Controlled release composition incorporating metal oxide glass comprising biologically active compound

Claim 2

A controlled release composition comprising one or more biologically active compounds incorporated into a metal oxide glass having a porous matrix, wherein: (a) the biologicaillty active compound is selected from the group consisting of microbicide, marine antifouling agent, and agricultural pesticide; and (b) the metal oxide glass is prepared by polymerizing one or more metal alkoxide monomers of formula (I) (R.sup.2).sub.n M.sub.1.sup.+m (OR.sup.1).sub.3 (I) optionally in the presence of one or more metal alkoxide monomers of formula (II) (R.sup.5).sub.y R.sup.4 R.sup.3 M.sub.2.sup.30 x OR.sup.1 (II) wherein: M 1 and M 2 are independently selected from Silicon, aluminum, zirconium, titanium, tin, vanadium, and iron; R 1 =(C 1-4 ),ailyl; R 2 , R 3 , R 4 and R 5 are independently selected from OR 1 , (C 1-12 )alkyl, substituted (C 1-12 )alkyl, (C 2-10 )alkenyl, halosubstitutod (C 2-10 )atlkenyl, (C 3-10 )alkyiiyl, halosubstituted (C 3-10 )alkynyl, phenyl, substituted phenyl, (C 7-10 )aralkyl; m and x are independently 3 or 4; n=m-3; and y=x-3; with the proviso that at least one of R 2 , R 3 , or R 5 must be present and is other than OR 1 ; and with the proviso that when the biologically active compound is an agricultural pesticide, at least one metal alkoxide monomer of formula (II) is present where R 3 or R 4 is not OR 1 .

Claim 3

The composition of claim 1 wherein the biologically active compound is a microbicide or marine antifouling agent selected from the group consisting of: 5-chloro-2-methyl-3-isothiazolone; 2-methyl-3-isothiazolone; 2-n-octyl-3-isothiazolone; 4,5-dichloro-2-n-octyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 3-iodo-2-propynyl butyl carbamate; 1,2-dibromo-2,4-dicyanobutane; methylene-bis-thiocyanate; 2-thiocyanomethylthiobenzothiazole; 2,4,5,6-tetrachloroisophthalonitrile; 5-bromo-5-nitro-1,3-dioxane; 2,2-dibromo-3-nitrilopropionamide; 3-bromo-1-chloro-5,5-dimethylhydantoin; 1,2-benzisothiazolin-3-one; 2-methyl-4,5-trimethylene-3-isothiazolone; 3,4,4'-trichlorocarbanilide; manganese ethylenebisdithiocarbamate; zinc dimethyl dithiocarbamate; 2-methyl-4-t-butylamino-6-cyclopropylamino-s-triazine; 2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyl dichlorophenyl urea; zinc ethylenebisdithiocarbamate; copper thiocyanate; 4,5-dichloro-2-n-octyl-3-isothiazolone; N-(fluorodichloromethylthio)-phthalimide; N,N-dimethyl-N'-phenyl-N'-fluorodichloromethylthio-sulfamide; zinc 2-pyridinethiol-1-oxide; tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide; 2 3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine; 3-iodo-2-propynyl butyl carbamate; diiodomethyl p-tolyl sulfone; bis dimethyl dithiocarbamoyl zinc ethylenebisdithiocarbamate; phenyl (bispyridil) bismuth dichloride; 2-(4-thiazolyl)-benzimidazole; pyridine triphenyl borane; phenylamides; halopropargyl compounds; and 2-haloalkoxyaryl-3-isothiazolones.

Claim 4

The composition of claim 2 wherein the biologically active compound is a microbicide selected from the group consisting of: 2-methyl-3-isothiazolone; 5-chloro-2-methyl-3-isothiazolone; 2-n-octyl-3-isothiazolone; 4,5-dichloro-2-n-octyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 1,2-benzisothiazolin-3-one; 2-methyl-4,5-trimethylene-3-isothiazolone; 3-iodo-2-propynyl butyl carbamate; and 3,4,4'-trichlorocarbanilide.

Claim 5

The composition of claim 1 wherein the metal alkoxide monomer of Formula II is selected from the group consisting of: tetramethoxy orthosilicate, tetraethoxy orthosilicate, methyltriethoxy orthosilicate, methyltrimethoxy orthosilicate, phenyltriethoxy orthosilicate, octyltriethoxy orthosilicate, phenyltrimethoxy orthosilicate, dimethyldiethoxy orthosilicate, bis(trimethoxysilyl)methane, bis(triethoxysilyl)ethane, bis(trimethoxysilyl)hexane, 3-butenyltriethoxy silane, methacryloxypropyl triethoxysilane, methacryloxypropyl trimethoxysilane, triethoxyaluminum, methyldiethoxyaluminum, triusopropoxyaluminum, tetraethoxyzirconium, methyltriethoxyzirconium, tetran-butoxyzirconium, tetra-t-butoxyzirconium, tetramethoxytin, tetraethoxytin, tetramethoxyvanadium, tetraethoxyvanadium, tetraethoxytitanium, tetramethoxytitanium, tetraethoxyiron, and mixtures thereof.

Claim 6

The composition of claim 1 wherein the biologically active compound is an agricultural pesticide selected from the group consisting of: dithiocarbamate derivatives; nitrophenol derivatives; heterocyclic structures; halogenated fungicides; fungicidal antibiotics; diphenyl sulfone; dodine; methoxyl; 1-thiocyano-2,4-dinitrobenzene; 1-phenylthiosemicarbazide; thiophanate-methyl; cymoxanil; acylalanines; phenylbenzamide; amino acid derivatives; methoxyacrylates; propamocarb; imazalil; carbendazim; myclobutanil; fenbuconazole; tridemorph; pyrazophos; fenarimol; fenpiclonil; pyrimethanil; carboxylic acid derivatives; carbamic acid derivatives; substituted ureas; substituted triazines; diphenyl ether derivatives; anilides; oxyphenoxy herbicides; uracils; nitriles; dithiopyr; thiazopyr; acephate; aldicarb; alpha-cypermethrin: azinphos-methyl; bifenthrin; binapacryl; buprofezin; carbaryl; carbofuran; cartap; chlorpyrifos; chlorpyrifos methyl; clofentezine; cyfluthrin; cyhexatin; cypermethrin; cyphenothrin; deltamethrin; demeton; demeton-S-methyl; demeton-O-methyl; demeton-S; demeton-S-methyl sulfoxid; demephion-O; demephion-S; dialifor; diazinon; dicofol; dicrotophos; diflubenzuron; dimethoate; dinocap; endosulfan; endothion; esfenvalerate; ethiofencarb; ethion; ethoate-methyl; ethoprop; etrimfos; fenamiphos; fenazaflor; fenbutatin-oxide; fenitrothion; fenoxycarb; fensulfothion; fenthion; fenvalerate; flucycloxuron; flufenoxuron; fluvalinate; fonofos; fosmethilan; furathiocarb; hexythiazox; isazophos; isofenphos; isoxathion; methamidophos; methidathion; methiocarb; methomyl; methyl parathion; mevinphos; mexacarbate; monocrotophos; nicotine; omethoate; oxamyl; parathion; permethrin; phorate; phosalone; phosmet; phosphamidon; pirimicarb; pirimiphosethyl; profenofos; promecarb; propargite; pyridaben; resmethrin; rotenone; tebufenozide; temephos; TEPP; terbufos; thiodicarb; tolclofos-methyl; triazamate; triazophos; and vamidothion.

Claim 7

The composition of claim 1 further comprising an inert material.

Claim 8

A controlled release composition comprising one or more biologically active compounds incorporated into an organo-metal oxide glass having a porous matrix, wherein: the biologically active compound is selected from the group consisting of microbicide, marine antifouling agent, and agricultural pesticide; and the organo-metal oxide glass is prepared by polymerizing, in the presence of a hydroxylic compound which is incorporated into polymer as a crosslinking or a pendant group, one or more metal alkoxide monomers of formula (I); (R.sup.2).sub.n M.sub.1.sup.+m (OR.sup.1).sub.3 (I) optionally in the presence of one or more metal alkoxide mionomers of formula (II): (R.sup.5).sub.y R.sup.4 R.sup.3 M.sub.2.sup.+x OR.sup.1 (II) wherein; M 1 and M 2 are independently selected from silicon, aluminum, zirconium, titanium, tin, vanadium, and iron; R 1 =(C 1-4 )alkyl; R 2 , R 3 , R 4 and R 5 are independently selected from OR 1 , (C 1-12 )alkyl, substituted (C 1-12 ))alkyl, (C 2-10 )alkrenyl, halosubstituted (C 2-10 )alkenyl, (C 3-10 )alkynyl, halosubtittuted (C 3- C 10 )alkynyl, phenyl, substituted phonyl, (C 7-10 )aralkyl; m and x are independently 3 or 4; n=m-3; and y=x-3; and wherein the hydroxylic compound is selected from the group consisting of (C 4-20 )alkyl alcohols; (C 7-10 )aralkyl alcohols; (C 2-20 )glycols; poly(ethylene glycol) alkyl ethers; polyethylene glycol) aralkyl ethers; and poly(ethylene glycol) Bryl ethers.

Claim 9

A controlled release composition comprising one or more biologically active compounds incorporated into an organo-metal oxide glass having a porous matrix, wherein: the biologically active compound is selected from the group consisting of microbicide, marine antifouling agent, and agricultural pesticide; and the organo-metal oxide glass is prepared by polymerizing, in the presence of a hydroxylic compound which is incorporated into polymer as a crosslinking or a pendant group, one or more metal alkoxide monomers of formula (I); (R.sup.2).sub.n M.sub.1.sup.+m (OR.sup.1).sub.3 (I) optionally in the presence of one or more metal alkoxide mionomers of formula (II): (R.sup.5).sub.y R.sup.4 R.sup.3 M.sub.2.sup.+x OR.sup.1 (II) wherein; M 1 and M 2 are independently selected from silicon, aluminum, zirconium, titanium, tin, vanadium, and iron; R 1 =(C 1-4 )alkyl; R 2 , R 3 , R 4 and R 5 are independently selected from OR 1 , (C 1-12 )alkyl, substituted (C 1-12 ))alkyl, (C 2-10 )alkrenyl, halosubstituted (C 2-10 )alkenyl, (C 3-10 )alkynyl, halosubtittuted (C 3- C 10 )alkynyl, phenyl, substituted phonyl, (C 7-10 )aralkyl; m and x are independently 3 or 4; n=m-3; and y=x-3; and wherein the hydroxylic compound is selected from the group consisting of (C 4-20 )alkyl alcohols; (C 7-10 )aralkyl alcohols; (C 2-20 )glycols; poly(ethylene glycol) alkyl ethers; polyethylene glycol) aralkyl ethers; and poly(ethylene glycol) Bryl ethers.

Claim 10

The composition of claim 7 wherein the biologically active compound is selected from the group consisting of: 5-chloro-2-methyl-3-isothiazolone; 2-methyl-3-isothiazolone; 2-n-octyl-3-isothiazolone; 4,5-dichloro-2-n-octyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 3-iodo-2-propynyl butyl carbamate; 1,2-dibromo-2,4-dicyanobutane; methylene-bis-thiocyanate; 2-thiocyanomethylthiobenzothiazole; 2,4,5,6-tetrachloroisophthalonitrile; 5-bromo-5-nitro-1,3-dioxane; 2,2-dibromo-3-nitrilopropionamide; 3-bromo-1 -chloro-5,5-dimethylhydantoin; 1,2-benzisothiazolin-3-one; 2-methyl-4,5-trimethylene-3-isothiazolone; 3,4,4'-trichlorocarbanilide; dithiocarbamate derivatives; nitrophenol derivatives; heterocyclic structures; halogenated fungicides; fungicidal antibiotics; diphenyl sulfone; dodine; methoxyl; 1-thiocyano-2,4-dinitrobenzene; 1-phenylthio-semicarbazide; thiophanate-methyl; cymoxanil; acylalanines; phenylbenzamide; amino acid derivatives; methoxyacrylates; propamocarb; imazalil; carbendazim; myclobutanil; fenbuconazole; tridemorph; pyrazophos; fenarimol; fenpiclonil; pyrimethanil; carboxylic acid derivatives; carbamic acid derivatives; substituted ureas; substituted triazines; diphenyl ether derivatives; anilides; oxyphenoxy herbicides; uracils; nitriles; dithiopyr; thiazopyr; acephate; aldicarb; alpha-cypermethrin; azinphos-methyl; bifenthrin; binapacryl; buprofezin; carbaryl; carbofuran; cartap; chlorpyrifos; chlorpyrifos methyl; clofentezine; cyfluthrin; cyhexatin; cypermethrin; cyphenothrin; deltamethrin; demeton; demeton-S-methyl; demeton-O-methyl; demeton-S; demeton-S-methyl sulfoxid; demephion-O; demephion-S; dialifor; diazinon; dicofol; dicrotophos; diflubenzuron; dimethoate; dinocap; endosulfan; endothion; esfenvalerate; ethiofencarb; ethion; ethoate-methyl; ethoprop; etrimfos; fenamiphos; fenazaflor; fenbutatin-oxide; fenitrothion; fenoxycarb; fensulfothion; fenthion; fenvalerate; flucycloxuron; flufenoxuron; fluvalinate; fonofos; fosmethilan; furathiocarb; hexythiazox; isazophos; isofenphos; isoxathion; methamidophos; methidathion; methiocarb; methomyl; methyl parathion; mevinphos; mexacarbate; monocrotophos; nicotine; omethoate; oxamyl; parathion; permethrin; phorate; phosalone; phosmet; phosphamidon; pirimicarb; pirimiphos-thyl; profenofos; promecarb; propargite; pyridaben; resmethrin; rotenone; tebufenozide; temephos; TEPP; terbufos; thiodicarb; toldlofos-methyl; triazamate; triazophos; and vamidothion.

Claim 11

The composition of claim 7 wherein the biologically active compound is a microbicide selected from the group consisting of: 2-methyl-3-isothiazolone; 5-chloro-2-methyl-3-isothiazolone; 2-n-octyl-3-isothiazolone; 4,5-dichloro-2-n-octyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 1,2-benzisothiazolin-3-one; 2-methyl-4,5-trimethylene-3-isothiazolone; 3-iodo-2-propynyl butyl carbamate; and 3,4,4'-trichlorocarbanilide.

Claim 14

The method of claim 10 wherein the biologically active compound is selected from the group consisting of 5-chloro-2-methyl-3-isothiazolone; 2-methyl-3-isothiazolone; 2-n-octyl-3-isothiazolone; 4,5-dichloro-2-n-octyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 3-iodo-2-propynyl butyl carbamate; 1,2-dibromo-2,4-dicyanobutane; methylene-bis-thiocyanate; 2-thiocyanomethylthiobenzothiazole; 2,4,5,6-tetrachloroisophthalonitrile; 5-bromo-5-nitro-1,3-dioxane; 2,2-dibromo-3-nitrilopropionamide; 3-bromo-1 -chloro-5,5-dimethylhydantoin; 1,2-benzisothiazolin-3-one; 2-methyl-4,5-trimethylene-3-isothiazolone; 3,4,4'-trichlorocarbanilide; dithiocarbamate derivatives; nitrophenol derivatives; heterocyclic structures; halogenated fungicides; fungicidal antibiotics; diphenyl sulfone; dodine; methoxyl; 1-thiocyano-2,4-dinitrobenzene; 1-phenylthiosemicarbazide; thiophanate-methyl; cymoxanil; acylalanines; phenylbenzamide; amino acid derivatives; methoxyacrylates; propamocarb; imazalil; carbendazim; myclobutanil; fenbuconazole; tridemorph; pyrazophos; fenarimol; fenpiclonil; pyrimethanil; carboxylic acid derivatives; carbamic acid derivatives; substituted ureas; substituted triazines; diphenyl ether derivatives; anilides; oxyphenoxy herbicides; uracils; nitriles; dithiopyr; thiazopyr; acephate; aldicarb; alpha-cypermethrin; azinphos-methyl; bifenthrin; binapacryl; buprofezin; carbaryl; carbofuran; cartap; chlorpyrifos; chlorpyrifos methyl; clofentezine; cyfluthrin; cyhexatin; cypermethrin; cyphenothrin; deltamethrin; demeton; demeton-S-methyl; demeton-O-methyl; demeton-S; demeton-S-methyl sulfoxid; demephion-O; demephion-S; dialifor; diazinon; dicofol; dicrotophos; diflubenzuron; dimethoate; dinocap; endosulfan; endothion; esfenvalerate; ethiofencarb; ethion; ethoate-methyl; ethoprop; etrimfos; fenamiphos; fenazaflor; fenbutatin-oxide; fenitrothion; fenoxycarb; fensulfothion; fenthion; fenvalerate; flucycloxuron; flufenoxuron; fluvalinate; fonofos; fosmethilan; furathiocarb; hexythiazox; isazophos; isofenphos; isoxathion; methamidophos; methidathion; methiocarb; methomyl; methyl parathion; mevinphos; mexacarbate; monocrotophos; nicotine; omethoate; oxamyl; parathion; permethrin; phorate; phosalone; phosmet; phosphamidon; pirimicarb; pirimiphos-ethyl; profenofos; promecarb; propargite; pyridaben; resmethrin; rotenone; tebufenozide; temephos; TEPP; terbufos; thiodicarb; tolclofos-methyl; triazamate; triazophos; and vamidothion.

Claim 17

The method of claim 12 wherein the biologically active compound is selected from the group consisting of: 5-chloro-2-methyl-3-isothiazolone; 2-methyl-3-isothiazolone; 2-n-octyl-3-isothiazolone; 4,5-dichloro-2-n-octyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 4,5-dichloro-2-cyclohexyl-3-isothiazolone; 3-iodo-2-propynyl butyl carbamate; 1,2-dibromo-2,4-dicyanobutane; methylene-bis-thiocyanate; 2-thiocyanomethylthiobenzothiazole; 2,4,5,6-tetrachloroisophthalonitrile; 5-bromo-5-nitro-1,3-dioxane; 2,2-dibromo-3-nitrilopropionamide; 3-bromo-1-chloro-5,5-dimethylhydantoin; 1,2-benzisothiazolin-3-one; 2-methyl-4,5-trimethylene-3-isothiazolone; 3,4,4'-trichlorocarbanilide; dithiocarbamate derivatives; nitrophenol derivatives; heterocyclic structures; halogenated fungicides; fungicidal antibiotics; diphenyl sulfone; dodine; methoxyl; 1-thiocyano-2,4-dinitrobenzene; 1-phenylthio-semicarbazide; thiophanate-methyl; cymoxanil; acylalanines; phenylbenzamide; amino acid derivatives; methoxyacrylates; propamocarb; imazalil; carbendazim; myclobutanil; fenbuconazole; tridemorph; pyrazophos; fenarimol; fenpiclonil; pyrimethanil; carboxylic acid derivatives; carbamic acid derivatives; substituted ureas; substituted triazines; diphenyl ether derivatives; anilides; oxyphenoxy herbicides; uracils; nitriles; dithiopyr; thiazopyr; acephate; aldicarb; alpha-cypermethrin; azinphos-methyl; bifenthrin; binapacryl; buprofezin; carbaryl; carbofuran; cartap; chlorpyrifos; chlorpyrifos methyl; clofentezine; cyfluthrin; cyhexatin; cypermethrin; cyphenothrin; deltamethrin; demeton; demeton-S-methyl; demeton-O-methyl; demeton-S; demeton-S-methyl sulfoxid; demephion-O; demephion-S; dialifor; diazinon; dicofol; dicrotophos; diflubenzuron; dimethoate; dinocap; endosulfan; endothion; esfenvalerate; ethiofencarb; ethion; ethoate-methyl; ethoprop; etrimfos; fenamiphos; fenazaflor; fenbutatin-oxide; fenitrothion; fenoxycarb; fensulfothion; fenthion; fenvalerate; flucycloxuron; flufenoxuron; fluvalinate; fonofos; fosmethilan; furathiocarb; hexythiazox; isazophos; isofenphos; isoxathion; methamidophos; methidathion; methiocarb; methomyl; methyl parathion; mevinphos; mexacarbate; monocrotophos; nicotine; omethoate; oxamyl; parathion; permethrin; phorate; phosalone; phosmet; phosphamidon; pirimicarb; pirimiphos-ethyl; profenofos; promecarb; propargite; pyridaben; resmethrin; rotenone; tebufenozide; temephos; TEPP; terbufos; thiodicarb; tolclofos-methyl; triazamate; triazophos; and vamidothion.

Claim 18

A method of controlling or inhibiting the growth of pests at a locus comprising introducing into or onto the locus to be protected an effective amount of the compositions of claim 1.

Claim 19

A method of controlling or inhibiting the growth of pests at a locus comprising introducing into or onto the locus to be protected an effective amount of the compositions of claim 7.