IT201800010481A1 - DISPERSIONS OF DITHIOCARBAMATES IN OIL - Google Patents

Description

DISPERSIONS OF DITHIOCARBAMATES IN OIL

TECHNICAL FIELD

The present invention relates to an oil dispersion of dithiocarbamates comprising a polyamide obtained by reacting a fatty acid and a di- or tri-carboxylic acid with a polyamine in specific molar ratios.

The present invention also relates to the use in agriculture of the oil dispersion of dithiocarbamates comprising the aforementioned polyamide.

STATE OF THE ART

Dithiocarbamates (DTCs) are the most important group of organic fungicides for the control of plant diseases. DTCs are characterized by a broad spectrum of activity against various pathogens, by a low acute toxicity towards mammals and by low production costs. Due to their known chemical instability at elevated temperatures in the presence of moisture, DTCs are normally sold in the form of solid formulations, such as dispersible powders and granules, or dispersions in oil.

Agrochemical Oil Dispersions (ODs) are stable suspensions in organic fluids of agrochemical active ingredients, such as pesticides and crop protection chemicals, and are usually intended for dilution with water prior to use. Oil dispersions are particularly useful for the formulation of solid, oil-insoluble active ingredients and for hydrolytically unstable compounds in aqueous compositions, such as dithiocarbamates.

A disadvantage of oil dispersions, in particular of dithiocarbamates, is that these formulations are not stable over time and show phase separations during storage. Thus, even at room temperature, there are often effects of aggregation, marked increase in viscosity, gel formation or pronounced sedimentation of the suspended solid. In the worst cases, the effects are irreversible, that is, even under high shear agitation, it is not possible to make the formulation homogeneous again.

A common method of solving this problem is to add a stabilizer to the dispersions which can act as a thickener by increasing the viscosity of the system or can act as a dispersant by reducing the sedimentation rate of the particles, or can have both effects.

The typical stabilizer for organic systems without water includes organophilic clays, such as Bentone®. Organophilic clays are obtained from natural clays such as smectites, hectorites or montmorillonites made to react with quaternary ammonium compounds, so that they become organophilic and therefore compatible with non-aqueous media.

Other known stabilizers are surfactants, vegetable oil derivatives, silica derivatives and synthetic polymers.

For example, WO 2000/072681 describes an essentially anhydrous liquid formulation of dithiocarbamates containing: at least one active principle of the class of dithiocarbamates, an essentially anhydrous oil phase, a polyhydroxystearic acid or a derivative thereof and / or an alkyl or alkenyl ether of ethoxylated glycerin , which act as stabilizers, and possibly an anionic surfactant.

US 2009/202648 discloses a dispersion comprising: a dispersed phase comprising ethylene bis (dithiocarbamate); a continuous phase comprising a liquid immiscible in water; and, as stabilizer, a polyacrylate, salified with a metal cation, having a molecular weight between about 150 and about 15,000 Dalton.

US 2011/237591 refers to fungicidal formulations for plant protection comprising: a) dimethomorph and b) at least one dithiocarbamate; in the form of concentrated suspensions in a liquid organic diluent and in the presence of at least one surfactant. Suitable stabilizers include silicates, modified silicates, organic thickeners, for example those based on hydrogenated fatty acids and fatty acid derivatives, and thickeners based on synthetic polymers.

WO 2012/167322 refers to an oil-based suspension for agricultural use comprising an active principle in the form of very fine particles suspended in an oil; and, as stabilizer, at least one surfactant selected from fatty acid condensates and polyalkylene glycols or fatty acid condensates and polyalkylene glycol ethers. Dithiocarbamates are mentioned among the active ingredients of interest.

WO 2016/153913 discloses an agrochemical formulation comprising a pesticide or a mixture of pesticides, including dithiocarbamates, and an adjuvant composition comprising an oil and a derivative of a natural maleate oil obtained from the reaction between a natural maleate oil and a compound comprising at least one among polyoxyalkylene glycols, monoalkyl polyoxyalkylene glycols, polyether amines, alkylene amines, alkanol amines etc. Polyamines, such as ethylene diamine, diethylene tetramine, triethylene diamine and triethylene tetramine, are included among the alkylene amines.

Unfortunately, all of these stabilizers exhibit drawbacks and problems that reduce their applicability and performance.

Some do not provide the dispersions with adequate stability in terms of sedimentation in the desired temperature range and for a sufficient time.

Others significantly increase the viscosity of the dispersion and must be dosed very carefully.

Organophilic clays must be carefully dispersed and require the presence of a chemical activator to function as anti-sedimentation agents. If the organophilic clay is not dispersed well or chemically activated, there is a poor cohesive strength and therefore a limited physical stability of the product.

Furthermore, the handling of most of these stabilizers is very difficult and / or harmful, because they are mostly very fine and light powders or extremely viscous liquids.

Finally, they are difficult to dissolve / homogenize in the dispersions without causing the formation of gels or lumps and, therefore, a continuous and careful monitoring of the formulation process is necessary.

For these reasons, there is still a need to find a stabilizer that improves the physical stability of the oil dispersions of the fungicides of the dithiocarbamate family without showing the aforementioned problems. Now, we have found that oil dispersions of dithiocarbamates can be stabilized using an oil-soluble polyamide obtained by reacting in a specific ratio a fatty acid and a polyamine and, subsequently, by reacting the aminoamide thus obtained with a di- or tri acid. -carboxylic.

This polyamide facilitates the preparation of dithiocarbamate oil dispersions and their storage, even in hot climates, for their effective use in agronomic applications.

As far as the Applicant is aware, none of the documents of the state of the art describe the use of the polyamide of the invention as a stabilizer for the dispersions of dithiocarbamates in oil.

The expression "dispersion of dithiocarbamate oil" means a concentrated dispersion based on an organic vehicle in which one or more dithiocarbamates are suspended. Additional agrochemical active ingredients may be present in the dispersion.

DESCRIPTION OF THE INVENTION

The object of the present invention is therefore an oil dispersion of dithiocarbamates comprising: from 5.0 to 60% by weight of at least one fungicide of the dithiocarbamate family, from 10 to 90% by weight of an oil and from 0.05 to 10% by weight of a polyamide obtained by reacting:

a) a mole of a polyamine having n amino groups with exchangeable hydrogens, wherein n is an integer between 2 and 6;

b) from 1 to n-1 moles of a saturated or unsaturated C6-C30 aliphatic monocarboxylic acid, or an ester thereof;

and, subsequently, by reacting the remaining residual amino groups with exchangeable hydrogens of the aminoamide thus obtained with:

c) from 0.3 to 1.0 moles of a C2-C10 di- or tri-carboxylic acid or of the corresponding anhydride for each mole of remaining amino groups. A further object of the invention is a method for the preparation of an oil dispersion of dithiocarbamates comprising:

i) preparing a mixture containing at least one fungicide of the dithiocarbamate family and an oil;

ii) adding the above described polyamide to the mixture;

wherein the oil dispersions of dithiocarbamates comprise from 5.0 to 60% by weight of said fungicide, from 10 to 90% by weight of oil and from 0.05 to 10% by weight of said polyamide.

Another object of the invention is a method for the treatment of plants, crops and fields comprising the use of the dithiocarbamate oil dispersion described above.

DETAILED DESCRIPTION OF THE INVENTION

Preferably, the dithiocarbamate oil dispersion of the invention comprises: from 7.0 to 60% by weight of at least one fungicide of the dithiocarbamate family, from 20 to 80% by weight of an oil and from 0.1 to 5.0 % by weight, more preferably from 0.2 to 3.0% by weight, of the polyamide described above.

The fungicide of the dithiocarbamate family can be chosen, for example, from amobam, asomate, azithiram, carbamorph, cufraneb, cuprobam, disulfiram, ferbam, metam, nabam, tecoram, thiram, urbacide, ziram, dazomet, etem, milneb, mancopper, mancozeb, maneb, metiram, polycarbamate, propineb and zineb. The preferred fungicides of the dithiocarbamate family are: mancozeb, maneb, thiram and ziram. Mancozeb is the most preferred.

Oil is a liquid organic vehicle insoluble in water and can be one of those oils commonly used in agriculture to make dispersions in oil for agricultural use. The oils suitable for use in the dispersions of the invention are, for example:

• linear or branched paraffins C8-C30 carbon atoms with boiling points above 140 ° C (paraffin oils), for example octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, their mixtures or their mixtures with homologs with higher boiling points, such as hepta-, octa-, ninth-decane, eicosane, eneicosan, docosan, tricosan, tetracosan, pentacosan and the branched chain isomers;

• mineral oils, or mineral oil distillation fractions (petroleum), such as blends of linear or branched C14-C30 hydrocarbons with open chain;

• C7-C18 aromatic or cycloaliphatic hydrocarbons, which can be substituted or unsubstituted, for example mono- or polyalkylsubstituted benzenes or mono- or poly-alkylsubstituted naphthalenes;

• vegetable oils, such as liquid triglycerides such as olive oil, castor oil, palm oil, sesame oil, corn oil, rice oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil , linseed oil, sunflower oil, safflower oil, or even their transesterification products, for example alkyl esters, such as the methyl ester of rapeseed oil or the ethyl ester of rapeseed oil;

• oils of animal origin, such as whale oil, cod liver oil or mink oil;

• liquid esters of monoalcohols or C1-C12 polyols, for example butanol, noctanol, i-octanol, dodecanol, cyclopentanol, cyclohexanol, cycloctanol, ethylene glycol, propylene glycol and benzyl alcohol, with carboxylic or polycarboxylic acids C2-C10 as caproic acid , capric acid, caprylic acid, pelargonic acid, succinic acid and glutaric acid, or with aromatic carboxylic acids such as benzoic acid, toluic acid, salicylic acid and phthalic acid. The esters usable in the oil dispersions of the invention are, for example, benzyl acetate, the ethyl ester of caproic acid, the ethyl ester of pelargonic acid, the ethyl or methyl ester of benzoic acid, methyl, propyl or butyl ester of salicylic acid, diesters of phthalic acid with saturated aliphatic or alicyclic C1-C12 alcohols, such as dimethyl, dibutyl and diisocyl esters of phthalic acid;

• liquid amides obtained from amines, such as C1-C5 alkylamines or alkanolamines, reacted with C6-C18 carboxylic acids;

• their blends.

According to a particular embodiment, the oil is selected from paraffinic oils, mineral oils, in particular those having an aromatic portion lower than 8% by weight, vegetable oils or their transesterification products, and from mixtures of these oils .

In a preferred embodiment of the invention, the polyamine a) has n amino groups with exchangeable hydrogens, wherein n is an integer between 3 and 4. More preferably, n is 3.

Preferred polyamines include polyalkylene polyamines, for example those having formula I:

H2N [(CH2) xNH] yH I

where x is an integer between 1 and 6 and y is an integer between 1 and 5.

Examples of preferred polyalkylene polyamines of formula I are those in which x is 2 or the polyethylene amines, such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and their mixtures. Other preferred polyalkylene polyamines are polyethyleneimines with an average molecular weight of less than about 300 daltons, which exhibit a low degree of branching.

More preferably, polyamine a) is a polyethylene amine selected from diethylene triamine, triethylene tetramine, and their mixtures. Even more preferably, the polyamine a) is diethylene triamine.

The aliphatic monocarboxylic acid C6-C30 b) (or its ester) can be both unsaturated and saturated.

Examples of C6-C30 aliphatic unsaturated monocarboxylic acids suitable for the preparation of the polyamide of the invention include unsaturated and polyunsaturated aliphatic carboxylic acids with from 6 to 30 carbon atoms. Examples of these acids are palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid and the like.

Examples of C6-C30 aliphatic saturated monocarboxylic acids include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, docosanoic acid and the like.

Blends of aliphatic C6-C30, saturated and unsaturated monocarboxylic acids can also be used.

In a preferred embodiment of the invention, the C6-C30 aliphatic monocarboxylic acid b) is a mixture of C12-C22 aliphatic monocarboxylic acids, saturated and unsaturated.

In a more preferred embodiment of the invention, the C6-C30 monocarboxylic acid b) is a mixture of C12-C22 saturated and unsaturated aliphatic monocarboxylic acids, containing at least 40% by weight, preferably at least 60% by weight, of oleic acid.

Particularly preferred sources of monocarboxylic acids or mixtures thereof are natural oils, such as coconut oil, mustard oil, palm oil, olein, soybean oil, canola oil, tall oil, sunflower oil, and mixtures thereof.

Mixtures of monocarboxylic acids obtained as a byproduct in the biodiesel production process are further suitable sources of aliphatic C6-C30, saturated and unsaturated monocarboxylic acids.

In a preferred embodiment of the invention, the polyamine is reacted with a saturated or unsaturated C6-C30 aliphatic monocarboxylic acid or a mixture of C6-C30 aliphatic monocarboxylic acids, obtained by hydrolysis of the above sources.

Preferably, the source of monocarboxylic acids is selected from tall oil, rapeseed oil, soybean oil, by-products of the biodiesel production process and their mixtures.

The preparation of the aminoamide can be carried out according to methods well known to those skilled in the art. For example, by heating the polyamine a) and the monocarboxylic acid b) (or an ester thereof) up to 250 ° C, preferably between 140 and 180 ° C, in the presence or not of a suitable hydrocarbon solvent such as toluene or xylene and by azeotropically distilling the water formed, with or without catalysts, such as p-toluenesulfonic acid, zinc acetate, zirconium naphthenate or tetrabutyl titanate. Usually, the end point of the reaction is considered to have been reached when the acid number of the reaction mass, determined by the standard method ASTM D1980-87, is lower than 30 mgKOH / g, preferably lower than 10 mgKOH / g.

When the polyamine used is diethylene triamine, in the first stage one mole of diethylene triamine is preferably reacted with 1.4 - 2.0 moles of C6-C30 aliphatic monocarboxylic acid.

The di- or tri-carboxylic acid or the corresponding anhydride c), which can be reacted with the aminoamides described above to form the polyamide of the present invention, preferably have 3 to 8 carbon atoms, more preferably have 4 atoms carbon.

Examples of suitable C2-C10 di- or tri-carboxylic acids include succinic acid, malonic acid, ethylene dioxyacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid; citric acid, aconitic acid, citraconic acid, carboxymethyl oxysuccinic acid and lactoxysuccinic acid; phthalic acid; and their mixtures.

Preferably, the C2-C10 c) di- or tri-carboxylic acid is a C3-C8 dicarboxylic acid. Particularly suitable di-carboxylic acids for the realization of the present invention are fumaric acid, malonic acid, maleic acid, or their corresponding anhydrides; and their mixtures. Maleic acid (and its anhydride) is the most preferred C3-C8 di-carboxylic acid.

The aminoamide containing amino groups with replaceable hydrogens and the di- and / or tri-carboxylic acid (or the corresponding anhydride) described above can be condensed at a temperature ranging from about 120 to about 250 ° C, preferably from about 140 at about 200 ° C, while the water formed is distilled. The final point of the reaction is considered to have been reached when the total amine value of the reaction mixture, determined by the standard method ASTM D2074-12, is lower than 60 mgKOH / g, preferably lower than 40 mgKOH / g, more preferably lower than 20 mgKOH / g.

Preferably, the acid number of the polyamide thus obtained, determined with the standard method ASTM D1980-87, is lower than 70 mgKOH / g, more preferably it is comprised between 15 and 60 mgKOH / g.

In the preferred embodiment of the invention, the remaining amino groups with exchangeable hydrogens of the polyamide are reacted with 0.4 to 0.9 mol, more preferably 0.4 to 0.7 mol, of C2-C10 acid of - or tri-carboxylic, preferably di-carboxylic, for each mole of remaining amino groups.

In the most preferred embodiment of the invention, the remaining amino groups with exchangeable hydrogens are reacted with 0.4 to 0.9 mol, more preferably 0.4 to 0.7 mol, of maleic acid (or its anhydride ) for each mole of residual amino groups.

Particularly suitable for the realization of the present invention is the polyamide obtained by reacting:

a) one mole of diethylene triamine;

b) from 1.4 to 2 moles of a mixture of C12-C22 aliphatic monocarboxylic acids, saturated and unsaturated or of their esters;

and, subsequently, by reacting the remaining amino groups with exchangeable hydrogens of the aminoamide thus obtained with:

c) from 0.4 to 0.7 moles of maleic acid or its anhydride for each mole of remaining amino groups.

The polyamides described above show unexpectedly high stabilization performances of dispersions in dithiocarbamate oil, in particular in the presence of vegetable oils and paraffinic oils.

In a preferred embodiment, the dithiocarbamate oil dispersion of the invention further comprises from 5 to 30% by weight, preferably from 5 to 20% by weight, of at least one surfactant. Surfactants are used not only to improve dispersion and to emulsify oil upon dilution in water, but also to increase suspension stability, wettability and penetration, and to promote mixing and stability of the suspension / emulsion after dilution with water.

Suitable surfactants can be anionic, cationic, nonionic, ampholytic and mixtures thereof.

Suitable surfactants are, for example, nonionic emulsifiers and dispersants, such as:

• aliphatic, saturated and unsaturated alcohols, polyalkoxylated, for example polyethoxylated and / or polypropoxylated, such as alcohols with from 8 to 24 carbon atoms in the alkyl radical and an average degree of alkoxylation from 1 to 50, preferably from 3 to 20;

• polyalkoxylated arylalkylphenols, such as for example polyalkoxylated tristyrylphenol, with an average degree of alkoxylation ranging from 3 to 50, preferably from 5 to 25;

• polyalkoxylated alkylphenols having one or more alkyl radicals, such as for example nonylphenol or tri-sec-butylphenol polyalkoxylates, and an average degree of alkoxylation ranging from 2 to 40, preferably from 4 to 20;

• fatty acids or polyalkoxylated glycerides containing hydroxy-fatty acids, such as castor oil, having an average degree of alkoxylation between 3 and 40;

● esters of sorbitan or sorbitol with fatty acids or esters of sorbitan or polyalkoxylated sorbitol;

• polyalkoxylated amines;

• two and three block copolymers, for example from alkylene oxides, such as those from ethylene oxide and propylene oxide, having an average molar mass between 200 and 8000 g / mol, preferably from 1000 to 4000 g / mol;

• alkyl-polyglycosides or polyalkoxylated alkyl-polyglycosides.

Preferred non-ionic surfactants are polyalkoxylated saturated and unsaturated aliphatic alcohols, in particular alkoxylated aliphatic alcohols with 8-14 carbon atoms in the alkyl group and 3 to 20 ethylene oxide and / or propylene oxide units; polyalkoxylated arylalkylphenols and two- and three-block copolymers, in particular polyethylene oxide / polypropylene oxide copolymers with an average molar mass of 1000 to 4000 g / mol.

Anionic surfactants are also suitable, for example:

• polyalkoxylated nonionic surfactants which have been ionically modified, for example by converting the free terminal hydroxyl function of the alkylene oxide block into a sulphate or phosphate ester;

• alkali and alkaline earth metal salts of alkylaryl sulphonic acids having a straight or branched alkyl chain;

• alkali and alkaline earth metal salts of paraffin-sulphonic acids and chlorinated paraffin-sulphonic acids;

• polyelectrolytes, such as lignosulfonates, naphthalenulfonate and formaldehyde condensates, and polystyrenesulfonates;

• anionic esters of alkyl-polyglycosides, such as alkyl-polyglucosides sulphoxuccinates or citrates;

• alkali and alkaline earth metal salts of esterified sulfosuccinic acid, once or twice with aliphatic, cycloaliphatic and / or aromatic alcohols, linear or branched, or esterified once or twice with adducts of alcohols and alkylene oxides.

Preferred anionic surfactants are the polyalkoxylated nonionic surfactants which have been ionically modified, the alkali and alkaline earth metal salts of the alkylaryl sulfonic acids having a straight or branched chain alkyl and the anionic esters of alkyl polyglycosides.

Examples of cationic and ampholytic surfactants are: quanternary ammonium salts, alkyl amino acids, and ampholytic betaines and imidazolines.

Nonionic surfactants are the preferred surfactants for the practice of the present invention.

The dithiocarbamate oil dispersion of the invention can further comprise from 0.55 to 50% by weight, preferably from 2 to 30% by weight, of at least one other agrochemical active ingredient.

The most suitable agrochemical active ingredients for dispersion of dithiocarbamates in oil are, for example, additional fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, arachnicides, insect growth regulators, repellents, antibiotics, plant growth regulators, nutrients vegetables and their mixtures.

Examples of fungicides that can be mentioned are:

2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoro-methoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxyanilide; 2,6-dichloro-N- (4-trifluoro-methylbenzyl) -benzamide; (E) -2-methoxymino-N-methyl-2- (2-phenoxyphenyl) -acetamide; 8-hydroxyquinoline sulfate; methyl (E) -2- {2- [6- (2-cyanophenoxy) -pyrimidine-4-yloxy] -phenyl} -3-methoxyacrylate; methyl (E) -methoxyimino [alpha (o-tolyloxy) -o-tolyl] -acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, captaphonate methyl, captaphonate , chloroneb, chloropicrin, chlorothalonil, chlozolinate, cymoxanil, cyproconazole, cyprofuram, carpropamide, dichlorophen, diclobutrazole, dichlofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dinethoficonazole, dimethyrimol, dinethomorphine, diphenocene, dinethomorphine , edifenphos, epoxyconazole, ethirimol, etridiazole, fenarimol, fenbuconazole, fenfuram, phenitropan, fenpiclonil, fentin acetate, fentin hydroxide, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilumamide, phosphylum-alphide, flusilum-alphide, flusilum-alphetine , fuberidazole, furalaxyl, fenhexamide, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, im ibenconazole, iminoctadine, iprobenfos (IBP), iprodion, isoprothiolan, iprovalicarb, kasugamycin, copper-based preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, copper-oxine and Bordeaux mixture ; mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metsulfovax, mydobutanil, nitrothalisopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxycarboxine, pefurazoate, penconipyrim, propenamarazole, propenamarazole, propenamarazole, penconipyrimar, p propiconazole, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), quinoxyfen, sulfur and sulfur-based products, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-triadoliadhyl-methyl-methyl , triazoxide, trichlamide, tricyclazole, tridemorph, trifiumizole, triforin, triticonazole, trifioxystrobin, validamycin A, vinclozolin, ciproconazole, dodine, fenamidone, fenexamide, fluopicolide, fluoxastrobin, triforin, triticonazol azoxystrobin, acibenzolar-S-methyl, cyprodinil, mandipropamid, fenpropidin, boscalid, kr hexoxim-methyl, pyraclostrobin, dimetomorf, fenpropimorf, metraphenone, tolclofos-methyl and 2- [2- (1-chloro-cyclopropyl) -3- (2-chlorophenyl) - 2-hydroxypropyl] - 2, 4-dihydro- [l , 2,4] -triazole-3-thione.

Examples of bactericides that can be mentioned are:

bronopol, dichlorophen, nitrapyrin, kasugamycin, octhilinon, furanecarboxylic acid, oxytetracycline, probenazole, streptomycin, teclophthalam, copper sulfate and and other copper based products.

Examples of insecticides, acaricides and nematicides that can be mentioned are:

abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, 4-bromo-2- (4-chlorfenil) -1- (ethoxymethyl) -1- 5- (trifluoromethyl) -pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophosa, bufencarb, buprofezin, butocarboxine, butylpyridaben, cadusafos, carbulfocurbion, carbulfocarbaryl, paper chlaretoxyfos, chlorfenvinphos, chlorfluazuron, chlormephos, N - [(6-chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethane imidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythinente, clofanente , cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazin, deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diphthalon, diphthion , disulfoton, emamectin, esfe n valerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalonerate, flythonufenox, flythonufiprox, flythonurin, flythonufenox fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos, bexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxamrinathion, ivermectin, maltrifac methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monochrome phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenophos, promecarb, propapbos, propoxur, prothiophos, prothoate, py metrozine, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, salithion, ebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupflenzy thiamethoxam, thiodicarb, thiofanox, thiomethon, thionazine, thuringiensin, tralomethrin, transfluthrin, triarathen, triazophos, triawron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMrinC, xylylcarathen, triazophos, triawron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMrinC, xylylcarbate alfacypermethrine, alphametrine and metaflumizone.

Examples of herbicides that can be mentioned are:

anilides, such as diflufenican and propanil; arylcarboxylic acids, such as dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; esters of aryloxy-phenoxy-alkanoic acids, such as diclofop-methyl, fenoxapropethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones, such as chloridazon and norflurazon; carbamates, such as chlorpropham, desmedipham, phenrnedipham and propham; chloroacetanilides, such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroarylines, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas, such as chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as mefenacet; sulfonylureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron-methyl, and tribenhyl; thiocarbamates, such as butylate, cycloate, diallate, EPTCL, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such as atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones, such as hexazinon, metarnitron and metribuzin; and others, such as aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoqual, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosapribur, sodium bisulfon, bisulfon-bisulfon, sodium flufenacet, foramsulfuron, iodosulfuron methyl sodium, isoxadifen ethyl, isoxaflutole, mefenpyr diethyl, mesosulfuron methyl, sulcotrione, mesotrione, prosulfuron, florasulam, clodinafop propargil, pinoxaden, trinexapac ethyl, profethoximazamide, imoxydimazamide, profethoxamide

Examples of plant growth regulators that may be mentioned are chlorcholine chloride and ethephon.

Examples of repellents that may be mentioned are diethyl-toluamide, ethylhexane-diol and buto-pyronoxyl.

Other classes of pesticides suitable for the formulation of the dithiocarbamate oil dispersions of the invention are known to those skilled in the art or can be found, for example, in "The Pesticide Manual", 15th edition, The British Crop Protection Council, 2009, and in the literature cited therein.

Examples of plant nutrients that can be added to the dithiocarbamate oil dispersion of the invention are conventional inorganic or organic fertilizers used to provide plants with macro- and / or micronutrients, such as: ammonia salts, such as ammonium sulphate, ammonium bisulfate, ammonium salts of carboxylic acids, ammonium chloride, ammonium carbonate, ammonium phosphate, urea and urea derivatives; sources of phosphorus, such as phosphoric salts, for example monoammonium phosphate, diammonium phosphate; sources of potassium, such as potassium phosphate and mono- or dipotassium carbonate; compounds containing micronutrients and secondary substances such as zinc, manganese, magnesium, iron, calcium, nickel, molybdenum, sulfur, boron and their chelates in the form of salts; polycarboxylic acids, such as citric acid; protein derivatives and protein hydrolysates; and their mixtures. Preferred plant nutrients are monoammonium phosphate, diammonium phosphate, ammonium sulfate, sulfur, urea and urea derivatives.

In order to further improve the stability of the composition, the dithiocarbamate oil dispersion of the invention can comprise from 0.01 to 5% by weight of a thickener. Suitable thickeners are for example thickeners based on natural polymers, such as cellulose derivatives; hydrogenated castor oil or polyhydroxystearic acid; bentons and modified silica. Natural oils and their derivatives are the preferred thickeners. The dispersion in oil according to the invention can comprise from 0.5 to 35% by weight of adjuvants commonly used in this field and well known to those skilled in the art, such as wetting agents, anti-drift agents, penetrating agents and adhesives.

In addition to each of the aforementioned components, the aforementioned dispersion in oil can also comprise from 0.1 to 10% by weight of other agronomic additives and substances commonly used for "crop management", such as water-soluble vehicles and / or deflocculants. (e.g. kaolin, lignin-based compounds) and / or defoamers (e.g. silicon-based), antifreeze agents, dyes (e.g. azo dyes), preservatives (e.g. biocides and / or antioxidants), fillers, perfumes, evaporation inhibitors, pH regulators, etc.

The oil suspensions according to the invention can be prepared with known methods.

In the method of the invention, the solid active ingredients are preferably used in the form of a very fine powder, i.e. as a micronized powder with particles having an average size of less than 50 microns, preferably less than 20 microns, more preferably less than 10 microns, or they can be brought to this average particle size at any stage of the preparation of the dispersion.

In one embodiment, it is possible to prepare the dispersion by means of a first coarse grinding, in the presence of the oil, of the active ingredient and a subsequent wet grinding, so that the dithiocarbamate particles have an average size of less than 50 microns, preferably less than 20 microns. The grinding can be carried out in a colloidal or ball or sand mill, preferably in a ball mill.

In a further embodiment, it is possible to prepare the dispersion by mixing the oil, any other liquid additives and the solid ingredients previously ground to an average particle size of about 20 to 50 microns in a dry mill and then, optionally, by subjecting the mixture to a fine treatment in a wet mill, for example in a ball mill or a sand mill, in order to bring the average size of the dithiocarbamate particles to values below 20 microns, preferably below 10 micron.

The polyamide described is preferably added after grinding but, since it does not increase the viscosity of the dispersion of the invention, it can also be added before grinding. It can be poured into the liquid as it is, preferably heated to a temperature above 40 ° C, or it can be pre-dispersed or pre-dissolved in oil and then added to the ground mixture.

The dithiocarbamate oil dispersions of the invention have a Brookfield RV® viscosity at 25 ° C and 20 rpm of at least 300 mPa * s, preferably of at least 1000 mPa * s and usually less than 25,000 mPa * s, preferably less than 10,000 mPa * s.

The oil dispersion of dithiocarbamates can be diluted with water or aqueous solutions of agronomic compounds before use to produce a sprayable composition, to be used for the treatment of plants or crops. Dilution in water usually generates suspensions, emulsions, suspoemulsions or solutions of dithiocarbamates at a concentration of at least 0.001 g / l. It may be advantageous to add to the obtained aqueous composition further agrochemical active substances and / or adjuvants and additives conventionally used for the application, for example adhesives or anti-drift agents.

The invention also relates to the sprayable aqueous compositions obtained by diluting the oil dispersions of dithiocarbamates of the present invention.

The invention also relates to a method which comprises applying to plants or crops or soils an effective amount of sprayable aqueous compositions obtained by diluting the dithiocarbamate oil dispersions of the present invention. The application can be done by spray equipment from the ground or in the air. The amount of dithiocarbamates applied is within a relatively wide range. It basically depends on the nature of the desired effect. In general, the application rates are at least 0.01 g of active ingredient per hectare of land surface.

EXAMPLES

Characterization methods

The acid number was determined according to the standard method ASTM D1980-87.

The total amine value was determined according to the ASTM D2074-12 standard method.

Brookfield RV® viscosity (mPa * s) was determined at 25 ° C and 20 rpm using a Brookfield RV® viscometer.

Ingredients

The following ingredients were used in the Examples:

• Tall oil fatty acids (TOFA);

• Diethylene triamine (DETA);

• Triethylene tetramine (TETA)

• Maleic anhydride (MA);

• Citric acid, anhydrous;

• Fumaric acid;

• Mancozeb, 85% by weight of active substance;

• Methiram, 85% by weight of active substance;

• BANOLE, paraffin oil, from Total SA;

• EDC 95/11, hydrocarbon, C15-C20, n-alkanes, isoalkanes, cyclics, aromatic content <0.03%, from Total SA;

• FLUID GENERA 9, paraffin oil, from Total SA;

• Soy lecithin;

• CHIMIPAL AC / 9, ethoxylated fatty alcohol from Lamberti S.p.A.;

• EMULSON AG / CAL E, alkylbenzen sulfonate, from Lamberti S.p.A.;

• ESATERGE 15 S5, alkoxylated fatty alcohol, from Lamberti S.p.A.;

• AEROSIL 200, hydrophilic fumed silica, from Evonik Resource Efficiency GMBH;

• FLUIDIFIER FD, polyester based dispersant, from Lamberti S.p.A. Preparation of Polyamides

Polyamide 1

842.4 g of TOFA were loaded into a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical propeller stirrer and heated to about 50 ° C. Then 187.6 g of DETA was added. The temperature of the mixture was brought to 160 ° C under a nitrogen atmosphere and maintained for 3 hours. At the end of the reaction, the acid number of the aminoamide was lower than 10 mgKOH / g.

Subsequently, the reaction mass was cooled to about 80 ° C and 151.4 g of MA were slowly added. The reaction temperature was again increased to 180 ° C and maintained at this value for 60 min. The polyamide thus obtained had a total amine content lower than 26 mgKOH / g and an acid number of about 18 mgKOH / g. The polyamide was then diluted in EDC 95/11, to a final concentration of 65% by weight based on the weight of the solution.

Polyamide 2

In a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical propeller stirrer, 650.2 g of TOFA i were charged and heated to about 50 ° C. Then 146.2 g of TETA was added. The temperature of the reaction mixture was brought to 160 ° C under a nitrogen atmosphere and maintained for 3 hours. At the end of the reaction, the aminoamide had an acid number lower than 20 mgKOH / g.

Subsequently, the mass was cooled to about 90 ° C and 98.1 g of MA was slowly added. The reaction temperature was maintained at 90 ° C for 60 minutes. The polyamide thus obtained had a total amine content lower than 50 mgKOH / g and an acid number lower than 45 mgKOH / g.

The polyamide was then diluted in EDC 95/11, to a final concentration of 65% by weight based on the weight of the solution.

Polyamide 3

578 g of TOFA were loaded into a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical propeller stirrer and heated to about 50 ° C. Then 103.2 g of DETA was added. The temperature of the mixture was brought to 160 ° C under a nitrogen atmosphere and maintained for 3 hours. At the end of the reaction, the acid number of the aminoamide was lower than 20 mgKOH / g.

Subsequently, the reaction mass was cooled to about 140 ° C and 192 g of Citric Acid were slowly added. The reaction temperature was again increased to 160 ° C and maintained at this value for 60 min. The polyamide thus obtained had a total amine content lower than 20 mgKOH / g and an acid number of about 40 mgKOH / g.

The polyamide was then diluted in EDC 95/11, to a final concentration of 65% by weight based on the weight of the solution.

Polyamide 4

578 g of TOFA were loaded into a 2000 ml glass reactor equipped with a Dean-Stark apparatus and a mechanical propeller stirrer and heated to about 50 ° C. Then 103.2 g of DETA was added. The temperature of the mixture was brought to 160 ° C under a nitrogen atmosphere and maintained for 3 hours. At the end of the reaction, the acid number of the aminoamide was lower than 20 mgKOH / g.

Subsequently, 116.1 g of Fumaric Acid was slowly added. The reaction temperature was increased to 180 ° C and maintained at this value for 120 min. The polyamide thus obtained had a total amine content lower than 20 mgKOH / g and an acid number of about 40 mgKOH / g.

The polyamide was then diluted in EDC 95/11, to a final concentration of 65% by weight based on the weight of the solution.

Stability of Oil Dispersions

The dithiocarbamate / oil blends were prepared by vigorously mixing the oil, surfactants and agrochemical active ingredient. The mixtures were then ground with a ball mill until an optimal particle size distribution (D50 <2 μm; D90 <5 μm; determined with a Malvern Mastersizer 2000 laser light diffraction spectrometer) was achieved. The recipes, in grams per 100 g, of the dispersions in dithiocarbamate oil are summarized in Table 1. The stabilizers of the invention (Polyamides 1-5) or the comparative stabilizers (Aerosil 200 and Fluidificante FD) were added after grinding as such or pre-dissolved / pre-dispersed at a concentration of 25% by weight in oil.

Table 1

All oil dispersions were homogeneous and did not show lumps or gels.

The stability tests (storage stability test) were carried out at room temperature and at 54 ° C on each dispersion in oil to monitor the appearance of the dispersions over time, in particular to highlight the presence or absence of an oil phase or a creamy phase in the composition, the presence or absence of aggregations or sediments and the presence or absence of supernatants. For this purpose, about 100 ml of the agrochemical oil dispersions were sealed in glass containers and left to rest at room temperature (rt) and in an oven at 54 ° C. Table 2 reports the test results. The term "Thixotropic" means that the dispersion has become significantly more viscous, but is still flowing after stirring. The term "Gel" means that the dispersion has become extremely viscous and is no longer free flowing, even after stirring. Table 2

* Comparative

The results show that the polyamides of the invention do not increase the viscosity of the oil dispersions, do not form gels or lumps during dissolution and have good stabilization performance.

The dispersions of dithiocarbamate oil according to the invention can be easily prepared and show good stability over time, even at high temperatures. These dispersions are pourable, even after a long period of storage, and dispersible in water with minimal agitation and have a low tendency to form films in water, which can easily block the filters of the sprayers nozzles.

Claims (10)

CLAIMS 1) Dispersion in oil of dithiocarbamates comprising: from 5.0 to 60% by weight of at least one fungicide of the dithiocarbamate family, from 10 to 90% by weight of an oil and from 0.05 to 10% by weight of a polyamide obtained by reacting: a) a mole of a polyamine having n amino groups with exchangeable hydrogens, wherein n is an integer between 2 and 6; b) from 1 to n-1 moles of a saturated or unsaturated C6-C30 aliphatic monocarboxylic acid, or an ester thereof; and, subsequently, reacting the remaining amino groups with exchangeable hydrogens of the aminoamide thus obtained with: c) from 0.3 to 1.0 moles of a C2-C10 di- or tri-carboxylic acid or of the corresponding anhydride for each mole of remaining amino groups. 2) The oil dispersion of dithiocarbamates of claim 1), comprising: from 7.0 to 60% by weight of at least one fungicide of the dithiocarbamate family, from 20 to 80% by weight of an oil and from 0.1 to 5 0% by weight of said polyamide. 3) The oil dispersion of dithiocarbamates of claim 1), wherein said polyamine a) is a polyalkylene polyamine of formula I: H2N [(CH2) xNH] yH I where x is an integer between 1 and 6 and y is an integer between 1 and 5. 4) The oil dispersion of dithiocarbamates of claim 3), in which said polyamine a) is a polyalkylene polyamine of formula I in which x is 2, or a polyethylene amine. 5) The oil dispersion of dithiocarbamates of claim 1), wherein the C6-C30 b) monocarboxylic aliphatic acid b) is a mixture of C12-C22 aliphatic monocarboxylic acids, saturated or unsaturated. 6) The oil dispersion of dithiocarbamates of claim 1), wherein the C2-C10 c) di- or tri-carboxylic acid c) is a C3-C8 di-carboxylic acid. 7) The oil dispersion of dithiocarbamates of claim 1), wherein said oil is selected from the group consisting of linear or branched C8-C30 paraffins with boiling points higher than 140 ° C (paraffin oils); mineral oils; aromatic or cycloaliphatic hydrocarbons C7-C18; vegetable oils or their transesterification products; oils of animal origin; liquid esters of mono-alcohols or C1-C12 polyols with C2-C10 carboxylic or polycarboxylic acids; liquid amides obtained from amines, such as C1-C5 alkylamines or alkanolamines, reacted with C6-C18 carboxylic acids; and their mixtures. 8) The oil dispersion of dithiocarbamates of claim 7), wherein the oil is selected from paraffinic oils, mineral oils, vegetable oils or their trans-esterification products, and their mixtures. 9) The oil dispersion of dithiocarbamates of claim 1), further comprising from 5 to 30% by weight of at least one surfactant. 10) Method for the treatment of plants, crops and fields including the use of the dispersion in oil of dithiocarbamates of claims 1) -9).