WO2000042845A1

WO2000042845A1 - Use of natural substances to prevent the leaching of agrochemical active ingredients

Info

Publication number: WO2000042845A1
Application number: PCT/EP2000/000193
Authority: WO
Inventors: John P. E. Anderson; Wolfgang Wirth
Original assignee: Bayer Aktiengesellschaft
Priority date: 1999-01-20
Filing date: 2000-01-13
Publication date: 2000-07-27
Also published as: DE19901944A1; AU2663800A

Abstract

The invention relates to the use of biodegradable, organic natural substances on the basis of lignin and/or lignocellulose, which are well suited for preventing agrochemical active ingredients from leaching into the soil after application.

Description

Use of natural substances to prevent leaching of agrochemical active substances

The present invention relates to the new use of certain natural substances based on lignin and / or lignocellulose to prevent leaching of agrochemical active substances.

Most agrochemical active ingredients are organic substances that are largely insoluble in water. They are therefore generally converted into formulations by adding auxiliaries which are dispersible in aqueous systems and can be absorbed by the plants. At the same time, the problem arises that formulations of this type may seep away or be washed out after application by soil moisture or rainwater, and the active components are no longer available at the actual place of action.

Various methods have been described which aim to reduce this undesired leaching out of agrochemical active substances after their application. It has already become known that the mobility and thus the leaching of agrochemical active substances in the soil can be reduced by using formulations in which the active substances are chemically bound to wood derivatives containing hydroyl groups, such as sawdust or lignin (see Tappi Vol. 54 ; 1293-1294 (1971) and FR-PS 1 544 406). However, it is disadvantageous that the preparation of these preparations is quite complex.

In addition, undesirable decomposition of the active components is also observed in some cases.

It has now been found that biodegradable, organic natural substances based on lignin and / or lignocellulose can be used in order to agrochemical agents to prevent their undesirable leaching in the soil.

It is extremely surprising that the substances which can be used in accordance with the invention achieve a much better anti-leaching effect in agrochemical active substances in the soil than when using the structurally similar, known substances for the same purpose. It is also unexpected that no chemical decomposition of the active components is observed.

The use of the substances which can be used according to the invention is notable for a number of advantages. The leaching of the agrochemical active ingredients after their application in the soil is reduced to such an extent that they are almost completely available at the desired action location. It is also favorable that the substances which can be used according to the invention are inexpensive and biodegradable

Products. It should also be emphasized that the application of the substances which can be used according to the invention is unproblematic for the operating personnel, even without special safety precautions.

As biodegradable organic natural substances which can be used according to the invention

Based on lignin and / or lignocellulose, preference is given to substances of this type which have a high adsorption capacity. Bark flour, coconut flour and coconut fiber, as well as lignin and peat in finely comminuted form are particularly preferred. Bark flour from conifers such as spruce, pine and fir is very particularly preferred. The substances which can be used according to the invention are used in finely comminuted form.

As mentioned, the substances which can be used according to the invention are suitable for preventing the undesired leaching of agrochemical active substances in the soil. Agrochemical active substances are to be understood here to mean all substances customary for plant treatment. Fungicides, bactericides, Insecticides, acaricides, nematicides, herbicides, plant growth regulators, plant nutrients and repellents.

Examples of fungicides are:

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-

N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3 methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP),

Aldimoφh, ampropylfos, anilazine, azaconazole,

Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S,

Bromuconazole, bupirimate, buthiobate, calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate

(Quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,

Cymoxanil, cyproconazole, cyprofuram,

Dichlorophen, diclobutrazole, dichlofluanid, diclomezin, dicloran, diethofencarb,

Difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,

Edifenphos, epoxyconazole, ethirimol, etridiazole,

Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimoφh, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil,

Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folet, Fosetyl-Aluminum, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox,

Guazatine,

Hexachlorobenzene, hexaconazole, hymexazole,

Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,

Kasugamycin, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,

Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol, Ofurace, oxadixyl, oxamocarb, oxycarboxin,

Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozen (PCNB)

Tebuconazole, Tecloftalam, Tecazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemoφh, Trififoroline, Trififoroline, Trififoroline, Trififorolinol, Trififoroline, Trififoroline, Trififoroline, Trififoroline, Trififorolinol, Trififoroline, Trififoroline, Trififoroline, Trififoroline, Trififorolinol, Trififorolinol, Trififorolinol, Trififoroline, Trififoroline, Trififoroline, Trififoroline, Trififoroline, Trififorumolinol Ziram

8-tert-butyl-2- (N-ethyl-Nn-propylamino) methyl-l, 4-dioxa-spiro- [4,5] decane, N- (R) - [1 - (4- Chloφhenyl) -ethyl] -2,2-dichloro-1-ethyl-3t-methyl-1 r-cyclopropanecarboxamide (mixture of diastereomers or individual isomers), [2-methyl-l - [[[l- (4-methylphenyl) -ethyl] -amino] -carbonyl] -propyl] -carbamic acid- 1-methylethyl ester,

1-methyl-cyclohexyl-1-carboxylic acid- (2,3-dichloro-4-hydroxy) -anilide, 2- [2- (l-chloro-cyclopropyl) -3- (2-chloro-phenyl) -2-hydroxypropyl] - 2,4-dihydro- [l, 2,4] - triazole-3-thione and l- (3,5-dimethyl-isoxazole-4-sulfonyl) -2-chloro-6,6-difluoro- [1,3 ] -dioxolo- [4,5-f] - benzimidazole.

Examples of bactericides are:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Examples of insecticides, acaricides and nematicides are:

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz,

Avennectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, 4-bromo-2- (4-chloro-phenyl) -1 - (ethoxymethyl) -5- (trifluoromethyl) -lH-pynole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox , Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chlorinyl) - 3-pyrid -methyl] -N'-cyano-N-methyl-ethanimidamide, Chloφyrifos, Chloφyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromhrin, Dyrethrin M, Demeton-S, Demeton-S-methyl, diafenthiuron, diazinone, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,

Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenproxophonin, Flufenproxofonhonof, Fufionfonium, Fufenionfonium, Flufenproxofonon, Flufenproxuron, Fufionatex, Fufion, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox,

Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,

Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,

Naled, NC 184, Nitenpyram,

Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,

Parathion A, Parathion M, Penriethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Prome- carb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymophroos, Pyrachl

Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,

Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,

Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temefos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiamethoxan, Thiodicarb,

Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Transfluthrin,

Triarathes, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,

Vamidothione, XMC, xylylcarb, zetamethrin.

Examples of herbicides are:

Anilides, e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, e.g. Chloridazon and norflurazon;

Carbamates, e.g. Chloφropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides, e.g. Alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines, e.g. Oryzalin, pendimethalin and trifluralin; Diphenyl ethers, e.g. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and Oxyfluorfen; Ureas, e.g. Chlorotoluron, diuron, fluometuron, isopro turon, linuron and methabenzthiazuron; Hydroxylamines, e.g. Alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Imidazolinones, e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles, e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, 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; Thiol carbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne and

Terbutylazin; Triazinones such as hexazinone, metamitron and metribuzin; Other, such as, for example, aminotriazole, 4-amino-N- (l, l-dimethylethyl) -4,5-dihydro-3- (l-methylethyl) -5-oxo-lH-l, 2,4-triazole-l- carboxamide, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Chlorcholine chloride and ethephon are examples of plant growth regulators.

Examples of plant nutrients are customary inorganic or organic

Fertilizer for supplying plants with macro and / or micronutrients called.

Examples of repellents are diethyltolylamide, ethylhexanediol and butopyronoxyl.

The substances which can be used according to the invention can be applied as such or in the form of formulations, such as granules, tablets, moldings, powders, pastes or suspensions. They can also be incorporated into formulations of agrochemical active ingredients.

The formulations are prepared by customary methods, ie by mixing the substances which can be used according to the invention with customary formulation auxiliaries, such as organic solvents, emulsifiers, preservatives, plasticizers, binders, dyes and also water.

Suitable organic solvents here are all customary organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the agrochemical active ingredients well. Preferably mentioned are aliphatic and aromatic, optionally halogenated hydrocarbons, such as toluene,

Xylene, Solvesso ^® , Bonesperse NA ^® , Indulin AT ^® , mineral oils such as white spirit, Petroleum, alkylbenzenes and spindle oil, also carbon tetrachloride, chloroform, methylene chloride and dichloroethane, also esters, such as ethyl acetate, also lactams, such as N-methylpynolidone, N-octylpynolidone and N-methylcaprolactam, and also alkane carboxamides, such as decanecarboxylic acid dimethyl amide and redimethyl amide and also octancarboxamide Dimethylformarnide.

Suitable emulsifiers are customary surface-active substances present in formulations of agrochemical active substances. Examples include ethoxylated nonylphenols, polyethylene glycol ethers of linear alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, and also fatty acid esters, alkyl sulfonates, alkyl sulfates, aryl sulfates and carboxylic acid amides, such as decanecarboxylic acid dimethyl amide.

All substances usually present for this purpose in plant treatment agents can be considered as preservatives. May be mentioned as examples

Preventol® and Proxel®.

Usable substances of this type which can be used in formulations of agrochemical active substances are suitable as plasticizers. Examples include phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters, tri-n-butyl phosphate, and also adipic acid esters such as di- (ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as Butyl oleate, and also glycerol ether, higher molecular weight glycol ether and glycerol ester and p-toluenesulfonic acid ester.

All adhesives usually present in formulations of agrochemical active substances can be considered as binders. Examples include acrylic resin, vinyl resin such as polyvinyl acetate, polyester resin, polycondensation resin, polyaddition resin, polyurethane resin, alkyd resin, modified alkyd resin, phenolic resin, hydrocarbon resin such as inden-coumarone resin, silicone resin, drying oils and physically drying adhesives based on natural and / or synthetic resin. Possible dyes are soluble or sparingly soluble color pigments, such as, for example, titanium dioxide, carbon black, zinc oxide or blue pigments.

The formulations are prepared by mixing the components with one another in the ratios desired in each case.

For the production of solid formulations, such as granules, tablets or other shaped bodies, the substances which can be used according to the invention are preferably used in grain sizes of up to 4 mm. In the production of powders, the general procedure is to grind the solid products initially obtained. If the production of liquid formulations, such as suspensions or pastes, is desired, the substances which can be used according to the invention are preferably used in particle sizes from 0.05 to 10 mm.

If the intention is to produce formulations which, in addition to substances which can be used according to the invention, also contain agrochemical active substances in solid form, these are used either in finely ground form or as a solution or suspension in an organic solvent. If the agrochemical active ingredients are substances that are liquid at room temperature, there is no need to use organic solvents. It is also possible to use solid agrochemical active ingredients in the form of melts.

The temperatures during the preparation of the formulations can be varied within a certain range. In general, temperatures between 0 ° C and 80 ° C, preferably between 10 ° C and 60 ° C.

In the preparation of formulations, the procedure is such that the substances which can be used according to the invention are mixed intensively with the other components with stirring. The order in which the components are mixed together is arbitrary. The resulting niche can be removed using conventional methods. - lü ¬

which are converted into the desired forms of preparation. For example, by extrusion and optionally drying, e.g. Manufacture granules, tablets or other shaped bodies. If the production of powders is intended, the resulting product can be ground, if necessary after drying. It is also possible to produce pastes by pressing the premix in a suitable consistency. It is also possible to prepare liquid formulations by suspending the premix in finely divided form in the liquid phase desired in each case.

For the preparation of the formulations, customary devices are considered which are used for

Preparation of agrochemicals can be used.

The content of the substances which can be used according to the invention can be varied within a substantial range in the formulations. In formulations in which no agrochemical active substances are present, the content of substances which can be used according to the invention is generally between 5 and 90% by weight, preferably between 10 and 85% by weight. If agrochemical active substances are also present in the formulations, the content of substances which can be used according to the invention is generally between 0.5 and 80% by weight, preferably between 2 and 15% by weight.

The substances which can be used according to the invention can be applied either as such or in the form of formulations, if appropriate after prior dilution, e.g. as granules, tablets, moldings, powders, pastes or suspensions. The application takes place according to usual methods, e.g. by spreading, laying out, implanting, working into the ground, spreading, spraying or pouring.

The application rate of substances which can be used according to the invention can be varied within a relatively wide range. It depends on the respective agrochemical active ingredients and their content in the agents used. You bet Substances which can be used according to the invention are generally present in amounts of between 0.1 and 20 kg / ha, preferably between 0.2 and 2 kg / ha.

The invention is illustrated by the following examples.

Manufacturing examples

example 1

72 g of spruce bark flour with an average grain size of 0.2 mm, 2 g of ¹⁴ C-marked imidacloprid, 20 g of Bonesperse NA® and 6 g of dibutyl-naphthalene-sulfonic acid sodium (low salt) are mixed at room temperature with stirring. 100 g of a formulation with an active ingredient content of 2% by weight are obtained in the form of a powder.

Example 2

72 g of powdered lignin with an average grain size of <0.2 mm, 2 g '^ -labeled imidacloprid, 20 g of Bonesperse NA ^® and 6 g of dibutyl-naphthalene-sulfonic acid sodium (low salt) are mixed at room temperature with stirring. You get

100 g of a formulation with an active ingredient content of 2% by weight in the form of a powder.

Comparative Example I

98 g of quartz sand with an average grain size of 2 mm, 2 g of ¹⁴ C-labeled imidacloprid and 20 ml of acetonitrile are mixed at room temperature with stirring. The solvent is then allowed to evaporate at room temperature. You get

100 g of a formulation with an active ingredient content of 2% by weight in the form of a granular solid substance.

Example of use A

To test the leaching behavior, 250 mg of a formulation are placed in a chromatography column (diameter 3 cm) which had previously been filled to a height of 70 cm with 50 g quartz sand. Then 30 ml of water are applied to the column head every 7 days. The eluate flowing out of the column is collected and its radioactive content

Analyzed active ingredient.

The formulations used and the test results are listed in the following table.

The test results are average values of 5 repetitions.

The maximum deviation was <3%.

Claims

claims

1. Use of biodegradable, organic natural substances based on lignin and or lignocellulose to prevent the undesired leaching of agrochemical active substances in the soil.

2. Use according to claim 1, characterized in that bark flours, coconut flour, coconut fibers, lignin or peat are used as biodegradable, organic natural substances.

3. A method for preventing the undesirable leaching of agrochemical active substances in the soil, characterized in that substances are applied according to claim 1.