Frorm the data in Table 1, it can be concluded that the treated paper samples stabilized chlorine very well over a 36-day period.

Freshly chlorinated paper samples (white and brown) were also challenged with

S. aureus bacteria (ATCC 6538). Control samples consisted of treated, but unchlorinated paper, and wntreated, but chlorinated paper. The data are presen ted in Table 2.

TABLE 2. INACTIVATION OF S. AUREUS BY PAPER SAMPLES

Sample Ty pe 1 Min Log 5 Min Log 10 Min Log 30 Min Log

Reduction Reduction Reductiom Reduction

White Contr 0 0 0 0

White Cl 0.1 3.0 >5.42 >5.4

Brown Comtr 0 0 0 0

Brown Cl 1.9 4.6 >5.3 >5.3

From. the data in Table 2, it can be concluded that both kimds of treated paper were effective in Idilling the bacteria. An untreated control which was subjected to the same chlorination procedure produced a reduction of about 1 Log durirag a 1 hour contact, but it is clear that most of the inactivation of the bacteria by the chlorirmated treated samples can be attributed to the bound chlorine on the hydantoin moiety.

Similar results have been obtained for commercial paper file folders. ) -20- N :

EXAMPLE «4

PREPARATION OF BIOCEDAL COTTON

Swatches of Style 400 Bleached 100% Cotton Print Cloth (Testfabrics, Inc.) were treated with 3-triethoxysilylpropyl-5,5-dimethyllnydantoin, prepared as described in

Example 1, in the following manner. A treatment bath was prepared containing 5.0 g of 3-triethoxysilylpropyl-5,5-dimethylhydantoin, 3.0 g of potassium thiocyanate, 50 mL of ethanol, and 50 mL of water. After 1 hour of equil-bration of the bath mixture, the cotton swatches were soaked in the bath for 10 min. A_fter partially drying in air at ambient temperature, the swatches were cured for 1 hour at 95°C. The swatches were then soaked ma 0.5% liquid detergent solution for 15 min, rinsed with tap water, and allowed to dry in air at ambient temperature. It was found that this treatment produced an average percent weight gain of the swatches of 5.5 £ 0.6%; for an identical treatment except with the omission of KSCN the average weight gain -was 4.7 + 0.3%. The swatches were charged with chlorine by soaking in a 10% CLO ROX solution for 30 min at ambient temperature, rinsed thoroughly with chlorine-dema nd-free water until test strips showed less than 0.2 mg/L of free chlorine in the wash water, and then dried in air at ambient temperature. It was found that the average chlorine loading on the swatches was 0.61 + 0.14%; without the use of KSCN the average chlorine loading was 0.49 + 0.07%.

The swatches were stored in a vacuum desiccator uratil use.

For comparison purposes, a biocidal quaternary ammonium compound (dimethyloctadecyltrimethoxysilylpropylammoniure ~~ chloride, Aldrich ~~ Chemical

Company) was also used to treat cotton swatches in a bath similar to that described above (with and without KSCN). The average weight % acld on was 14.7%.

Treated cotton swatches were challenged with S aureus (ATCC 6538) and

Escherichia coli (ATCC 2666) at a concentration Of between 108 and 109 CFU/mL in pH 7 phosphate buffer solution using a modified version of AATCC Method 100. The swatches were quenched with 0.02 N sodium thiosulfate solution at contact times of 10, 30, 60, and 120 min. Serial dilutions of the solutions contacting the swatches were plated on nutrient agar, incubated for 48 hours at 37°C, and. plate counts were made to determine the presence of viable bacteria. It was found that al I S. aureus colonies (>5.7 logs) were inactivated by the swatches treated with 3-triethawxysilylpropyl-5,5-dimethylhydantoin (with or without KSCN in the treatment bath) in the contact time interval 10-30 minutes; whereas, the swatches treated with the quaternary ammonium salt experienced only a

1.8 log reduction at 30 minutes. The contr ol sample (cotton soaked in 10% bleach, rinsed, and dried) gave only a 0.4 log reduction at 30 minutes. It was found that all

E.coli (>5.9 logs) were inactivated by the svwatches treated with 3-triethoxysilylpropyl- 5,5-dimethylhydantoin (with or without KSCIN in the treatment bath) in the contact time > interval 60-120 minutes; whereas, the swatches treated with the quaternary ammonium salt experienced only a 2.5 log reduction in thi s contact time interval. The control sample (cotton soaked in 10% bleach, rinsed, and dried) gave a 0 log reduction at 120 minutes. :

It can be concluded that cotton cloth treated with 3-triethoxysilylpropyl-5,5- dimethylhydantoin (with or without KSCIN in the treatment bath) is biocidal.

Furthermore, the hydantoin derivative is more effective than the biocidal quat, and it seems to be somewhat more effective against tthe Gram positive bacterium S. aureus than against the Gram negative bacterium E. coli.

Washing tests have demonstrated that the cotton cloth treated by the 3-triethoxysilylpropy!-5,5-dimethylhydantoin retains about 34% of its bound chlorine after 50 wash cycles. A 1% bleach solution c an be used for chlorination if the time of contact 1s 30 minutes.

A stability test during dry storage was also conducted on cotton samples coated with 3-triethoxysilylpropyl-5,5-dimethylhydantoin. One half of the samples were coated in a bath containing 8% of the 3-triethoxyst lylpropyl-5,5-dimethylhydantoin in 50% ethanol in water solution. The other half were treated in the same manner except that

KSCN was added to the treatment bath as descxibed above. The chlorination conditions and analytical method of measuring chlorine loadings were the same as discussed above.

The samples were stored in plastic bags at ambient temperature; the bags were not air- tight. The average chlorine loading for the samples treated in the presence of KSCN declined from 0.776% to 0.680% over a period of 50 days. For the samples not treated in the presence of KSCN, the decline was from 0.620% to 0.540% over the same 50 day period. It can be concluded that the coated cotton samples were fairly stable to loss of chlorine in dry storage.

Finally, tensile strength tests were run or coated cotton fibers. It was found that the average decline in tensile strength upon coating the cotton fibers with 3- triethoxysilylpropyl-5,5-dimethylhydantoin was about 8.7%; chlorination caused a further loss of only 0.6%. In this case the measurements were made upon the day of chlorination. A further decline in strength would be expected with time after chlorination and with frequency of rechlorination, since bleaching is known to cause slow degradation in cotton fibers.

EXAMPLE 5

PREPARATION AND TESTING OF A REPRESENTATIVE SILOXANE

<CCOMPOUND

A polymeric form of 3-chlomopropylsiloxane was prepared as follows. In a 500 mL flask, 72.14 g (0.3 mol) of 3-chloropropyltriethoxysilane was mixed with 100 mL of ethanol, and while stirring the mix#ure, 77.8 g of concentrated hydrochloric acid were added dropwise. The mixture was then refluxed for 5 hours followed by removal of water and ethanol to produce a viscous oil. The oil was held at 80°C under vacuum (about 30 mm Hg) for 15 hours. The polymer (41.0 g) was obtained in 99% yield per unit based upon the structure proposed below.

T 7

EE CL (Le

CH: fe 2 ik oH ) Ho

Cl Cl

An elemental analysis based upon the proposed structure yielded: Caled. for

C3H7Si0,ClL: C, 26.00; H, 5.05; Cl, 25.63. Found: C, 28.67; H, 4.85; Cl, 26.56. 1H

NMR (dg-DMSO) 6 0.76 (2H), 1.79 (2H), 3.33 (1H), 3.60 (2H).

Then the potassium salt of 5,5-cdimethylhydantoin was prepared by slowly adding 1498¢g (0.267mol) of potassium hydroxide to 34.21 g (0.267 mol) of 5,5- dimethylhydantoin in 100 mL of DMF with stirring in a 500 mL flask. The mixture was further stirred at ambient temperature for 30 minutes. Then 37.0 g (0.267 mol per unit) of the polymer of 3-chloropropylsiloxane in 100 mL of DMF were added to the mixture, which was held at 100°C for 6 hours wath stirring. The potassium chloride salt produced 40 and the DMF solvent were removed bey filtration and evacuation, respectively, to give 59.2 g crude yield (96.4%) of viscous oil. The viscous oil was further held at 150°C under vacuum (about 30 mm H g) for 8 hours. The polymer product was a white s olid at ambient temperature produced in high yield based upon the structure proposed below. ° or oH

Tro gio— ® {

CH, CH R= he 0)

HN ik The ve rp co

R R

An elemental analysis based upon the proposed structure yielded: Caled.. for

CgH14SiN204: C, 41.74; H, 6.09; N, 12.17; CI, 0.00. Found: C, 41.69; H, 6.1 4; N, 12.03; Cl, <0.25. TH NMR (dg-DMSO) 8 0.52 (2H), 1.26 (6H), 1.52 (2H), 3.29=-3.36 (3H), 8.16 (1H); IR (KBr) 774, 1122, 1281, 1352, 1422, 1452, 1709, 1772, 2935, 2977, 3000-3600 cml. The infrared bands at 1709 and 1772 cm! are indicative o 1 the presence of the hydantoin ring in the siloxane polymer.

The siloxane polymer described above was coated onto 100% cotton fabric. This was accomplished by soaking swatches of the material for about 2 minutes at am bient temperature in a bath containing 5 g of the polysiloxane, 70 mL of ethanol, and 40 nal of water. The swatches were cured at 130°C in air for 20 minutes, then soaked in 1.5% liquid detergent for 15 minutes at ambient temperature, and then rinsed thoroughly with water. After drying in air at 50°C for 30 minutes, the swatches were then soaked ira 5%

CLOROX at ambient temperature for 45 minutes, rinsed thoroughly with water, and cried in air at 50°C for 30 minutes to remove any free chlorine present. An iodometric/thiosulfate titration iradicated a chlorine loading on the cotton materizml of about 0.42%.

A biocidal evaluation of representative cotton swatches using the procedure outlined in Example 4 showed that the treated material produced a 1.7 log reductiom of 40 S. aureus bacteria within a contact time range of 10-30 minutes, but a 7.6 log reduc:-tion (total inactivation) within the range of 30-60 minutes. Thus a longer contact time was required for the chlorinated siloxane polymer coating than for the silane monomer coating described in Example 4, but the chlorine loading was also lower by 14.3%, so this result was not unexpected.

TABLE 3. EFFECTS OF WASHING TESTS ON COTTON COATED SWATCHES

Coating Type Chlorination Chlorination Washing | Average (Polymer, P) Loading % op | Ne | ve | os | ex

IE ES A" TR ST op | Ne | Ye | so | oos wes or | we [owe | os | es p | we | Ne | 10 | 20 or | ve | ove | 5 | oss or | ve | ve | 10 | ox op | ove | ove | so | ous

Finally, a wash test was performed on swatches of cotton containing the monomer 3-triethoxysilylpropyl-5,5-dimesthylhydantoin coating and the polysiloxane coating, each chlorinated and unchlorinated, for comparison purposes. Two treatment baths were prepared, one containing an 8%6 solution of 3-triethoxysilylpropyl-3,5-dimethylhydantoin in a 50% solution of ethanol im water, the other containing an 8% solution of siloxane polymer prepared as described above in a 66.7% solution of ethanol in water. Identical cotton swatches were soaked in the two baths for 2.5 minutes at am bient temperature, cured in air at 130°C for 20 minutes, soaked in 1.5% liquid detergent at ambient temperature for 15 minutes, rinsed thoroughly with water, and dried in air at 50°C for 30 minutes. Then one-half of the swatches of each type were chlor inated by soaking them in 5% CLOROX at ambient temperature for 45 minutes. These cFilorinated samples were rinsed thorou ghly with water and dried in air at 50°C for 30 minutes to remove all occluded free chlorine. lodometric/thiosulfate titrations were performed on representative sam ples to determine initial chlorine loadings. The average chlorine loading for the silane monomer-coated samples was 0.61%; for the siloxane polymer- coated samples, tlxe average chlorine loading was 0.40%. Then all types of coated swatches were subjected to laundry washing cycles using AATCC Test Method 61 (Test 2A Procedure). Samples were evaluated after 5, 10, and 50 washing cycles for retention of the coatings. Those samples not chlorinated before washing were chlorinated by the procedure described above in order to assess how much chlorine could be loaded after variable num bers of washing cycles. Those chlorinated before washing were divided into two groups with half being assessed for chlorine loading without rechlorination, the other half being rechlorinated and then assessed for chlorine loading.

Three observations are clearly evident from the data in Table 3. First, beth the silane and the siloxane coatings are partially lost upon successive washmings. Second, prechlorination reduces the rate of loss, probably due to increasing the Inydrophobicity of the surface, thus reducing the rate of hydrolysis loss of the siloxane coatings. Third, the siloxane coating, which is not chlorinated to as high a level as the silane one upon initial chlorination, is lost at a slower rate than is the silane coating. For all o=f the coatings, at least partial biocidal efficacy would be regenerated upon rechlorination after 50 washing 35 cycles. Most probably, a low concentration of bleach added to washimg cycles should maintain biocidal activity of the cotton material for the lifetime of the manterial.

EXAMPLE 6

ALTERNATIV EPREPARATION AND TESTING OF A REPRESENTATIVE

SILOXANE COMPOUND

To a one-neck round-bottom flask were added 35 g of 3-triethox ysilylpropyl-5 5- : dimethylhydantoin, prepared as described in Example 1, 18 mL of etlnanol, 36 mL of water, and 0.25 to 0-SmL of dilute hydrochloric acid (1:1 by volume) suach that the final pH was in the range 3.5 to 5.5. The mixture was refluxed with stirring- for 5 hours and then poured into an open beaker which was left in a vacuum oven at 60°C for 3 hours, then 100°C for 3 hours, then at 130°C for 2 hours, and finally at 170°C for 2 hours. T he resulting glossy solid was a polymeric form of 3-trihydroxysilylpropyl-5 .5- dimethylhydantoin. The material was not characterized other than by its performance as noted below.

The polymeric material prepared as described above was then used to coat the surfaces of military tenting, wood, glass. aluminum, and cotton. For the military tenti ng material, 2 g of the polymer were dissolved in 40 mL of ethanol to produce a 5% solution. Swatches of tenting material cut into 3-cm x 4-cm rectangles were soaked in the polymer solution for 2 to 3 minutes and then dried at ambient temperature for 48 hou rs.

Then the polymer coating was chlorinated by soaking the swatches in 10% CLOROX for 30 minutes at ambient temperature. Following rinsing and drying at ambient temperatuxe, - the chlorine loading on the surface of each swatch was determined usimg iodometric/thiosulfate titration. The loading averaged 4.2 X 1016 Cl atoms per cm? afer initial chlorination. Some of the swatches were reduced in thiosulfate and recharged.

The average chlorine loading following the recharge was 5.3 X 1016 Cl atoms per cn?.

The swatches were not tested for biocidal efficacy, but in our experience, any surface containing a chlorine loading of at least 1 X 1016 atoms per cm? will be biocidal.

The same polymeric material wa s then coated onto wood (Tulip Poplar). In this case a 2.8% solution of the polymer in ethanol was used. Blocks of the wood havimg dimensions 5 cm X 3.8 cm X 1.9 cm were coated with the polymer solution using: a cotton swab. The blocks were dried in air and then cured at 120°C for 1 hour. Th en chlorination was performed by soaking in 10% CLOROX for 30 minutes at ambient temperature. Following thorough rinsing with water and drying in air, an iodometric/thiosulfate titration indicated that the average chlorine loading was 1.57 X 1017 Cl atoms per cm?, which should give excellent biocidal efficacy. Analogo-us treatment of glass (FISHER microscope slides) and aluminum (REYNOLDS Heavy Duaty

Foil) gave chlorine loadings averaging 1.32 X 1017 Cl atoms per cm? and 1.15 X 1017 Cl atoms per cm?, respectively.

Also, a solution containing 2.5 g of the polymer in 100 mL of ethanol (2.5%) w~as sloshed in a plastic (PET) bottle and therm poured out. The solution was allowed to dry «on the inside surface of the bottle, then cured for 1 hour at 65°C. Then the bottle was filled with 10% CLOROX for 30 minutes at arnbient temperature, Following thorough rinsimg with water and drying in air, 2 iodometric/thios-ulfate titration indicated that the average chlorine loading was 5.3 X 1016 CI atoms per cn?

Finally, 100% cotton fabric swatches vavere tested. In this case 10 mL of the refluxed solution of polymer (the solid was not isolated) were mixed with 100 mL of a 50% ethanol/50% water solution in a beaker. T he cotton swatches (7 g) were soaked in the solution for 3 minutes, then partially dried in air at ambient temperature, and then cured at 150°C for 30 minutes. After soaking in 5% CLOROX for 20 minutes, the swatches were rinsed and dried at ambient tempesrature. The average chlorine loading of several swatches was determined by iodometrac/thiosulfate titration to be 0.438% CI.

Then the other treated swatches were subjected to laundry washing cycles using AATCC

Test Method 61 (Test 2A Procedure) followed by analytical determination of chlorine loading as a function of the number of wash cyc les. After S, 10, and 50 wash cycles the chlorine loadings averaged 0.282%, 0.279%, arid 0.165%, respectively. A loading of even 0.165% CJ should exhibit reasonable biocidal efficacy.

EXAMPLE 7

PREPARATION OF AND COATING WITH A REPRESENTATIVE

SILANE COMP*OUND

The potassium salt of 2,2,5,5-tetramethmylimidazolidin-4-one was prepared by refluxing a solution of 142g (0.1 mol) of 2,2,5,5-tetramethylimidazolidin-4-one in 130 mL of xylene until all of the solid was dissoBved. Then a solution of 5.6 g (0.1 mol) of potassium hydroxide in 6.46 mL of distilled, deionized water was added dropwise over a period of about 15 minutes, and the mixture wass refluxed for an additional 2 hours until about 98% of the water produced in the reaction was removed. The solvent was removed under vacuum leaving the white solid potassium salt of 2,2,5,5-tetramethylimidazolidin- 4-one. Then 100 mL of anhydrous DMF was aadded to the salt, and the mixture was heated to 100°C until all solid was dissolved. Then 24.1g (0.1 mol) of chloropropyltriethoxysilane were added dropwise to the mixture at 1000C over a period of 45 minutes, and the mixture was held at 100°«C for an additional 12 hours. Then the mixture was filtered at ambient temperature to remove the potassium chloride produced in the reaction, and the DMF solvent was remove«d under vacuum. The crude product, 3- triethoxysilylpropyl-2,2,5,5-tetramethylimidazolidlin-4-one (32.1 g; 92.6% crude yield), was a light brown viscous liquid which was used directly without further purification.

The crude product above was then coated onto cotion fabric. Swatches of cotton were soaked in a bath containing 8.0 g of the crude product, 45 mL of ethanol, and 45 mL of water for about 2 minutes, and then dried at ambient temperature in air. Then the swatches were cured at 100°C for 45 minutes, soaked in 1.5% liquid detergent zat ambient temperature for 15 minutes, rinsed thoroughly with water, and dried at 50°C.

Chlorination was performed on the swatches using 5% CLOROX at ambient te mperature for 45 minutes. Then the swatches were rinsed thoroughly with water and dried in air at 45°C for 30 minutes. lodometric/thiosulfate titration indicated an averages chlorine loading of 0.114% for the cotton swatches. Although the initial chlorine loadi ng of this coating on cotton is lower than that of the 3-triethoxysilylpropyl-5,5-dimethyldhydantoin coating discussed in Example 4, its stability over time of storage and during washing is expected to be greater.

EXAMPLE 8

PREPARATION OF AND COATING WITH A REPRESENTATIVE SILANE

COMPOUND

To 100 mL of ethanol in a 250 mL flask were added 76.6 g (0.4 mol) of dichloro- 3-chloropropylmethylsil ane (Gelest, Inc.) dropwise at ambient temperature over a period of 30 minutes. The mixture was then refluxed while stirring for 2 hours, and the excess ethanol was removed. The crude product (chloropropyldiethoxymethylsilane), 81.6 g, was obtained as a viscous oil in 96.9% yield. Then 33.2 g (0.2 mol) of the potas sium salt of 5,5-dimethylhydantoin, prepared as described in Example 1, were mixed with 42.1 g (0.2 mol) of the chloropropyldiethoxymethylsilane in 150 mL of anhydrous D>MF in a 500 mL flask, and the reaction mixture was held at 110°C for 8 hours. The p otassium chloride produced in the reaction was removed by filtration, and the DMF by vacuum distillation. The 3-diethoxymethylsilylpropyl-5,5-dimethylhydantoin product «56.47 g, 93.5% yield) was then used without further purification to coat cotton swatch es. The swatches were soaked in a 10% solution of the 3-diethoxymethylsilylpropyl-5,5- dimethylhydantoin in 66 .7% ethanol in water for 2.5 minutes at ambient temperature and then cured in air at 140°C for 15 minutes. The treated swatches were then soaked in 1.5% liquid detergent at ambient temperature for 15 minutes, rinsed thorouglaly with water, and dried in air at 50°C for 30 minutes. The swatches were then chlorimated by soaking in 5% CLOROX at ambient temperature for 45 minutes, rinsed thoroughly with water, and dried in air at 50°C to remove all occluded free chlorine. The chlorine loading was determined by iodometric/thiosulfate titration to be 0.733%. This magnitude of

Joading should give excellent biocidal performance. Furthermore, the increased hydrophobicity of the coating due to replacement of one ethoxy (hydroxy) group by the methyl alkyl group may render the surface rmore resistant to removal during washing than for the coating described in Example 5. Multi-washing cycles have not yet been performed for the coating described in this example. ‘

EXATMPLE 9

PREPARATION OF AND COATING WITH A REPRESENTATIVE SILANE

COMPOUND CONTAINING AN AMINES FUNCTIONAL GROUP IN THE LINKER

To 11.06 g (0.05 mol) of 3-aminopropyltriethoxysilane in 75 mL of ethanol were added 9.52 g (0.05 mol) of 3-(2'-chloroeth=1)-5,5-dimethylhydantoin. The mixture was refluxed for 5 hours, and then the ethanol solvent was removed under reduced pressure to give 18.10g of a brown viscosus oil (87.9% yield of 3-[2-(3- triethoxysilylpropyl)aminoethyl]-5,5-dimetlaylhydantoin hydrochloride which was used without further purification.

A bath containing 5.0 g of the crude product described above in 100 mL of a 50% ethanol/water solution was prepared. Cotton swatches were soaked in the bath for 30 minutes. The swatches were then cured at 95°C for 1 hour, followed by soaking in 1.5% liquid detergent for 15 minutes, and ri nsing thoroughly with water. After drying at 50°C, the swatches were chlorinated with & 5% solution of CLOROX for 5 minutes at ambient temperature. Following a thorough rinse with water, the swatches were held at 50°C in air until dry and then further dried In air overnight at ambient temperature. The chlorine loading was determined to be 0.44%% by iodometric/thiosulfate titration.

The crude product from above was also used to treat sand. Sand (Ottawa Sand

Standard, 20-30 mesh, Fisher Chemicals) was stirred in a bath containing 5% of the crude product and 100 mL of a 50% ethanol/-water solution for 30 minutes at ambient temperature. The treated sand was collected by filtration, cured at 9 5°C in air for 1 hour, soaked in methanol for 10 minutes, rinsed with water, and then dried at 45°C in air for : 2 hours. The sand was then chlorinated bby exposure to 50% CLOROX solution for 15 minutes. After thorough rinsing with water and drying at 50°C in air for 2 hours, the chlorine loading was found to be 0.11% by iodometric/thiosulfate titration. 3 0-

EXAMP LE 10

ODOR CONTROL PROPERTIES OF NON-WOVEN MATRIX COATED WITH A

REPRESENTATIVE CHLORIN_ATED SILANE COMPOUND 3-triethoxysilylpropyl-5,5-dimethylhydantoin, prepared as described in

Example 1, was used to treat non-woven pads consisting of 1 gram of a wood pulp matrix such as is used in diapers and incontinence products. A 5% solution prepared in a distilled water and ethanol 1:1 mixture was applied to pads of the wood pulp fibers, and they were then left to soak for 5 minutes. Excess solution was vacuum suctioned from the pads, which were then dried in an oven at 90°C for two hours. Untreated pads were also subjected to exposure to water and ethanol as controls, and were similarly dried.

Dried coated test samples and uncoeated control pads were then treated by exposure to 10% sodium hypochlorite solution for 15 minutes, after which they were rinsed exhaustively with distilled water, and tkhen vacuum dried to remove any unbound, free chlorine. Additional control pads consisted of wood pulp coated with 3- triethoxysilylpropyl-5,5-dimethylhydantoin but not exposed to the hypochlorite bleach charge. These were rinsed thoroughly along with the test articles, and dried under the same conditions. All dried pads were then left for 48 hours on the bench of a laboratory fume hood before being used in the experiments.

All test and control pads were then exposed to an inoculum designed to generate ammonia odor as a result of bacterial action On urine, simulating events in an infant or adult human diaper. Each inoculum consisted of 1 mL of pooled human female urine, supplemented with 50 mg of urea, mixed witha 0.1 mL of a culture of Proteus mirabilis bacteria, and spread evenly over the surface of” the pad. All pads were then kept at 37°C for six hours in individual containers sealed with parafilm. At the end of this period the samples were removed from the incubator, and the amount of ammonia gas in the head space above each pad was measured as an indicator of the degree of odor generated in the urine. Ammonia measurements were made usiE1g a Drager gas sampling device.

All control samples at the end of the incubation showed more than 30 ppm of ammonia present in the head space above the pads. In the case of the pads coated with 3-triethoxysilylpropyl-5,5-dimethylhydantoin amd halogenated with chlorine, the samples showed no detectable ammonia (lower limit of detection, 0.25 ppm). Control samples had a powerful odor of ammonia, readily detected by the human nose, whereas the samples above the treated test pads had no detectable odor whatsoever.

VA 03/106466 PCE/USO3/18883

The results in this example show that halogenated 3-triethoxysilylpropyl-5.5- dimethylhydantoin can coat wood pulp fibers, and that this coating is highly effective in inhibiting microbial production of odor by suspensions ef bacteria in human urine.

Moreover, once applied to the fibers, this antimicrobial coatang is not readily removed by extensive washing, and subsequent drying. Coated non-w-oven matrices of wood pulp (cellulose) and other fibers should be excellent as components of diapers and incontinence pad devices which will resist the development of odors during normal use.

EXAMPLE 11

ANTIVIRAL PROPERTIES OF SURFACES COATED WITH REPRESENTATIVE A

CHLORINATED SILANE COMPO-UND

Soft and hard surfaces were treated by exposure to a solution of 3-triethoxysilylpropyl-5,5-dimethylhydantoin, as prepared in Example 1, and then halogenated with hypochlorite bleach, prior to being expose=d to a challenge inoculum of a virus (MS2 phage). After passage of measured contact times, recovery of viable infective virus particles was attempted from treated and control surfaces in order to demonstrate the inactivating efficacy of the halogenated sumfaces. Soft surfaces used in these experiments were swatches of woven cotton textiles, and slabs cut from a standard kitchen sponge. Hard surfaces used were porcelain and marble tiles.

For the preparation of antimicrobial textiles, fabric and sponge samples were immersed in 5% solution of 3-triethoxysilylpropyl-5,5-dimethylhydantoin and dried in a convection oven at 90°C for two hours. Chlorination of the coated cellulose materials was accomplished by placing them in the wash chamber of a standard, household washing machine, and processing them through a normal, cold water small load cycle, with one rinse. The washing solution contained 100 mL off CLOROX ULTRA (sodium hypochlorite) per load. This procedure was used to simulate an everyday process that could be used by the consumer to charge coated fibers of treated textiles in a home environment. Drying of each load was done in a dome:stic dryer for 30 minutes at medium heat setting. Successful chlorination of laundere d textiles was confirmed by iodometric/thiosulfate titration of the bound chlorine on swatches of each test material.

Uncoated, normal fabric was used as a control in these experiments. Chlorine contents were calculated and expressed as ppm CI*. These values for cotton were approximately 4000, and for the sponge slabs 1000-2000 ppm,

Hard surface samples were exposed to the 3-triethoxysilylpropyl-5.5- dirmethylhydantoin by using a sponge soaked in the 5% solution, before transfer to a drying oven at 90°C for two hours. Alternatively. test tiles were immersed in the 5% solution, before drying. Chlorination of hard surfaces was accomplished by sponging on a 10% solution of CLOROX bleach and allowineg the samples to stand for up to 20 minutes at room temperature before rinsing exhaustively with distilled water, and all owing them to dry at room temperature. Uncoated tiles were used as controls; they were exposed to hypochlorite before rinsing and dryin g. In addition, coated surfaces that rermained uncharged with chlorine were used as controls in challenge inocula expperiments. Chlorine bound to hard surfaces was destermined by iodometric/thiosulfate titration, and chlorine contents were expressed as pg Cl per square cm. These values wezre 3.3 for the porcelain, and 6.9 for the marble tile.

Challenge inocula for determination of antiviral activity of halogenated coatings we=te made with suspensions of MS2 virus harvested from lawns of Escherichia coli bacterial host cells on trypticase soy agar (TSA) plates using standard methods. The test protocol used was a slightly modified version of Method 100-1998 from the American

As sociation of Textile Chemists and Colorists (AATCC). One mL aliquots of a stock suspension of virus of known titer were applied to swatches of the textiles, 5cm in diameter, for defined contact times (ct) at room temperature. The swatches were then treated with 0.02 M sodium thiosulphate solution to neutralize any remaining active chBorine, and agitated in phosphate buffered water for recovery of infective virus particles. Enumeration of recovered organisms was ac=complished by plating dilutions of thes recovery solution onto E. coli lawns on TSA. Each infective virus particle recovered in #his assay gives rise to a plaque of lysed host cells aftter 24 hours of incubation at 37°C.

By enumeration of visible plaques on the surface of thee agar plates, the proportion of the challenge inocula remaining after contact with the swatches was determined. The results ares expressed as Log 10 reductions in the test sampless when compared to the recovery fro m untreated control swatches.

Inoculation of hard surfaces was done using a protocol which was similar in primciple. It was modified to allow for the retention ©f the challenge inocula in contact with the hard test surface during the entire incubation yoeriod. This was accomplished by cre ating a "sandwich" of the inoculum suspension between a glass microscope cover slip anc the test article. By this means, losses of the inocula by evaporation were avoided,

‘ { and the exaact surface area in contact with the challenge organisms was readily calculated.

Recovery ef infective virus particles was again achieved by agitation. in recovery solution containing thiosulphate neutralizer, and the results again express ed as reductions in

Log 10 titer of the MS2 virus compared to the controls.

Results showed that cellulose textile and sponge samples coated with chlorinated 3-triethoxysilylpropyl-5,5-dimethylhydantoin showed a remarkable capacity to inactivate the tough viral particles of MS2 phage. Reductions of approxamately 4 logs were consistently achieved with cellulose substrates after 24 hours of contact. On hard surfaces ti ters were reduced by approximately 2 logs after contact times of as little as 6 hours. Small non-enveloped viral particles are particularly durables in the environment and generally not highly susceptible to chemical deactivation. These data therefore indicate tlmat antimicrobial surfaces created with halogenated 3-triethoxysilylpropyl-5,5- dimethylh=ydantoin will have demonstrable antiviral functions when used as a means of protecting environmental surfaces against persistent contamination by viruses.

EXAMPLE 12

ANTIFUNGAL PROPERTIES OF SURFACES COATED WITH A

REPRESENTATIVE CHLORINATED SILANE COMPOUND

Soft and hard surfaces were treated by exposure to a solution of 3-triethoxy silylpropyl-5,5-dimethythydantoin, prepared as described in Example I. The soft surfacees used for detection of antifungal properties were woven textiles composed of fibers of psolypropylene, cotton (cellulose), polyester, rayon, and slabs from a cellulose kitchen speonge. Hard surfaces prepared were polyvinylchloride (PVC) sheets, and porcelain and marble tiles. Challenge inocula of prepared surfaces «consisted of aliquots of stock suspensions of spores of Aspergillus niger (ATCC # 1004), a black mold, harvested from cultured lawns on Potato Dextrose Agar (PDA) pmwlates. Methods for preparatior of the halogen charged surfaces and protocols for challenge were as described in Example 11. In this case recovery of Aspergillus was accomplished by the plate dilution mezthod on PDA, and the results were expressed as log 10 reductions compared to the contro 1s. Contact times varied from 24-72 hours, considerabsly longer than was allowed foer other organisms because of the well established durability of black mold spores und €r a wide range of physical and chemical conditions.

ChRorine concentrations on the tested soft surfaces ranged from approximately 800 on the synthetic fibers up to 4000 ppm on ramyon fabrics. Hard surfaces were skiown to range from 4.1 pg per em? for the PVC, ups to 6.9 pg per cm? for the marble tiles. All of the soft and hard surfaces tested showed activity against

Aspergillus black mold. After contact times of 24 hours on cottor, reductions of § logs were observed an mold concentrations, with a 4 log reduction recorded for the sponge slabs. On syntlmetic fibers reductions of 5 logs (polypropylene, pol yester) were observed after 72 hours of contact. On hard surfaces the corresponding log reductions at 72 hours after spore inocualation were 4 (marble), 5 (porcelain), and 4 (vinyl).

These data indicate that effective control of spores of molds can be expected from the use of halogenated coatings of 3-triethoxysilylpropyl-5,5-dirmethylhydantoin on a variety of soft aand hard substrates. It is likely that the disadvanta-ges of odor and black discoloration as.sociated with mold growth can be avoided by use -of these coatings, and their periodic recharge by exposure to free halogen in bleach.

EXAMPLE 13

ANTI-YEAST PROPERTIES OF SURFACES COATED WITH A REPRESENTATIVE

HALOGENATED SILANE

Soft amd hard surfaces were treated by exposure to solutions of 3-triethoxysilylpropyl-5,5-dimethylhydantoin prepared as -descr-ibed in Example 1.

Challenge inocwla for determination of activity directed against yeasts consisted of suspensions of Candida albicans (ATCC # 102301) harvested from PDA plates.

Procedures for goreparation of halogen charged surfaces, plates, anad the exposure of test articles were as described in Example 11. Recovery of viable Cand™ida was accomplished by the plate dilution method on PDA.

All halogen charged surfaces expressed activity agairast inocula of yeast organisms in this test. Reductions in viable yeasts in plate counts were rapid on cotton surfaces (5 logs in two hours of contact), but took longer on synth etic textiles (4 logs in 24 hours on polyester). On hard surfaces reductions of up to 4 logs took place in 6 hours of contact.

These results indicate that antimicrobial coatings consi sting of halogenated 3-triethoxysilylpropyl-5,5-dimethylhydantoin can be expected to exert powerful anti- yeast activities «on soft and hard surfaces. Yeasts, such as Candidea, are known to cause dermal irritatiors in diapers, to cause severe odors, and to colonize= and persist on many surfaces in biofalm slime layers. Products containing these compounds may therefore be useful in reducirg the clinical and nuisance significance of yeast microbes.

EXAMPLE 14

ANTI BACILLUS (BACTERIAL) SPORE ACTIVITY OF SURFACES COATED WITH

A REPRESENTATIVE HALOGENATED SILANE COMPOUND

Soft and hard surfaces were treated by exposure to solutdons of 3-triethoxysilylpropyl-5, 5-dimethylhydantoin, prepared as described in ExampRe 1, and charged with chlorine as described in Example 11. Challenge inocula for the detection of activity versus bacterial spores were prepared from suspensions of spores of Bacillus subtilis. Recovery of viable organisms from challenged surfaces was done on TSA plates, and enumeration vas accomplished by the plate dilution method.

The most signifi cant reductions in viable B. subiilis spore counts or textile substrates were obtained after prolonged exposures on cotton and on polyester (>2 logs in 96 hours), while spores im contact with cellulose sponge were depleted by >5 logs in the same contact period. Om hard surfaces reductions up to 4 logs were seen on marble, vinyl, and porcelain wher contact times were extended to 96 hours.

These results indi cate that chlorine-charged antimicrobial surfaces prepared with 3-triethoxysilylpropyl-5,5 -dimethylhydantoin coatings are effective even on the most resistant stages of bacteria, the spores of anaerobic organisms, provided sufficien tly long contact is allowed. This may be useful in the killing of spores trapped in nom-woven matrix air filters, for example, or in the matrix used for filtration of other protective devices, in air duct surfaces, and in other situations where occupational expossure of workers to such organisms is a hazard, or in the circumstances where de=liberate distribution of such spores may be introduced in acts of biological warfare or bioterrorism.

EXAMPLE 15 ~~ CHLORINE BINDING BY A REPRESENTATIVE SILANE COMPOUND ON HARD

AND SOFT SURFACES

A variety of swrfaces were coated with the 3-triethoxysilylpropyl-5,5- dimethylhydantoin monomner, prepared as described in Example 1, then cured at various temperatures, and chlorinated with dilute solutions of CLOROX using similar procedures to those discussed in previous examples. The surfaces were then evaluated foor their efficacies in loading chlorine either quantitatively by jodometric/thiosulfate titration or qualitatively by colorimetric visualization of exposure of the surfaces to potassium iodide and starch solution. The soft materials bound chlorine in the range of 500 to 5000 ppm expressed as CI*, while the hard surfaces bound it in the range of 5.8 X 1016 to 2.5 X 1017 Cl atoms per cm?.

The following materi als showed efficacy in chlorine binding in the study: glass, sand, ceramics, nylon, acrylonitrile, latex rubber, polyvinylchloride laminates, polyester, > polyurethane, TYVEK, silica gel, chitosan, chitin, Formica, unglazed porcelair, glazed porcelain, aluminum, silicora tubing, clear acrylic films, steel, cement grout, znd latex caulk. In fact, no material tested failed to bind chlorine after treatment.

This example demonstrates a great versatility of chlorine binding to surfaces treated with the 3-triethoxysi_lylpropyl-5.5-dimethylhydantoin monomer. The otlner silane monomers and siloxane poly mers which are the subjects of this invention shouled behave in similar fashion, and if a loading of at least 1 X 1016 atoms of Cl per cm= can be obtained, the surfaces will then exhibit biocidal activity.

EXAMPLE 16

ANTIMICROBIAL ACTIVITY OF TEXTILE SURFACES COATED WITHA

: 15 REPRESENTATIVE ACYCLIC SILANE COMPOUND

Cotton textiles were coated with 3-aminopropyltriethoxysilane by expeosure to aqueous solutions of 5% of this compound, followed by curing the woven fabric -at 100°C for 60 minutes in air, or by" use of a household dryer on high setting for 30 minutes.

Swatches of the treated faberic were charged with chlorine, and then challengged with suspensions of Staphylococcus aureus; enumeration of recovery was accomplishmed using the methods described in Ex ample 11. Chlorine contents of charged oven-cured textiles ranged up to S000 ppm (5 mg per g of material) immediately after drying, but dieninished to 2300 ppm in approximately 14 days at 20°C. Chlorine concentrations 1 n dryer- prepared swatches were nev-er higher than 2500 ppm, even when fresh. Reductions of viable organisms in freshly chlorinated oven-dried swatches were in excess o=f 4 logs, after as little as 15 minutes of contact. Longer contact times (30 minutes) were required to reach this level of efficacy in dryer-cured textiles.

These results indicate that acyclic siloxanes can bind to cellulose text-iles, and when charged with chlorine, can exhibit potent antimicrobial effects, but vevith less durability than with the cyclic N-halamine series. As a general rule, N-Cl or N-B3r bonds are always stronger when im cyclic molecules than they are in their acyclic analogs.

Nevertheless, these propertiess may find utility in the preparation of biocidal textiles that are subject to frequent recharge cycles stich as clothing and certain cleaning tools, such as mops and cloths.

While the preferred embodiment of the invention has been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the: invention.

Claims (84)

The embodiments of the invention in which an exc lusive property or privilege is claimed are defined as follows:

1. A compound having the structure (R-L)y—Si—(R4D4n wherein R1 is independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy. chloro, or C1-C4 ester group, wherein at least one R1 group 1s a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; wherein n = 1, 2, or 3; and wherein R is a heterocyclic N-halamine.

2. The compound of Claim 1, wherein L is a li nker alkylene, amine, or ether group, comprised of 1-13 carbons, 0-3 nitrogen or oxygzen atoms, or L is a linker alkylene group of 1-13 carbons and a carbamate, thiocarbannate, or urea functional group.

3. A compound having the structure T R— L— R= Rj wherein R1, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, whe rein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic N-halamine.

4. A compound having the structure T R— L— 7 R, Rs wherein R1, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, whe rein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; 2nd wherein R is a heterocyclic N-halamine having tthe structure

O Rs R4 N—— N ~~ O wherein IR4 and RS are independently selected from a CL -C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of chlorine or bromine.

5. Thee compound of Claim 4, wherein R1, R2, R3 are independently selected from a methyl, ethyl, phenyl, methoxy, ethoxy, or hydroxy group; wherein at least one of R1, R2, or R3 is a methoxy, ethoxy, or hydroxy group; and wherein R4 and R5 are independently sel ected from a methyl, ethyl, hydroxymethyl or pheny 1 group.

6. The compound of Claim 5, wherein R1, R2, and R3 are a methoxy or ethoxy group; R4& and RS are a methyl group, and L is a linker alkyl ene, amine, or ether group, comprised of 1-7 carbons and 0-1 nitrogen or oxygen atorms, or L is a linker alkylene group, comprised of 1-7 carbons and a carbamate, thicocarbamate, or urea functional group.

7. The compound of Claim 6, wherein R1, R2, R3 are a anethoxy group; X is chlorine; and L is a linker alkylene comprised of 3 carbons.

8. Tle compound of Claim 6, wherein R1, R2, R3 are a zmethoxy group; X is bromine; and L is a linker alkylene comprised of 3 carbons.

9. The compound of Claim 6, wherein R1, R2, and R3 are an ethoxy group; X is chlorine; anc L is a linker alkylene comprised of 3 carbons.

10. TE1e compound of Claim 6, wherein R1, R2, and R3 zare an ethoxy group; X is bromine; and L is a linker alkylene comprised of 3 carbons.

11. The compound of Claim 6, wherein R1, R2, and R3 are a methoxy group; X is chlorine; amid L is a linker amine or ether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

12. The compound of Claim 6, wherein R1, R2, and R3 are a methoxy group; X 1s bromine; and L is a linker amine or ether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

13. The compound of Claim 6, wherein R1, R2, and R3 are an ethoxy group; X is chlorine; and L is a linker amine or ether group comprised of 4 carbons, and nitrogen or o=ygen atom.

14. The compound of Claim 6, wherein R1, R2, and R33 are an ethoxy group; X is bromine; and L is a linker amine or ether group comprised of 4 carbons, and 1 nitrogen or oxygen atom.

15. The compound of Claim 6, wherein R1, R2, and R3 are a methoxy group; X is chlorine; and L is a linker alkylene group comprised of 4 car bons and a carbamate, thiocarbamatte, or urea functional group.

16. The compound of Claim 6, wherein R1, R2, and R33 are a methoxy group; X is bromine; and L is a linker alkylene group comprised of 4 car-bons and a carbamate, thiocarbama-te, or urea functional group.

17. The compound of Claim 6, wherein R1, R2, and R 3 are an ethoxy group; X is chlorine; and L is a linker alkylene group comprised of 4 caxbons and a carbamate, thiocarbama te, or urea functional group.

18. The compound of Claim 6, wherein R1, R2, and R_3 are an ethoxy group; X is bromirxe; and L is a linker alkylene group comprised of 4 caxbons and a carbamate, thiocarbamate, or urea functional group.

19. A compound having the structure T R— L Re Rs whesrein R1, R2, and R3 are independently selected fron a C1-C4 alkyl, aryl, C1-C4 alkaxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or

R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; whesrein L is a linker group; and wherein R is a heterocyclic amine having the structure Rs N R, J wherein R4, RS, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is chlorine or bromine.

20. The compound of Claim 19, wherein R1, R2, and R3 are a. methoxy, ethoxy, or hydroxy group; R4, RS, R6, and R7 are a methyl group; and L is a linker alkylene, amine, or ether group, comprised of [-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbamate, or urea functional group.

21. A compound having the structure (R-L)n Si (R1)an wherein R1 is independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one R1 group is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; whereinn = 1,2, or 3; and wherein R is a heterocyclic amine from at least one of an amide-linked hlmydantoin, imidazolidinone, oxazolidimone, isocyanurate, glycoluril, and triazinedione.

22. A compound having the structure ix Rs 42- AMENDEED SHEET wherein R1, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine from at least one of an amide-linked hydantoin, imi dazolidinone, oxazolidinone, isocyanurate, glycoluril, and trizzinedione.

23. A compound having the structure T R— SR Rs wherein RI], R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy. hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wh erein R is a heterocyclic amine having the structure Oo Rs Raq N—X N re 0 whereim R4 and R5 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethy-1 group; and wherein X is at least one of hydrogen, chlorine or= bromine.

24. A compound having the structure Tr R— L—$—F; Rs whereim R1, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or

(. R3 is a C1-<C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine having the structure A 0 N Ra R Re N 5 R, \ wherein R4, R5, R6, and R7 are‘independently selected from a C1-C4 alkyl, aryl, or hydroxym: ethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

25. The compound of Claim 24, wherein R1, R2, and R3 are a methoxy, ethoxy, or hydroxy group; R4, RS, R6, and R7 are a methyl group; and L is a linker alkylene, anmine, or ether group, comprised of 1-4 carbons, and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbamate, or urea functional group.

26. A compound having the structure i R— LR, Rs wherein R1, R2, and R3 are independently selected fxrom a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of Rl, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester grouap; wherein L is a linker group; and wherein R is a heterocyclic amine having the structure O J R Rg N 5 R; \ X wherein R4, R5, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

27. A compound having the structure ik R—— Re Rs wherein R1, R2, and R3 are independently selected fro m a C1-C4 alkyl, aryl, C1-C+ alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester groups wherein L is a linker group ; and wherein R is a heterocyclic amine having the structure pd O Oo Raq N xX 0) wherein R4 is at least one of a C1-C4 alkyl, aryl, or hyd roxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

28. The compound of Claim 27, wherein R1, R2, arad R3 are a methoxy, ethoxy~, or hydroxy group; R4 is a methyl, ethyl, or hydroxymethyl group; and L is a linker alkylene group, comprised of 1-3 carbons, or L is a Linker alkylene group, compri_sed of 1-3 carbons, and a carbamate, thiocarbamate, or urea. functional group.

29. A compound having the structure ik R— Re Rj; -45- AMENDED SHEET wherein RI, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester gxoup, wherein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1—-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine havEng the structure oO X \ N N— R7 Re Rs Ra wherein R4, R5, R6, and R7 are independ ently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

30. The compound of Claim 29, wherein R1, R2, and R3 are a methoxy, ethoxy or hydroxy group, R4, RS, R6, and R7 are a methyl group; and L is a linker alkylene, amine, or ether group, comprised of 1—4 carbons, and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprased of 1-4 carbons, and a carbamate, thiocarbamate, or urea functional group.

31. A compound having the structure i R— L FR Rs wherein Rl, R2, and R3 are independemtly selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2_ or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L 1s a linker group; and wherein R is a heterocyclic amine havang the structure

X \ Re N N N N oR, X X wherein R4 and RS are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is independently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

32. The compound of Claim 31, whereimm R1, R2, and R3 are a methoxy, ethoxy, or hydroxy group; R4 and RS are a methyl group; and L is a linker alkylene, amine, or ether group, comprised of 1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbamate, or urea functional group.

33. A compound having the structure it R— LR; Rs wherein R1, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine having either structure -47- AMENDED SHEET

O 0 X Jo X Pe ~ ~~ PY 1 bi " 0 | O ENP X wherein X is independently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

34. The compound of Claim 33, wherein R1, R2, and R3 are a methoxy, ethoxy, or hydroxy group; and L is a linker alkylene, amine, or ether group, comprised of 1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbaimate, or urea functional group.

3s. A compound having the structure i R— LR Rs wherein R1, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine having the structure -48- AMENDED SHEET oO ~ Pig ~~ X PY © er, Rs x wherein R4 and RS are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is independently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

36. The compound of Claim 35, wherein RI, R2, and R3 are a methoxy, ethoxy, or hydroxy group; R4 and RS are a methyl group; and L is a linker alkylene, amine, or ether group, comprised of 1-4 carbons and 0-1 nitrogen or oxygen atoms, or L is a linker alkylene group, comprised of 1-4 carbons, and a carbamate, thiocarbamate, or urea functional group.

37. A compound having the structure (Rn Si (Ry )a-n wherein R1 is independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one R1 group is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein 1 = 1, 2, or 3; and wherein R is an amino alkylene or polyamino alkylene group comprising at least one of an N-chloro or an N-bromo group.

38. A compound having the structure -49- AMENDED SHEET

Tt

: . Rj wherein R1, R2, and R3 are independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group, wherein at least one of R1, R2, or R3 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; and wherein R is an amino alkylene or polyamino alkylene group comprising at least one of an N-chloro or an N-bromo group.

39. The compound of €laim 38, wherein R is an amino propyl group.

40. A siloxane, comprising the structure i Hoi R; wherein, n 2 2; R1 is at lesast one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic N-halamine.

41. A siloxane, comprising the structure Foire Ry wherein, n > 2; R1 is at lesast one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic N-halamine having the structure

Oo Rs R4 N— N _ X Oo wherein R4 and RS are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein > is at least one of hydrogen, chlorine or bromine. 42, A siloxane, comprisin g the structure ) Hoi Ry wherein, n > 2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine from at least one of a hydantoin, imidazolidinone, oxazolidinone, isocyanu rate, glycoluril, triazinedione, and piperidine.

43. A siloxane, comprisin g the structure Hogi Ri wherein, n > 2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydreoxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine having the structure -51- AMENDED SEMEET

O Rs R4 N—X N rd Oo wherein R4 and RS are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine or bromine.

44. A siloxane, comprising the structure FOS R1 wherein, n > 2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine having the structure X Ox pais R Rg N 5 R7 \ wherein R4, RS, R6, and R7 are independently selected from a C1-C4 alky 1, aryl, or hydroxymethyl gxoup; and wherein X is at least one of hydrogen, chlorine, or bromine.

45. A siloxane, comprising the structure -52- AMENDED» SHEET

Hoo Rr, wherein, n > 22; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein RR is a heterocyclic amine having the structure © N Rg N Rs R; \ X wherein R4, IRS, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlosrine, or bromine.

46. A siloxane, comprising the structure HOTS R wherein, n = 2; Rl is at least one of a ¢1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and wherein RR is a heterocyclic amine having the struacture pe O Oo Ry N X oO wherein R4 is at least one of a C1-C4 alkyl, aryl, or hydroxymethyl! group; and wherein X is at least one of hydrogen, chlorine, or bromine.

47. A siloxane, comprising the structure ] ro R, wherein, n 2 2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or (C1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine havimg the structure O X AN N N— R7 Re Rg R4 whesrein R4, RS, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxyrmethyl group; and wherein X is at least one of hydrogen, chlordne, or bromine.

48. A siloxane, comprising the structure :

) HOS R; wherein, n 2 2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1 -C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine having the structure X \ Re N N nN / rR X 4X wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; wherein X is independently selected from at least one of hydrogen, chlorine, brornine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

49. A siloxane, comprising the structure FOS Ri wheresin, n 2 2; R1 is at least one of a C1-C4 alkyl, aryl, C 1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; wherein L is a linker group; and whewrein R is a heterocyclic amine having either structure

OQ 0 X BY X Jo ~~ ~~ QO AA X wherein X is independently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

50. A siloxane, comprising the structure Hoi R; wh erein, n > 2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or «C1-C4 ester group; wherein L is a linker group; and whereir R is a heterocyclic aminc havang the structure O 1 0) Ar, Rs X wherein R4 and R5 are independently selected from a C1—C4 alkyl, aryl, or hydroxymethyl group; wherein X is independently selected from at lea st one of hydrogen,

chlorine, brozxmine, or hydroxymethyl; and wherein at least one X i s hydrogen, chlorine, or bromine.

51. A siloxane, comprising the structure ] HOTS R1 wherein, n > 2; R1 is at least one of a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, orC1-C4 ester group; wherein L is a linker group; and wherein R is a heterocyclic amine having the structure i Rs N R, J Re wherein R4, RS, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

52. A siloxane, comprising the structure Hos Ri wherein, n > 2; R1 is at least one of a C1-C4 alkyl, aryl, €1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; and wherein R is an amino alkylene or polyamino alkylene group comprising at least one of an N-chloro or an N-bromo group.

53. A chemically modified substrate, comprising the structure toi wherein, n > 2; L is a linker group; and wherein R is a h_eterocyclic N-halamine.

54. A chemically modified substrate, comprising thes structure Hogi 1 wh erein, n> 2; L is a linker group; and wherein R is a heterocyclic amine having the structure Oo Rs Ry N— N ~~ X Oo wherein R4 and RS are independently selected frorm a C1-C4 alkyl, aryl, or hydroxym_ethyl group; and wherein X is at least one of hydrogen, chlorine or bromine.

55. A chemically modified substrate, comprising th e structure .58- AMENDED SHEET

I I HOTS T wherein, n > 2; L is a linker group; arid wherein R is a heterocyclic amine from at least one of a hydantoin, imidazolidinone, oxazolidinone, isocyanurate, glycoluril, triazinedione, and piperidine.

56. A chemically modified substrate, comprising the structure ) I HOST T wherein, n > 2; L is a linker group; and wherein R is a heterocyclic amine having the structure O Rs Ra N—X N pd 0 wherein R4 and R5 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine or bromine.

-59. AMENDED SHEET

57. A chemically modified substrate, comprisimg the structure ogi wherein, n > 2; L is a linker group; and wherein IR is a heterocyclic amine having the structure X ON ha R Rs N 5 R; wherein R4, RS, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one off hydrogen, chlorine, or bromine.

58. A chemically modified substrate, compris ing the structure HO I wherein, n > 2; L is a linker group; and wherein R is a heterocyclic amine having the structure

Oo / Rg N Rs R5 \ X wherein R4, RS, R6, and R7 are imdependently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

59. A chemically modified substrate, comprising the structure Hogi 1 wherein, n = 2; L is a linker grou p; and wherein R is a heterocyclic amine having the structure rd 0 0 Ry MN @) X wherein R4 is at least one of a «C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

60. A chemically modified substrate, comprising the structure

) BA wherein, n > 2; L is a linker group; and wherein R is a heterocyclic amaine having the structure ©) AN —- g N N—— R7 Re Rs R4 wherein R4, R5, R_6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

61. A chemical Jy modified substrate, comprising the structure THO wherein, n > 2; L is a linker group; and wherein R is a heterocyclic amirae having the structure

X \ Rs N N A R X 4X wherein R4 and RS are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is independently selected from at least one of hydrogen, chlorine, broamine, or hydroxymethyl; and wherein at least one X is hydmogen, chlorine, or bromine.

62. A chemically modified substrate, comprising the structure THOS wherein, n > 2; L is a linker group; and wherein R is a heterocyclic amine h aving either structure O O ~~ ~~ 0 ue X wherein X is independently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

63. A chemically modified substrate, comprising the structure TOT I wherein, n > 2; L is a linker group; amd wherein R is a heterocyclic amine having the structure @)

~~. pig ~~ X N N EN Rs X wherein R4 and RS arc independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is imdependently selected from at least one of hydrogen, chlorine, bromine, or hydroxymethyl; and wherein at least one X is hydrogen, chlorine, or bromine.

64. A chemically modified substrate, comprising the structure

Hogi wherein, n > 2; L is a linker group; and wherein R is a heterocyclic amine having the structure i Rs N R, LT h wherein R4, R5, R6, and R7 are independently selected from a C1-C4 alkyl, aryl, or hydroxymethyl group; and wherein X is at least one of hydrogen, chlorine, or bromine.

65. A chemically modified substrate, comprising the structure (R-Ln(R)yi——Si—(O)g—— wherein m=0, l,or2;n=1,2, or 3;p=1,2,0r 3; and m+ n + p = 4; wherein R is a heterocyclic N-halamine; wherein L is. a linker group; and wherein R1 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group.

66. A chemically modified substmate, comprising the structure (R-Ln(R)mi——Si—(O)g— wherein, m=0,1,0or2;n=1,2,0r 3;p=1, 2, or 3; and n + n+ p = 4; wherein R is a heterocyclic amine from at least one of a hydantoin, imidazolidinone, oxazolidinone, isocyanurate, glycoluril, tria=zinedione, and piperidine; L is a linker group; and R1 is a C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group. -65- : AMENDED SHEET

67. A chemically modified substrate, comprising the structure ) Hogi wherein, n > 2; R is an amino alkylene or polyaminoe alkylene group comprising at least o ne of an N-chloro or an N-bromo group.

68. A chemically modified substrate, comprising: the structure (RIn(R1 Jn——Si—(0)g—— wherein, m=0, l,or2; n=1,2,0r3; p=1, 2, or 3 ; R1 is independently selected from a C1-C4 alkyl, aryl, C1-C4 alkoxy, hydroxy, chloro, or C1-C4 ester group; and R is an am ino alkylene or polyamino alkylene group comprising at least one N-chloro or N-brormo group.

69. A method for making a modified substrate, c omprising: applying a solution of a compound of Claim 1, and water, to a substrate; drying the solution; and curing the substrate at an elevated temperature to provide a modified substrate.

70. The method of Claim 69, wherein the solution further comprises an alcohol.

71. The method of Claim 69, wherein the solutioen is an alkaline solution.

72. A method for making a modified substrate, c omprising: applying a solution of a compound of Claim 21, and water, to a substrate; drying the solution; and curing the substrate at an elevated temperature to provide a modified substrate.

73. A method for making a modified substrate, c-omprising: -66- AMENDED SHEET applying a solution of a silane having a pendant heterocyclic amine, and water, to a substrate; drying the solution; curing the substrate at an elevated temperature; amd halogenating the heterocyclic amine with an exidative halogen compound to provide a modified substrate.

74. A method for making a modified substrate, comprising: applying a solution of a compound of Claim 37, and water, to a substrate; drying the solution; and curing the substrate at an elevated temperature to provide a modified substrate.

75. A method for making a modified substrate, comprising: applying a solution of a silane having a pendant aminoalkylene or polyamino alkylene group, and water, to a substrate; drying the solution; curing the substrate at an elevated temperature; ard halogenating the amino group with an oxidative halogen compound to provide a naodified substrate.

76. A method for making a modified substrates, comprising: applying a solution of a compound of Claim 40, a nd water, to a substrate: drying the solution; and curing the substrate at an elevated temperature to provide a modified substrate.

77. A method for making a modified substrates, comprising; applying a solution of a siloxane of Claim 42, anc water, to a substrate; drying the solution; and curing the substrate at an elevated temperature to provide a modified substrate.

78. A method for making a modified substrate: comprising: applying a solution of a siloxane having a pendarat heterocyclic amine, and water, tO a substrate; drying the solution; curing the substrate at an elevated temperature; an_d halogenating the heterocyclic amine with an oxidative halogen compound to provide a modified sumbstrate.

79. A method for making a modified substrate, comprising: applying a sol ution of a siloxane of Claim 52, and water, to a subs trate; drying the solwtion; and curing the subestrate at an elevated temperature to provide a modifaed substrate.

80. A method for making a modified substrate, comprising: applying a solution of a siloxane having a pendant amino alkylene or polyamine alkylene group, and vvater, to a substrate; drying the sol ution; curing the substrate at an elevated temperature; and halogenating the amino group with an oxidative halogen compo und to provide a modified substrate.

81. A chemical moiety, comprising a silicon atom covalently Ibonded to: an oxygen atom; and a N-containing group through a linker group; wherein the N-containing group is convertible to a N-chleoro-containing or N-bro mo-containing group that renders the chemical moiety biocidal; and wherein the N-containing group is a hydantoin, an imidazolidinone, an oxazoelidinone, a glycoluril, an isocyanurate, a tria zinedione, or a piperi dine group, with the proviso that the hydantoin is limked at the amide group when not biocidal, but linked at either the amide or imide group when biocidal; and wherein the linker group is an alkylene, amine, or ether group, comprised of one to thirteen carbon atoms, zero to three nitrogen or oxygen atoms, or the limker group is an alkylene group of one to thirteen carbon atoms an d a carbamate, thiocarbamate, or urea group.

82. The compounds described in Examples 1,2 and 5 to 9. 63- AMENDED SHEET

83. A chemically modified substrate substantially as herein deescribed and as illustrated with reference to Examples 3, 5 and 10 to 16.

84. A method for making a modified substrate substant@mally as herein described and as illustrated with reference to Examples 3, 4- and 10 to 16. -69- AMENDED SHEET