WO1997017847A1 - Polysaccharide ether esters which release active ingredients - Google Patents

Abstract

The invention relates to systems comprising polysaccharide ether esters and agrochemical active ingredients which optionally contain common additives and are biodegradable.

Description

 Drug-releasing polysaccharide ether esters

The present invention relates to biodegradable active ingredient-releasing systems made from thermoplastically processable polysaccharide ether esters and agrochemical active ingredients and their use for plant treatment.

The incorporation of active ingredients into thermoplastically processable polymers is known. However, it cannot be predicted from the outset whether an active substance-polymer system will release the active substance to a sufficient extent and over a sufficiently long time. In addition, after the end of the treatment, the polymer carrier with residual active ingredient remains on the plants or in the soil and has to be disposed of in a complex manner (see US Pat. No. 4,743,448, US Pat. No. 4,666,767, US Pat. No. 5,201,925).

Biodegradable carrier systems which release agrochemical active substances have also become known (see WO 91/3940, EP-A 344 1 18, EP-A 404 727,

DE-A 3 936 191). However, with these systems, drug release is still completely satisfactory.

It would therefore be desirable to use a polymer that is as completely biodegradable and thermoplastically processable as a carrier for active agrochemical substances and that has sufficient mechanical properties in addition to good release properties of the active substance even without the addition of synthetic polymers.

The present invention therefore relates to systems composed of polysaccharide ether esters and agrochemical active substances, which may contain customary additives.

As polysaccharide ether esters, those of the following general structural formula may be mentioned

Polysaccharide OR where Polysaccharide-O represent the substituted OH groups of a polymeric saccharide unit and

R is either a mono- and / or polymeric substituent of structure X:

X = -A-B-A'- where

A and A 'represent a linear polyether chain of the following structures:

A = (-DO) _n and A = (-DO) _m H in the

D represents a linear aliphatic or aromatic branched or unbranched chain having 2 to 11 carbon atoms and n is an integer equal to or greater than 0, m is an integer equal to or greater than 1, and

in der E ein aromatisches oder aliphatisches Kohlenstoffgerust das gegebenenfalls mit weiteren Substituenten versehen sein kann ist, wobei das Verhältnis von A' zu B gleich oder größer 0, 1 ist, oder R ist entsprechend dem Substitutionsgrad pro Saccharideinheit mit X gleich H (Wasserstoff) und/oder Alkyl mit 1 bis 4, vorzugsweise 1 bis 2 C- Atomen. Diese Polysaccharidetherester werden hergestellt, indem zuerst das Polysaccharid mit Alkalilauge aktiviert wird. Diese Aktivierung kann durch die Synthese und Isolierung eines Alkalipolysaccharids geschehen oder alternativ durch Herstellung eines wasserfeuchten Alkalipolysaccharids oder einer Suspension des Polysaccharids in wassermischbaren Lösungsmitteln und anschließender Zugabe einer wassrigen Alkalilösung. B is a dicarboxylic acid of the following structure:

in which E is an aromatic or aliphatic carbon skeleton which may optionally be provided with further substituents, the ratio of A 'to B being equal to or greater than 0.1, or R corresponding to the degree of substitution per saccharide unit with X being H (hydrogen) and / or alkyl with 1 to 4, preferably 1 to 2 carbon atoms. These polysaccharide ether esters are prepared by first activating the polysaccharide with an alkali metal hydroxide solution. This activation can take place by the synthesis and isolation of an alkali polysaccharide or alternatively by producing a water-moist alkali polysaccharide or a suspension of the polysaccharide in water-miscible solvents and then adding an aqueous alkali solution.

Also activating treatments such as B. with liquid ammonia or ultrasound are possible.

Before the etherification and esterification reaction begins, the water and / or solvent-moist alkali polysaccharide is subjected to a solvent wash, as a result of which a defined alkali content can be set.

The activation can also be carried out by spraying on an aqueous alkali lye. The epoxide is grafted onto the cellulose activated in this way and the water present in the reaction mixture is preferably distilled off before the reaction with the dicarboxylic acid anhydride.

The reaction with the dicarboxylic acid anhydrides is carried out in suspension media. It is surprising that the dicarboxylic acid anhydride reacts in a two-phase reaction (liquid-solid) with the polysaccharide in standard organic solvents, since comparable reactions could only be carried out in activating and strongly swelling solvents such as acetic acid and pyridine.

As an alternative to activation with alkali metal hydroxide solution, the reaction of the polysaccharide with the dicarboxylic acid anhydride can also be carried out with organic amines. For this purpose, the polysaccharide or the alkali-free cellulose ether is stirred in the suspension medium with the amine as catalyst and the dicarboxylic acid anhydride is added to this suspension or solution. This creates the dicarboxylic acid monoester of the polysaccharide or the polysaccharide ether.

In suspension media such as DMSO, DMAc or DMF, the product goes into solution during the reaction with the dicarboxylic acid anhydride. In the next step, the still free carboxyl group of the resulting dicarboxylic acid monoester is reacted with alkylene oxides. The proportions can be chosen so that the free carboxylic acids are fully or only partially reacted with alkylene oxide. The free acid groups can also serve as starters for a polymeric ether structure.

If amine was used for activation, it also serves as a catalyst in this reaction step. Accordingly, small amounts of amine can be added at this point when alkali is activated.

For the synthesis is technically accessible cellulose, such as. B. wood pulp and cotton sinters of any molecular weight or other cellulose-containing products such as Sawdust, suitable. Furthermore, native and soluble starches of any provenance and pretreatment as well as amylose, amylopectin, alginate, glycogen, carraghenate, chitin, chitosan, guar as splits or flour, locust bean gum, pectin, xylan, xanthan, pullulan, dextran and laevan are suitable. Be used as polysaccharide cellulose ethers is cellulose ethers are suitable as methyl cellulose or ethyl cellulose, or benzyl cellulose with average degrees of substitution less than / equal to 2.5, hydroxyethyl cellulose, hydroxypropyl cellulose, dihydroxypropyl cellulose, hydroxybutylcellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylhydroxybutyl, Ethylhydroxypropylcellulose, ethyl, carboxyalkyl, sulfoalkyl cellulose, cyanoethyl cellulose and their mixed ethers.

Suitable dicarboxylic acid anhydrides are anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, trimellitic anhydride and isatoic anhydride. Preferred epoxides are monoepoxides such as ethylene oxide, propylene oxide,

1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, stearic acid glycidyl ether, epoxy butyl stearate, lauryl glycidyl ether, glycidyl methyl ether , Glycidyl ethyl ether, glycidyl propyl ether, glycidyl butyl ether, glycidyl tertiary butyl ether, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, butadiene monoxide, glycidol, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane-3-glycidoxysilane-3-glycidoxysilane-3-glycidoxysilane-3 epoxypropane, diethyl-ß, γ-epoxypropyl phosphate, 4- (2,3-epoxypropyl) morpholine, styrene oxide and phenoxypropylene oxide.

Details on the preparation of the polysaccharide ether esters can be found in DE-A 4 404 840 or EP application 95 101 474, the contents and examples of which are hereby expressly incorporated by reference.

Insecticides, fungicides and herbicides may be mentioned as active agrochemicals.

In the case of insecticides, preference should be given to organic phosphorus compounds such as phosphoric acid esters, carbamates, pyrethroids, urea derivatives such as benzoylureas, triazines, agonists or antagonists of the nicotinogenic acetylcholine receptors of insects.

The pyrethroids include:

Allethrin = 2,2-dimethyl-3- (2-methyl-1-propenyll) cyclopropane carboxylate of 2-methyl-4-oxo-3- (2-propenyl) -2-cyclopenten-1-yl. Barthrin = 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropane carboxylate of (6-chloro-1,3-benzodioxol-5-yl) methyl.

Bioresmethrin = 2,2,3- (2-methyl-l-propenyl) carboxylate of [5- (phenyl-methyl) -3-furanyl] methyl.

Bromethrin = 2- (2,2-dibromovinyl) -3,3-dimethylcyclopropane carboxylate of (5-benzyl-3-furyl) methyl.

Cycloethrin = 2,2-dimethyl-3- (2-methyl-propenyl) -cyclopropane-carboxylate of 3- (2-cyclopenten-1-yl) -2-methyl-4-oxo-2-cyclopenten-1-yl.

Dimethrin = 2,2,3- (2-methyl-1-propenyl) carboxylate of 2,4-dimethylbenzyl.

Pyresmethrin = trans - (+) - 3-carboxy-α, 2,2-trimethylcyclopropane-acrylate of 3 - [(5-benzyl-3-furyl) methyl] methyl. Resmethrin = 2,2,3- (2-methyl-1-propenyl) carboxylate of (5-benzyl-3-furyl) methyl.

Tetramethrin = 2,2,3- (2-methyl-1-propenyl) carboxylate of (1,3,4,5,6,7-hexahydro-1,3-di-oxo-2H-isoindol-2-yl ) methyl. K-othrin = 2,2-dimethylcyclopropane carboxylate of (5-benzyl-3-furyl) methyl trans - (+) - 3-cyclopentylidene-methyl.

Permethrin (FMC 33297) (NRDC 143) = 2,2-dimethylcyclopropane carboxylate of m-phenoxybenzyl-cis-trans - (+) - 3- (2,2-dichlorovinyl).

Cinerin I = 2,2,3- (2-methyl-1-propenyl) carboxylate of 2- (2-butenyl) -4-hydroxy-3-methyl-2-cyclopenten-1-one.

Pyrethrin I = 2,2,3- (2-methyl-1-propenyl) carboxylate of 4-hydroxy-3-methyl-2- (2,4-pentadienyl) -2-cyclopenten-1-one.

Cinerin II = 2,2,3- (2-methyl-1-propenyl) carboxylate of 2- (2-butenyl) -4-hydroxy-3-methyl-2-cyclopenten-1-one. Pyrethrin II = 2,2,3- (2-methyl-1-propenyl) carboxylate of 4-hydroxy-3-methyl-2- (2,4-pentadienyl) -2-cyclopenten-1-one.

Jasmohn I = 4 ', 5'-dihydropyrethrin-I.

Jasmolin II = 4 ', 5'-dihydropyrethrin-II.

Biothanometrin = 2,2-dimethyl-3- (2-cyclopentylvinyl) -cyclopropane-carboxylate of (5-benzyl-3-furyl) methyl.

Bioethanomethrin = 2- (2,2-dichlorovinyl) -3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) methyl.

Cypermethrin = 2- (2,2-dichlorovmyl) -3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) -cynomethyl. Decamethrin = 2- (2,2-dibromovinyl) -3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) -cyanomethyl.

ES-56 = 2,2,3- (2-methyl-1-propenyl) carboxylate of 2,3-dihydrofuran.

Fenpropanate (S-3206) = 2,2-dimethyl-3,3-dimethyl-cyclopropane-carboxylate of (3-diphenyl ether) cyanomethyl.

Fenvalerate (S-5602) = [(p-chlorophenyl) - (isopropyl)] acetate of (3-diphenyl ether) cyanomethyl.

(S-5439) = [(p-chlorophenyl) - (isopropyl)] - acetate of (3-diphenyl ether) methyl.

Cis-methrin = 2,2,3- (2-methyl-1-propenyl) carboxylate of 5-benzyl-3-furylmethyl. Phenothrin = 2,2,3- (2-methyl-1-propenyl) carboxylate of (3-phenoxybenzyl) methyl.

Cyfluthrin = 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate of 4-fluoro-3-diphenylether-cyanomethylol.

The carbamates include:

Aldicarb = 2-methyl-2- (methylthio) propanol-O - [(methylamino) carbonyi] oxime. Aldoxycarb = 2-methyl-2- (methylsulfonyl) propanol-O- [methylamino) carbonyl] oxime.

Aminocarb = methyl carbamate of 4-dimethylamino-3-methylphenyl.

Bendiocarb = N-methyl carbamate of 2,2-dimethyl-benzo-1,3-dioxol-4-yl.

Bufencarb = methyl carbamate of 3- (1-methylbutyl) phenyl and methyl carbamate of 3- (1-ethylpropyI) phenyl (3: 1).

Butacarb = methyl carbamate of 3,5-bis (1,1-dimethylethyl) phenyl. Butocarboxime = 3-methylthio-2-butane-O - [(methylamino) carbonyl] oxime.

Butoxycarboxime = 3-methylthio-2-butanone-O - [(methylamino) carbonyl] oxime.

2-sec-butylphenylmethyl carbamate = methyl carbamate of 2- (1-methylpropyl) phenyl. Carbanolates = methyl carbamates of 2-chloro-4,5-dimethylphenyl.

Carbaryl = methyl carbamate of 1-naphthalenyI.

Carbofuran = methyl carbamate of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl.

Cartap = carbamothicate of S, S '- [2- (dimethylamino) -1,3-propanediyl].

Decarbofuran = methyl carbamate of 2,3-dihydro-2-methylbenzofuran-7-yl. Dimetilan = dimethyl carbamate des - [(dimethylamino) carbonyl] -5-methyl-1H-pyrazol-3-yl.

Dioxocarb = methyl carbamate of 2- (1,3-dioxolan-2-yl) phenyl.

Ethiofencarb = methyl carbamate of 2-ethylthiomethylphenyl

Fenethacarb = methyl carbamate of 3,5-diethylphenyl formetanate = methyl carbamate of 3-dimethylaminoethylene aminophenyl

Formparanate = methyl carbamate of 3-methyl-4-dimethylamino-methylenaminophenyl

Isoprocarb = methyl carbamate of 2-isopropylphenyl.

Methiocarb = methyl carbamate of 3,5-dimethyl-4-methylthiophenyl. Methomyl = methyl N - [[(methylamino) carbonyl] oxy] ethane imidothioate. Mexacarbate = methyl carbamate of 4-dimethylamino-3,5-dimethylphenyl.

Nabam = 1,2-ethanediylbis (carbamodithioate) disodique.

Nitrile acarb = to Cl ₂ , (4,4-dimethyl-5-methylamino-carbonyloximino) pentanenitrile.

Oxamil = Memyl 2- (dimethylamino) -N - [[(methylamino) carbonyl] oxy] -2-oxoethaniminothioate.

Pirimicarb = dimethyl carbamate of 2- (dimethylamino) -5,6-dimethyl-4-pyrimidinyl.

Promecarb = methyl carbamate of 3-methyl-5- (1-methylethyl) phenyl.

Propoxur = methyl carbamate of 2- (1-methylethoxy) phenyl. Thiofanox = 3,3-dimethyl- (methylthio) -2-butanone-O - [(methylamino) carbonyl] oxime

Thiocarboxime = carbamate of 1- (2-cyanoethylthio) ethylene aminomethyl.

Thiram = diamides of acid tetramethylthoperoxydicarbonide.

Trimethylphenylmethyl carbamate = methyl carbamate of 3,4,5-trimethylphenyl. 3, 4-xylylmethyl carbamate = methyl carbamate of 3,4-dimethylphenyl.

3,5-xylylmethyl carbamate = methyl carbamate of 3,5-dimethylphenyl.

Organophosphorus compounds include: Acephate = O, S-Dimethylacetylphosphoroaminothioat.

Amidithione = S- (N-2-methoxyethylcarbamoylmethyl) dimethylphosphorodithioate. Amiton = S- [2- (diethylamino) ethyl] diethylphosphorothioate. Athidation = O, O-Diethyl-S-5-methoxy-2-oxo-1,3,4-thiadiazol-3-yl-methylphosphorodithioate.

Azinphos-ethyl = O, O-Diethyl-S - [(4-oxo-1,2,3-benzotriazin-3 (4H) -yl) methyl] phosphorodithioate. Azinphos-methyl = O, O-Dimethyl-S - [(4-oxo-1,2,3-benzotriazin-3 (4H) -yl) methyl] phosphorodithioate.

Azothioate = O, O-Dimethyl-O- [p- (p-chlorophenylazo) phenyl] phosphorothioate.

Bromophos = = - (4-bromo-2,5-dichlorophenyl) -O, O-dimethylphosphorothioate.

Bromophos-ethyl = = - (4-bromo-2,5-dichlorophenyl) -O, O-diethylphosphorothioate butonate = O, O-dimethyl-1-butyryl-1-butyryloxy.

Carbophenothione = S - [[(4-chlorophenyl) thio] methyl] -O, O-diuethylphosphorodithioate.

Chlorfenvinphos = 2-chloro-1- (2,4-dichlorophenyl) ethenyl phosphate of diethyl.

Chlormephos = S-chloromethyl-O, O-diethylphosphorodithioat Chlorphoxim = 7- (2-chlorophenyl) -4-ethoxy-3,5-dioxa-6-aza-4-phosphaoct-6-en-8-nitril-4-sulfur .

Chlorprazophos = O, O-Diethyl-O-3-chloro-7-methyl-pyrazolo [1,5-a] pyrimidin-2-yl-phosphorothioate.

Chlorpyrifos = O, O-Diethyl-0,3,5,6, -trichloro-2-pyridylphosphorothioat. Chlorpyrifos-methyl = O, O-dimethyl-O, 3,5,6-trichloro-2-pyridylphosphorothioate.

Chlorothiophos = O-2,5-dichloro-4- (methylthio) phenyl-O, O-diethylphosphorothioate

Coumaphos = O-3-chloro-4-methylcoumarin-7-yl-O, O-diethylphosphorothioate. Coumithoate = O, O-diethyl-O- (7,8,9,10-tetrahydro-6-oxo-6H-dibenzo [b, d] pyran-3-yl-phosphorothioate.

Cortoxyphos = 1-phenylethyl (E) -3 - [(dimethoxyphosphonyl) oxy] -2-butenoate.

Cruformate = 2-chloro-4- (1,1-dimethylethyl) phenylmethyl methyl phosphoramidate. Cyanofenphos - O-4-cyanophenyl-O-ethylphenylphosphonothioat.

Cyanophos = O-4-cyanophenyl-O, O-dimethylphosphorothioate.

Cyanthoate = O, O-Diethyl-S- [N- (1-cyano-1-methylethyl)] carbamoylmethylphosphorothioate.

Demephion = O, O-Dimethyl-O-2-methylthioethylphosphorothioat and the OkO-Dimethyl-S-2-methylthioethylphosphorothioat.

Demeton = O, O-Diethyl-O-2-ethylthioethylphosphorothioat and O, O-Diethyl-S-2-ethylthioethylphosphorothioat

Demeton-S-methyl = O, O-Dimethyl-S-2-ethylthioethylphosphorothioat.

Demetone S-methylsulfone = S-2-ethylsulfonylethyl-O, O-dimethylphosphorothioate. Demeton-S = O, O-Diethyl-S- [2- (ethylthio) ethyl] phosphorothioate.

Demetone-O = O, O-diethyl-O- [2- (ethylthio) ethyl] phosphorothioate.

Demetone-O-methyl = O, O-dimethyl-O- [2- (ethylthio) ethyl] phosphorothioate.

Dialifos = S- [2-chloro-1- (1,3-dihydro-1,3-dioxy-2H-isoindol-2-yl) ethyl] -O, O-diethylphosphorodithioate diazinon = O, O-diethyl-O- [6-methyl-2- (1-methylethyl) -4-pyrimidinyl] phosphorothioate.

Dichlorofenthion = O, O-diethyl-O- (2,4-dichlorophenyl) phosphorothioate. O-2,4-dichlorophenyl-O-ethylphenylphosphonothioate.

Dichlorvos = dimethyl 2,2-dichloroethenyl phosphate.

Dicrotophos = dimethyl-3- (dimethylamino) -1-methyl-3-oxo-1-propenyl phosphate.

Dimefox = oxide of bis (dimethylamino) fluorophosphine. Dimefox = oxide of bis (dimethylamino) fluorophosphine.

Dimethoate = O, O-Dimethyl-S- [2- (methylamino) -2-oxo-ethyl] phosphorodithioate.

1,3-Di- (methoxycarbonyl) -1-propen-2-yl dimethyl phosphate = dimethyl 3 - [(dimethoxyphosphinyl) oxy] -2-pentene dioate.

Dioxathione = S, S'-1,4-dioxane-2,3-diyl-O, O ', O'-tetraethyl-di- (phosphorodithioate). Disulfoton = O, O-Diethyl-S-2-ethylthioethylphosphorodithioat.

EPN = O-ethyl-O-4-nitrophenylphenylphosphonothioate.

Endothion = O, O-dimethyl-S- (5-methoxy-4-pyron-2-yl-methyl) phosphorothioate.

Ethion = O, O, O ", O" -Tetraehyl-S, S'-methylene-di (phosphorodithioate).

S-ethylsulfinylmethyl-O, O-diisopropyl phosphorodithioate. Ethoat-methyl = O, O-dimethyl-S- (N-ethylcarbamoyl-methyl) phosphorodithioate.

Ethoprophos = O-ethyl-S, S-dipropylphosphorodothioat.

Etrimfos = O- (6-ethoxy-2-ethyl-4-pyrimidinyl) -O, O-dimethylphosphorothioate.

Famphur = O, O-dimethyl-O-p- (dimethylsulfamoyl) phenyl phosphorothioate.

Fenchlorphos = O, O-DimethyI-O- (2,4,5-trichlorophenyl) phosphorothioate. Fensulfothione = O, O-diethyl-O-4- (methylsulfinyl) phenyl phosphorothioate.

Fenthion = O, O-dimethyl-O- [3-methyl-4- (methylthio) phenyl] phosphorothioate.

Fonophos = O-ethyl-S-phenylethylphosphonodithioate.

Formothion = S- [2- (formylmethylamino) -2-oxoethyl] -O, O-dimethylphosphorodithioate.

Fospirate = dimethyl-3,5,6-trichloro-2-pyridyl phosphate.

Fosthietan = diethyl-1,3-dithietan-2-yl-idene-phosphoramidate.

Heptenophos = 7-chlorobicyclo [3, 2.0] hepta-2,6-dien-6-yl dimethyl phosphate.

Iodofenphos = O-2,5-dichloro-4-iodophenyl-O, O-dimethyl-phosphorothioate. Isofenphos = 1-methylethyl-2 - [[ethoxy] - (1-methylethyl) amino [phosphmothioyl] -oxyjbenzoate.

Leptophos = O-4-bromo-2,5-dichlorophenyl-O-methylphenylphosphonothioate.

Lythidathione = O, O-Dimethyl-S- (5-ethoxy-2,3-dihydro-2-oxo-1,3,4-thiadiazol-3-yl-methyl) phosphotodithioate. Malathion = diethyl (dimethoxyphosphinothioyl) thiobutene dioate.

Mazidox = N, N, N ', N'-tetramethylphosphorodiamidique-acid.

Mecarbam = methyl ethyl [[(diethoxyphosphinothioyl) thio] acetal] carbamate.

Mecarphone = N-methylcarbonyl-N-methyl-carbamoyl-methyl-O-methylmethylphosphonodithioate. Menazon = S - [(4,6-diamino-1,3,5-triazin-2-yl) methyl] -O, O-dimethylphosphorodithioate. Mephosfolan = diethyl-4-methyl-1,3-dithiolan-2-yl-dinen-phosphoroamidate.

Methamidophos = O, S-dimethylphosphoramidothioate.

Methidation = S - [[5-methoxy-2-oxo-1,3,4-thiadiazol-3 (2H) -yI] methyl] -O, O-dimethylphosphorodithioate. Methocrotophos = dimethyl-cis-2- (N-methoxy-N-methyl) carbamoyl) -1-methyl vinyl phosphate.

2-Sulfur of 2-methoxy-4H-benzo-1,3,2-dioxaphosphorine.

Methyl carbophenotion = S - [[(4-chlorophenyl) thio] methyl] -O, O-dimethylphosphorodithioate. Mevinphos = methyl 3 - [(dimethoxyphosphinyl) oxy] -2-buenoate.

Monocrotophos = dimethyl-1-methyl-3- (methylamino) -3-oxo-1-propenyl phosphate. Morphotion = O, O-Dimethyl-S- (morpholino-carbonylmethyl) -phosphorodithioate. Naled = dimethyl-1,2-dibromo-2,2-dichloroethyl phosphate. Omethoate = O, O-Dimethyl-S- [2- (methylamino) -2-oxoethyl] phosphorothioate. Oxydimetone-methyl = S- [2- (ethylsulfinyl) ethyl] -O, O-dimethylphosphorothioate.

Oxydisulfoton = O, O-Diethyl-S- [2- (ethyl-sulfinyl) -ethyl] -phosphorodithioate. Parathion = O, O-diethyl-O-4-nitrophenyl phosphorothioate. Parathion-methyl = O, O-dimethyl-O-4-nitrophenyl-phosphorothioate. Phenkapton = O, O-Diethyl-S- (2,5-dichloro-phenylthiomethyl) phosphorodithioate. Phenthoate = ethyl α [(dimethoxyphosphinothioyl) thio] benzene acetate. Phorate = O, O-Diethyl-S-ethylthiomethyl-phosphorodithioate.

Phosalone = S - [[(6-chloro-2-oxo-3) (2H) -benzoxazolyl] - (methyl)] - O-diethylphosphorodithioate.

Phosfolan = diethyl-1,3-dithiolan-2-ylidene phosphoramidate. Phosmet = S - [(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl) methyl] -O, O-dimethylphosphorodithioate.

Phosnichlor = O, O-Dimethyl-O-4-chloro-3-nitrophenyl-phosphorothioate.

Phosphamidon = 2-chloro-3- (diethylamino) -1-methyl-3-oxo-l-propenyl phosphate of dimethyl. Phoxim = - [[Diethoxyphosphinothioyl) oxy] imino) -benzenacetonitriI.

Pirimiphos-ethyl = O- [2- (diethylamino) -6-methyl-4-pyrimidinyl)] - O, O-diethylphosphorothioate.

Pirimiphos-methyl = O- [2- (diethylamino) -6-methyl-4-pyrimidinyl)] - O, O-dimethylphosphorothioate. Profenofos = O- (4-bromo-2-chlorophenyl) -O-ethyl-S-propylphosphorothioate.

Propetamphos = (E) -1-methylethyl-3 - [[(ethylamino) methoxyphosphinothioyl] oxy] 2-butenoate.

Prothidathione = O, O-Diethyl-S- (2,3-dihydro-5-isopropyl-2-oxo-1,3,4-thiadiazol-3-yl-methyl) -phosphorodithioate. Prostoate = O, O-Diethyl-S- [2- (1-methylethyl) amino-2-oxoethyl] phosphorodithioate.

Quinalphos = O, O-Diethyl-O-2-quinoxalinylphosphorothioat.

Quinothione = O, O-Diethyl-2-methylquinolin-4-yl-phosphorothioate. Quintiofos - O-ethyl-O-8-quinolylphenyl phosphorothioate.

Sophamide = O, O-dimethyl-S- (N-methoxy-methyl) carbamoyl-methylphosphorodithioate

Sulfotepp = thiodiphosphate of tetraethyl. Sulfprofos = O-ethyl-O- (4-methylthiophenyl) -S-propylphosphorodithioate.

Temephos = O, O '- (Thiodi-4, 1-phenylene) -O, O, O', O'-tetramethyl-di (phosphorodithioate).

Tepp = diphosphate of tetraethyl.

Terbufos = S - [(1,1-dimethylethyl) thiomethyl] -O, O-diethylphosphorodithioate. Tetrachlorvinphos = trans-2-chloro-1- (2,4,5-trichlorophenyl) vinyl phosphate des

Dimethyl.

O, O, O ', O'-tetrapropyl dithiopyrophosphate = thiodiphosphate of tetrapropyl.

Thiometone = O, O-Dimethyl-S- [2- (ethylthio) ethyl] phosphorodithioate.

Thionazine = O, O-diethyl-O-pyrazinyl phosphorothioate. Triazophos = O, O-Diethyl-O- (phenyl-1H-1,2,4-triazol-3-yl) phosphorothioate.

Trichloronate = O-ethyl-O-2,4,5-trichlorophenyl-ethylphosphonothioate.

Trichlorphone = dimethyl (1-hydroxy-2,2,2-trichloro-ethyl) phosphonate.

Vamidothione = O, O-Dimethyl-S- [2- (1-methylcarbamoyl) ethyleneethyl] phosphorothioate. Benzoylureas include compounds of the formula (V): - 17th

wobei

in which

R ^{1 represents} halogen,

R ^{2 represents} hydrogen or halogen,

R ^{3 represents} hydrogen, halogen or C _1-4 alkyl,

R ^{4 is} halogen, 1-5 haloC _1-4 alkyl, C _1-4 alkoxy, 1-5 haloC _1-4 alkoxy, C _1-4 alkylthio, 1-5 halogen -C _1-4 alkylthio, phenoxy or pyridyloxy, which may optionally be substituted by halogen, C _1-4 alkyl, 1-5 haloC _1-4 alkyl, C _1-4 alkoxy, 1-5 -Halogen C _1-4 alkoxy, C _1-4 alkylthio, 1-5 halogen C _1-4 alkylthio.

Benzoylureas of the formula may be mentioned in particular:

The triazines include compounds of the formula

The agonists or antanogists of the nicotinogenic acetylcholine receptors of insects include the known compounds from, for example, European Offenlegungsschrift No. 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600, 192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389, German Offenlegungsschriften No. 3,639,877, 3,712,307; Japanese Laid-Open No. 3 639 877, 3 712 307, Japanese Laid-Open No. 03 220 176, 02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072; U.S. Patent Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686, 5,034,404; PCT applications No. WO 91/17 659, 91/4965; French Application No. 2 611 114; Brazilian application No. 88 03 621.

These compounds can preferably be represented by the general formula (I)

in which

R represents hydrogen, optionally substituted radicals from the group acyl, alkyl,

Aryl, aralkyl, heteroaryl or heteroarylalkyl;

A represents a monofunctional group from the series hydrogen, acyl, alkyl, aryl or represents a bifunctional group which is linked to the radical Z,

E represents an electron-withdrawing radical such as NO ₂ or CN,

X stands for the residues -CH = or = N-, the residue -CH = at the position of the

H atom can be linked to the radical Z;

Z for a monofunctional group from the series alkyl, -O-R, -S-R,

or represents a bifunctional group which is linked to the radical A or the radical X. Compounds of the formula (I) in which the radicals have the following meaning are particularly preferred:

R represents hydrogen and also optionally substituted radicals from the series acyl, alkyl, aryl, aralkyl, heteroaryl, heteroaryl alkyl. Formyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl-) - (aryl-) - phosphoryl, which in turn can be substituted, may be mentioned as acyl radicals.

Examples of alkyl which may be mentioned are C _1-10 -alkyl, in particular C _1-4 -alkyl, in particular methyl, ethyl, i-propyl, sec.- or t.-butyl, which in turn may be substituted.

Phenyl, naphthyl, especially phenyl, may be mentioned as aryl.

Phenylmethyl and phenethyl may be mentioned as aralkyl.

Heteroaryl with up to 10 ring atoms and N, O, S in particular N as heteroatoms may be mentioned as heteroaryl. Thienyl, furyl, thiazolyl, imidazolyl, pyridyl, benzothiazolyl may be mentioned in particular.

Heteroarylalkyl which may be mentioned are heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms.

Examples of preferred substituents are:

Alkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl, alkoxy with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methoxy , Ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy, alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio, haloalkyl with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 5, in particular 1 to 3 halogen atoms, the halogen atoms being identical or different and being halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine such as trifluoromethyl, hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; Cyano; Nitro; Amino; Monoalkyl and dialkylamino with preferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group, such as methylamino, methylethylamino, n- and i-propylamino and methyl-n-butylamino; Carboxyl; Carbalkoxy preferably having 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy; Sulfo (-SO ₃ H); Alkylsulfonyl preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methyl sulfonyl and ethylsulfonyl; Arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl and heteroarylamino and heteroarylalkylamino such as chloropyridylamino and chloropyridylmethylamino.

A particularly preferably represents hydrogen and also optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have the meanings given for R. A furthermore stands for a bifunctional group. Optionally substituted alkylene with 1-4, in particular 1-2, C atoms may be mentioned, the substituents listed above being mentioned as substituents and the alkylene groups being interrupted by heteroatoms from the series N, O, S. could be.

A and Z together with the atoms to which they are attached can form a saturated or unsaturated heterocyclic ring. The heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups. The heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. The alkyls are methyl, ethyl, n- and i-propyl and n -, i- and t-Butyl called. The heterocyclic ring contains 5 to 7, preferably 5 or 6, ring members.

Examples of the heteroeyclic ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine, hexahydro-1,3,5-triazine and morpholine, which may optionally be substituted by methyl. E stands for an electron-withdrawing radical, in particular NO ₂ , CN,

Haloalkylcarbonyl such as 1,5-halo-C _1-4 -carbonyl, in particular COCF ₃ may be mentioned. X stands for -CH = or -N =

Z stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where

R and the substituents preferably have the meaning given above.

an der Stelle von X einen gesättigten oder ungesättigten heterocyclischen Ring bilden. Der heterocyclische Ring kann weitere 1 oder 2 gleiche oder verschiedene Heteroatome und/oder Heterogruppen enthalten. Als Heteroatome stehen vorzugsweise Sauerstoff, Schwefel oder Stickstoff und als Heterogruppen N-Alkyl, wobei die Alkyl oder N-Alkyl-Gruppe vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatome enthält Als Alkyl seien Methyl, Ethyl, n- und i-Propyl und n-, i- und t-Butyl genannt Der heterocyclische Ring enthält 5 bis 7, vorzugsweise 5 oder 6 Ringglieder. In addition to the ring mentioned above, Z can together with the atom to which it is attached and the rest

form a saturated or unsaturated heterocyclic ring at the position of X. The heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups. The heteroatoms are preferably oxygen, sulfur or nitrogen and the hetero groups are N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. The alkyls are methyl, ethyl, n- and i-propyl and n-, i- and t-butyl called The heterocyclic ring contains 5 to 7, preferably 5 or 6 ring members.

Examples of the heterocyclic ring include pyrrolidine, piperidine, piperazine, hexamethyleneimine, morpholine and N-methylpiperazine.

Compounds of the general formulas (II) and (III) may be mentioned as particularly preferred compounds from the group of agonists and antagonists of the nicotinogenic acetylcholine formulations of insects:

in which n represents 1 or 2,

Subst. Stands for one of the substituents listed above for the preferred or particularly preferred meanings, in particular for halogen, very particularly for chlorine,

5 A, Z, X and E have the meanings given as preferred or particularly preferred above,

The following connections are specifically mentioned:

The following may be mentioned as fungicides:

 Sulfenanude such as dichlorofluoride (Euparen), tolylfluanid (Methyl euparen), Folpet, Fluorfolpet;

Benzimidazoles such as Carbendazim (MBC), Benomyl, Fuberidazole, Thiabendazole or their salts;

Thiocyanates such as thiocyanatomethylthiobenzothiazole (TCMTB), methylene bisthiocyanate (MBT); quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride,

Benzoyl-dimethyl-dodecyl-ammonium chloride, dodecyl-dimethyl-ammonium chloride, morpholine derivatives such as C ₁₁ -C ₁₄ -4-alkyl-2,6-dimethyl-morpholine homologous (tridemorph), (±) -cis-4- [3- tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorphohn (fenpropimorph), falimorph; Phenols such as o-phenylphenol, tribromophenol, tetrachlorophenol, pentachlorophenol,

3-methyl-4-chlorophenol, dichlorophene, chlorophene or their salts;

Azoles such as tridimefon, triadimenol, bitertanol, tebuconazole, propiconazole, azaconazole, hexaconazole, prochloraz, cyproconazole, 1- (2-chlorophenyl) -2- (1-chlorocyclopropyl) -3- (1,2,4-triazol-1-yl ) -propan-2-ol, 1- (2-chlorophenyl) -2- (1,2,4-triazol-1-yl-methyl) -3,3-dimethyl-butan-2-ol. Iodopropargyl derivatives such as iodopropargyl butyl carbamate (IPBC), chlorophenyl formal, phenyl carbamate, hexyl carbamate, cyclohexyl carbamate, iodopropargyloxyethylphenyl carbamate;

Iodine derivatives such as diiodomethyl-p-arylsulfones e.g. Diiodomethyl p-tolyl sulfone; Bromine derivatives such as bromopol;

Isothiazolines such as N-methylisothioazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one, N-octylisothiazolin-3-one (octilinones);

Benzisothiazolinones, cyclopentene isothiazolines;

Pyridines such as 1-hydroxy-2-pyridinthione, tetrachlor-4-methylsulphonylpyridine; Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil) and others microbicides with activated halogen group such as CI-Ac, MCA, tectamer, bromopol, bromidox;

Benzothiazoles such as 2-mercaptobenzothiazoles, see above or Dazomet;

Quinolines such as 8-hydroxyquinoline.

Particularly preferred insecticides are; Phosphoric acid esters such as azinphos-eteyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxypyrazole (TIA-230), chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, Dichlorvos, Dimethoate, Ethoprophos, Etrimfos, Fenitrothion, Fention, Heptenophos, Parathion, Parathion-methyl, Phosalone, Phoxion, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprofos, Triazophos and Trichlorphon.

Carbamates such as aldicarb, bendiocarb, BPMC (2- (1-methylpropyl) phenylmethylcarbamate), butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarbox. Pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin (FMC 54 800), cycloprothrin, cyfluthrin, decamethrione, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- ( chloro-2-trifluoromethylvinyl) cyclopropane carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin, fluvalinate, permethrin and resmethrin; Nitroimino and

Nitroimides such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol2-amine (imidacloprid).

Examples of herbicides are anilides, such as diflufenican and propanil, aryl carboxylic acids, such as, for example, dichloropicolinic acid, dicamba and picloram, aryloxyalkanoic acids, such as, for example, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr , MCPA, MCPP and triclopyr, aryloxy-phenoxy-alkanoic acid esters, such as Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl, azinones such as e.g. chloridazone and norflurazon, carbamates such as e.g. Chlorpropham, desmedipham, phenmedipham and propham, chloroacetanilides such as e.g. Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Pretilachlor and

Propachlor, dinitroanilines such as oryzalin, pendimethalin and trifluralin, diphenyl ether such as e.g. Acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen, ureas such as e.g. Chlorotoluron, Diuron, Flometuron, Isoproturon, Linuron and Methab enzthiazuron, Hydroxylamine, e.g. Alloxydim, Clethodim, Cycloxydim, Sethoxydim and Tralkoxydim,

Imidazohnones, e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin, nitriles such as e.g. Bromoxynil, dichlorobile and ioxynil, oxacetamides, e.g. Mefenacet, sulfonylureas, e.g. Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl, thiocarbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molmates, prosulfocarb, thiobvencarb and triallates, triazines, such as e.g. Atrazin, Cyanazin, Simazm, Simetryne, Terbutryne and Terbutylazin, Triazinone, e.g. Hexazinone, metamitron and metribuzin, others such as e.g. Aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid,

Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloride, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.

The systems according to the invention contain 0.1 to 30% by weight of active ingredient, preferably 1 to 20% by weight of active ingredient and particularly preferably 5 to 20% by weight of active ingredient. In addition to the carrier polymer, they can also contain other customary additives.

Such additives are fillers such as Table salt, carbonates such as calcium carbonate, hydrogen carbonate, aluminum oxides, silicas, clays, precipitated or colloidal silicon dioxide, phosphates.

Other suitable additives are lubricants and lubricants such as Magnesium stearate, stearic acid, talc, bentonite.

Suitable additives are the plasticizers which are usually used to plasticize solid vinyl resins. Suitable plasticizers are, for example, esters of phosphoric acid, such as esters of phthalic acid, such as

Dimethyl phthalate and dioctyl phthalate, and esters of adipic acid, such as diisobutyl adipate. Other esters, such as the esters of azelaic acid, maleic acid, ricinoleic acid, myristic acid, palmitic acid, oleic acid, sebacic acid, stearic acid and trimellitic acid, as well as complexed linear polyester epoxy polymers, plasticizers, and plasticizers The amount of

Plasticizer is up to about 50%, preferably about 10 to 30% by weight of the total composition.

Other additives are stabilizing agents and coloring materials. Suitable stabilizing agents are antioxidants and agents which protect the polymers from undesired degradation during processing. Some stabilizing agents, such as epoxidized soybean ols, also serve as secondary plasticizers. The additives can be used in a concentration of up to about 50% by weight. preferably up to about 20% by weight of the total composition can be used. In the production of the shaped bodies according to the invention, the various

Components are dry mixed according to known mixing methods and compression molded according to known extrusion or injection molding methods.

Furthermore, it is possible to mix the individual components by dissolving them in a common solvent and then to drop them in a suitable non-solvent or to remove the solvent from the solution by means of an evaporation extruder. In the case of precipitation, the solution is preferably introduced into a nozzle Precipitation bath pressed, the resulting coagulating material drawn off as threads (wet spinning process). The precipitation is preferably carried out by means of the known dry and wet spinning processes.

From a technical point of view, the choice of the processing method for producing the shaped bodies according to the invention is fundamentally based on the theological properties of the shaped body material and the shape of the desired structure. The processing methods can be adjusted according to the processing technology or the type of shaping. In process technology, the processes can be subdivided according to the theological conditions they run through.Then pouring, pressing, spraying and applying for viscous molded body materials and injection molding, extrusion (extrusion), calendering, rolling and, if necessary, kneading are considered for the type of shaping divided, the shaped bodies according to the invention can be produced by casting, dipping, pressing, injection molding, extruding, calendering, embossing, bending, deep drawing, spinning, etc.

These processing methods are known and require no further explanation.

The systems according to the invention are suitable, for example, for introducing crop protection agents such as fungicides or insecticides into the soil near the roots. There they are biodegraded as a depot preparation with controlled release of active ingredients and are completely degraded at the end of their effectiveness.

For this purpose, they are worked into the earth as flour, dust, granules or stuck into the ground as rods, balls, tablets or the like.

It is also possible to apply them in the form of foils, nets, tiles, fabrics, bands or rods. These systems can also be used to produce growing vessels for plants such as pots, tubs or the like.

The systems according to the invention can also be used for the treatment of individual plants, such as trees. For this purpose, they are preferably in the form of suitable shaped bodies such as rods, tablets, plates, foils, tiles, fabrics, strips, rivets, nails, clips, pins, needles, Hollow nailing, wires inserted into the sap flow of the plants. The shaped bodies are either inserted into the cavities made in the plant or simply into the plant Plant tissue pressed, pressed, beaten. They can also be pushed under carefully loosened bark or parts of plants, the bark or parts of plants then serving again for covering.

The systems according to the invention can also be used for the production of transcuticular agents. For this they are in the form of paints, film-forming pastes,

Films, foils, plasters applied to the surface of the plant.

Examples of suitable polymers are given below:

example 1

10.77 g of hydroxypropyl cellulose (MS = 0.92) are stirred in 300 g of dioxane with 0.2 ml of 1,8-diazabicyclo (5.4.0) undec-7-ene at 60 ° C for 0.5 hours. 37 g of phthalic anhydride dissolved in 50 g of dioxane are added dropwise to this suspension and the mixture is stirred at 60 ° C. for one hour. The reaction mixture is heated to 80 ° C. 43.5 g of propylene oxide are added dropwise and the mixture is stirred at 80 ° C. for 4 hours. This creates a solution of the cellulose ether ester in dioxane. The solution is then stirred into 1.51 isopropanol and the precipitated product is filtered and washed with isopropanol. The softening point is 130 ° C. The over

Solid-state NMR determined degree of substitution is 1.7 moles of phthalic acid and 2.75 moles of propyl groups per glucose unit. In the enzyme test, a glucose release of 85, 19 μg glucose / ml-h of the sample preincubated at 60 ° C. was found. In the composting test, the sample is completely degraded after four weeks. Example 2

9.68 g of hydroxyethyl cellulose (MS = 0.72) are stirred in 300 g of dimethyl sulfoxide with 0.2 ml of 1,8-diazabicyclo (5.4.0) undec-7-ene at 60 ° C for 0.5 hours. 37 g of phthalic anhydride dissolved in 50 g of dimethyl sulfoxide are added dropwise to this suspension and the mixture is stirred at 60 ° C. for one hour. The reaction mixture is heated to 80 ° C. 43.5 g of propylene oxide are added dropwise and the mixture is stirred at 80 ° C. for 4 hours.

This creates a solution of the cellulose ether ester in dimethyl sulfoxide. The solution is then stirred into 1.51 isopropanol and the precipitated product is filtered and washed with isopropanol. The melting point is 1 10 ° C. The degree of substitution determined by solid-state NMR is 2.0 mol of phthalic acid and 2.3 mol of propyl groups per glucose unit. In the enzyme test, a glucose-free setting of 80.1 μg glucose / ml-h of the sample preincubated at 60 ° C. was found. In the composting test, the sample is completely degraded after four weeks. Example 3

8.1 g of wheat starch and 15.15 g of triethylamine are stirred in 300 g of dimethyl sulfoxide at 60 ° C. for 0.5 hour. Then 37 g of phthalic anhydride in 50 g of dimethyl sulfoxide are added dropwise and the mixture is stirred at 60 ° C. for one hour. The reaction mixture is heated to 80 ° C. and 43.5 g of propylene oxide are added dropwise and the mixture is stirred for 1 hour

80 ° C stirred. The solution is then stirred into 1.51 acetone and the precipitated product is filtered off and washed with acetone. The softening point is 155 ° C. The degree of substitution determined by solid-state NMR is 2.3 mol of phthalic acid and 1.01 mol of propyl groups per glucose unit. In the enzyme test, a glucose-free setting of the sample preincubated at 60 ° C of 91.25 μg

Glucose / ml -h found In the composting test, the sample is completely degraded after four weeks.

Example 4

8.1 g of cotton sinter and 15.15 g of triethylamine are stirred in 300 g of dimethyl sulfoxide at 60 ° C. for 0.5 hour. 38.5 g of hexahydrophthalic anhydride in 50 g of dimethyl sulfoxide are then added dropwise and the mixture is stirred at 60 ° C. for 2 hours. The reaction mixture is heated to 80 ° C. and 43 , 5 g of propylene oxide were added dropwise and the mixture was stirred at 80 ° C. for 1 hour. The solution is then stirred into 1.51 isopropanol and the precipitated product is filtered and washed with isopropanol. The melting point is 120 ° C. The degree of substitution determined by solid-state NMR is 3.0 mol of hexahydrophthalic acid and 3.0 mol of propyl groups per glucose unit. In the enzyme test, a release of 70.6 μg of glucose / ml-h of the sample preincubated at 60 ° C. is found. In the composting test, the sample is completely degraded after four weeks. Example 5

1084 g of cotton sinters are alkalized in 22.51 isopropanol and 2.51 water and 0.63kg NaOH biscuits for 90 minutes at 25 ° C. Then it is washed with 101 isopropanol / water (80/20) and centrifuged and stirred again with 101 isopropanol and centrifuged The alkali cellulose thus produced has an alkali content of 6.8%. 49.1 g of ethylene oxide are metered into 130.1 g of the alkali cellulose thus obtained in a stirred autoclave under a nitrogen atmosphere and the mixture is stirred at 50 ° C. for 1.5 hours. 1000 ml of dimethylacetamide and 205 g of tetrahydrophthalic acid are then added to the reaction mixture and the mixture is stirred at 60 ° C. for 1.5 hours. The reaction mixture is heated to 80 ° C. and 215 g of propylene oxide are added dropwise and the mixture is stirred at 80 ° C. for 1 hour. The solution is then stirred into 101 isopropanol and the precipitated product is filtered and washed with isopropanol. The softening point is 160 ° C. The degree of substitution determined by solid-state NMR is 2.2 mol of tetrahydrophthalic acid and 1.8 mol of propyl groups per glucose unit. In the enzyme test, a glucose-free setting of 68.83 μg glucose / ml-h of the sample preincubated at 60 ° C. was found. In the composting test, the sample is completely degraded after four weeks.

Examples of suitable polymer systems are given below: Example 6 a) were used to produce active substance-containing molded articles according to the invention

Mixture of 278 parts by weight of imidacloprid, 1 part by weight of tebuconazole and 2 parts by weight of precipitated silicic acid and b) 719 parts by weight of a celiolulose hydroxypropyl phthalate with an average degree of substitution MS (average number of grafted monomers per glucose unit) of 2.36 and an average degree of substitution DS (average number of derivatized

OH groups per glucose unit) of 1.80 metered separately into a twin-screw extruder using differential scales. Furthermore, c) 100 parts by weight of the plasticizer triethylene glycol were metered into the screw by means of a pump.

The components were homogenized in the extruder at 140 ° C. to 150 ° C. within 4 minutes and the melt was extruded at a throughput of 3.8 kg / h, cooled with air and granulated.

After granulation, the molding compound containing the active ingredient is shaped into bars, pins, strips and plates using an injection molding machine at 160 ° C. Example 7

In the manner described in Example 6, a) a mixture of 294 parts by weight of imidacloprid, 1 part by weight of tebuconazole and 2 parts by weight of precipitated silica and b) 703 parts by weight of a cellulose hydroxypropyl phthalate (MS = 2.36 and DS = 1 , 80) extruded with c) 100 parts by weight of the plasticizer, lactic acid ethyl ester at 140 ° C. to 160 ° C. and then hosed down to form forin cores.

Example 8

In the manner described in Example 6, a) a mixture of 250 parts by weight of Fenamiphos (Nemacur) and 2 parts by weight of precipitated silica and b) 748 parts by weight of a cellulose hydroxypropyl phthalate (MS = 2.36 and

DS = 1.80) extruded at 140 ° C and hosed to form bodies.

Example 9

A mixture of 294 parts by weight of imidacloprid, 1 part by weight of tebuconazole and 2 parts by weight of precipitated silica with 703 parts by weight of a cellulose hydroxypropyl phthalate (MS = 1.80 and DS = 1.60) and with 100 parts by weight. Share the

Plasticizer of lactic acid extruded in the manner described in Example 6.

The melt strand was drawn off at a speed of 35 m / min, so that a cable with a diameter of approximately 1 mm was formed, and after cooling with air, it was wound onto a spool. By subsequently cutting the cable, pins with a length of 2 cm were produced.

Example 10

According to the procedure described in Example 9, a mixture of 250 parts by weight of Fenamiphos (Nemacur) and 2 parts by weight of precipitated silica with 748 parts by weight of a cellulose hydroxypropyl phthalate (MS = 1.80 and DS =

1.60) at 140 ° C to form a strand. Example 11

A mixture of 278 parts by weight of imidacloprid, 1 part by weight of tebuconazole and 2 parts by weight of precipitated silica with 719 parts by weight of the polymeric carrier material of a cellulose hydroxypropyl phthalate (MS = 2.36 and DS = 1.80) and melted with 100 parts by weight of the plasticizer triethylene glycol in the manner described in Example 6 in the extruder and mixed.

The melt was pressed at 155 ° C. through a 75 mm wide slot nozzle with a gap height of 0.5 mm, cooled by air blowing and drawn off by means of a Teflon conveyor belt at a speed of 5 / min. In this way, films with a thickness of approximately 50 μm were obtained.

Example 12

59.8 g (74.8 parts by weight) of a cellulose hydroxypropyl phthalate (MS = 1.80 and DS = 1.60) were melted in a kneader, type Haake Rheomix, at 140 ° C. and 50 μm and then a mixture of 20 g (25 parts by weight) of Fenamiphos (Nemacur) and 0.16 g (0.2 parts by weight) of precipitated silica were added.

For homogenization, kneading was carried out for a further 5 minutes at 110 ° C. after the active ingredients had been added.

The resulting active substance-containing mass was shaped in a press at 200 bar pressure and 120 ° C. into sheets with an area of 10 cm ² and a thickness of 2 mm.

Claims

claims 1 Systems consisting of polysaccharide ether esters and agrochemical active ingredients, which may contain conventional additives. 2 Systems according to claim 1, which contain as polysaccharide ether esters those of the following general structure: Polysaccharide-O-R where Polysaccharide-O represent the substituted OH groups of a polymeric saccharide unit and R is either a mono- and / or polymeric substituent of structure X: X = -A-B-A'- in which A and A are a linear polyether chain of the following structure: A = (-DO) _n and A '= (-DO) _m H in which D is a linear aliphatic or aromatic branched or unbranched chain with 2 to 11 carbon atoms and n is an integer equal to or greater than 0, m is an integer equal to or greater than 1, and B is a dicarboxylic acid of the following structure:

in which E is an aromatic or aliphatic carbon skeleton which may optionally be provided with further substituents, the ratio of A to B being equal to or greater than 0.1, or R being corresponding the degree of substitution per saccharide unit with X equal to H (hydrogen) and / or alkyl with 1 to 4, preferably 1 to 2, carbon atoms. 3. Systems according to claim 1, characterized in that they contain agonists or antagonists of the nicotinergic acetylcholine receptors of insects as agrochemical active ingredients. 4. A process for the preparation of the systems according to claim 1, characterized in that polysaccharide ether esters are mixed with agrochemical active ingredients and optionally additives with heating, kneaded or extruded until a homogeneous mixture has formed, or characterized in that the agrochemical active ingredients are optionally in the form of a solution during the synthesis of the polysaccharide ether esters. 5. Use of systems according to claim 1 for the treatment of plants and / or their habitat against plant pests, plant-damaging fungi or against undesirable plant growth.