EP2136623A2

EP2136623A2 - Agrochemical preparations

Info

Publication number: EP2136623A2
Application number: EP08748899A
Authority: EP
Inventors: Hans-Georg Mainx; Ansgar Behler
Original assignee: Cognis IP Management GmbH
Current assignee: Cognis IP Management GmbH
Priority date: 2007-04-21
Filing date: 2008-04-12
Publication date: 2009-12-30
Also published as: US20100087319A1; WO2008128666A3; DE102007018983A1; WO2008128666A2

Abstract

The invention relates to agrochemical preparations containing (a) active ingredients and (b) esters of hydroxycarboxylic acids.

Description

Agrochemical preparations

Field of the invention

The invention is in the field of agrochemicals and relates to novel compositions containing hydroxycarboxylic acid esters as emulsifiers or adjuvants.

State of the art

Commercially available crop protection agents can be formulated in very different ways. In general, concentrates are placed on the market which are emulsified or dispersed by the customer to an application concentration of 0.1 to 5% by weight in water and then sprayed onto the plants. The active ingredients contained in these formulations can either be present in dissolved form (EC or EW formulations), suspended or emulsified (SC or SE formulations) or used as solids (WP, WDG, EC formulations or spray powder). Over the last few years, in addition to the demand for particularly efficient active substances, another high performance criterion in the market has been the high toxicological and ecological compatibility of all formulation constituents, in particular the surfactant constituents (so-called "green products").

The object of the present invention was thus to provide new agrochemical preparations which, in addition to the known active ingredients, contain oil-soluble emulsifiers which at the same time are distinguished by the fact that they permit the stable incorporation of otherwise difficult-to-emulsify or disperse active ingredients Such adjuvants increase the properties of these active ingredients and also have a sufficiently high ecotoxicological compatibility. Description of the invention

The invention relates to agrochemical preparations containing

(a) Active substances and

(b) esters of hydroxycarboxylic acids.

Surprisingly, it has been found that esters of hydroxycarboxylic acids, especially esters based on citric acid, satisfy the complex requirement profile in an excellent manner. The esters are oil-soluble, have a high emulsifying and dispersing performance, and also allow the stable incorporation of active ingredients which otherwise can be emulsified or dispersed only by introducing high shear forces, and in many cases enhance the performance of these agents by enhancing penetration. In addition, they are easily and completely biodegradable and, in many cases, free from labeling in terms of point 15 of the EC Safety Gazette.

drugs

As active ingredients in the sense of the present invention, on the one hand (al) pesticides, i. Herbicides, insecticides and fungicides and, on the other hand, (a2) fatty substances and hydrocarbons, including mixtures of said groups. If differentiation is made here between two groups of active substances, then it is against the background that fatty substances and hydrocarbons are not only suitable as pesticides, but also represent classic carrier oils or solvents for the former group of active substances. A preferred embodiment of the present invention is therefore to use mixtures of groups (a1) and (a2). The individual groups of active ingredients are explained in more detail below:

Herbicides, fungicides and insecticides

The pesticides - as a generic term for herbicides, fungicides and insecticides, which may also be present in the agrochemical formulations, are preferably oil-soluble substances. Typical examples of suitable fungicides are azoxystrobin, benalabyl, carbendazim, chlorothalonil, cupfer, cymoxanil, cyproconazole, diphenoconazole, dinocap, epoxiconazole, fluazinam, flusilazole, flutriafol, folpel, fosetyl-aluminum, kresoxime-methyl, hexaconazole, mancozeb, Metalaxyl, metconazole, myclobutanil, ofurace, phentin hydroxide, prochloraz, pyremethanil, soufre, tebucanazole, and tetraconazole and mixtures thereof. As herbicides, alachlor, acloniphen, acetochlor, amidosulfuron, aminotriazole, atrazine, bentazone, biphenox, bromoxyl octanoates, bromoxynil, clethodim, chlodinoparpropargyl, chloridazon, chlorosulfuron, chlorotoluron, clomazone, cycloxydim, desdipham, dicamba, Dicyclofop-methyl, diurea, difluphenicanil, dimithenamid, ethofemesate, fluazifop, fluazifop-p-butyl, fluorochloridone, fluroxypyr, glufosinate, glyphosate, haloxyfop-R, ioxynil octanoate, isoproturon, isoxaben, metamitron, metazachlor, metolachlor, metsulfuron Methyl, nicosulfuron, notflurazon, oryzalin, oxadiazone, oxyfluorophen, paraquat, pendimethalin, phenmedipham, phenoxyprop-p-ethyl, propaquizafop, prosulfocarb, quizalofop, sulcotrione, sulphosate, terbutylazine, triasulftiron, trichloropyr, triflualin and triflusulforon-methyl, individually or to be used in a mixture. Finally, insecticides include biphthrine, carbofuran, carbosulfan, chlorpyriphos-methyl, chlorpyriphos-ethyl, β-cyfluthrin, λ-cyhalothrin, cyhexatin, cypermethrin, dicofol, endosulfan, τ-fluvalinate, α-methrine, δ-methrine, phenbutatin, pyrimicarb, Terbuphos and Tebuphenpyrad and their mixtures into consideration.

Furthermore, glyphosate can also be used as the active ingredient. Glyphosate is N- (phosphonomethyl) glycine, C ₃ H ₈ NO ₅ P, MW 169.07, melting point 200 ° C, LD ₅₀ (rat oral) 4320 mg / kg (WHO), a nonselective systemic Leaf herbicide, preferably in the form of its isopropylamine salt, for the total and semi-total control of grass weeds and weeds, including deep-rooted perennial species, in all arable crops, in fruit and vegetable crops. Viticulture is used. The structure is as follows:

O Il

HO-P-CH ₂ NHCH ₂ COOH

I oh

Glyphosate is understood as meaning all derivatives of glyphosate known to the person skilled in the art, that is to say preferably its mono- or diethanolamine salts of glyphosate. As cations continue sodium or potassium come into question. Of particular importance is the isopropylamine salt of glyphosate. Furthermore, any mixtures of these compounds can be used within the scope of the inventive use. Since glyphosate has only a low oil solubility, this active ingredient is preferably used with components other than tank mix adjuvants. Fat bites and hydrocarbons

As already explained above, fatty substances and hydrocarbons are also active substances under certain conditions, since they protect the plants from damage. First and foremost, however, they are typical carrier oils or solvents. The number of substances in question is correspondingly broad, the selection of which is critical only insofar as they comply with the toxicological and ecological regulations when used in nature. Preference is given to natural fats and oils or synthetic triglycerides, including especially rapeseed and sunflower oil. Instead of the glycerides, it is also possible to use the alkyl esters, especially the methyl esters. Also suitable are partial glycerides, fatty acids and fatty alcohols and fatty amines and fatty amides within the typical for the fatty substances C number range, that is 6 to 22. The hydrocarbons mainly mineral and white oils, alkyl aromatics and the known mixture of Solvesso ^® 100 (Fa. Exxon ) to mention.

hydroxycarboxylic

Esters of hydroxycarboxylic acids are known substances that can be obtained by the relevant methods of preparative organic chemistry. Usually, the synthesis is carried out by reacting the hydroxycarboxylic acids with the alcoholic components in the presence of acidic catalysts, wherein a component is initially introduced in excess and the water of condensation is removed continuously from the reaction equilibrium. Suitable starting materials are in principle all carboxylic acids which are substituted by a hydroxyl group. However, preference is given to lactic acid, malic acid, tartaric acid and, in particular, citric acid. Particularly preferred are esters of citric acid with

(bl) partial glycerides,

(b2) polyglycol ethers,

(b3) Polyglycol esters or (b4) ring-opening products of alpha-olefin epoxides

where the esters may be present as full or partial esters. Usually, technical mixtures are used which have a degree of substitution in the range of 1 to 2. Various types of suitable citric acid esters are described in more detail below: Esters of citric acid with partial glycerides

Esters of citric acid with partial glycerides (bl), ie mono- or diglycerides or their technical mixtures which still have a free hydroxyl group, preferably follow the formula (I),

OH

I

R ¹ OOC-CH ₂ CCH ₂ COOR ² (I)

COOR ³

in the R ^{1 is} a -CH ₂ -CH (OR ⁴ ) CH ₂ OR ⁵ group, R ² and R ^{3 are} independently of each other R ¹ or hydrogen, R ^{4 is} an acyl radical having 6 to 22, preferably 12 to 18 carbonato - and O or 1 to 3 double bonds and R ^{5 is} R ⁴ or hydrogen. Preferably, the partial glycerides are derived from fatty acids having 12 to 18 carbon atoms, especially technical coconut and palm fatty acids. Typical examples are the commercial products Lamegin ^® ZE 306, ZE Lamegin ^® 609 and Lamegin ^® ZE 618 (Cognis Germany GmbH & Co. KG).

Esters of citric acid with Polvslycolethern

Esters of citric acid with polyglycol ethers (b2), ie addition products of alkylene oxides to aliphatic alcohols which still have a free hydroxyl group at the end of the polyether chain, preferably follow formula (II),

OH

IR ⁶ OOC-CH ₂ CCH ₂ COOR ⁷ (II)

COOR ⁸

in the R ⁶ for a (EO) _nl (PO) _m i (EO) piR ⁹ -Gruρpe, R ⁷ and R ^{8 are} independently R ⁶ or hydrogen, R ^{9 is} an alkyl or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, and EO or PO stand for an ethylene or propylene oxide unit and the numbers nl, ml and pl independently for numbers from 1 to 100, preferably 2 to 10, wherein the sum (nl + ml + pl) must be different from zero. Preferably, for the esterification addition products of 1 to 10 moles of ethylene oxide and O to 2 moles of propylene oxide - the distribution can be carried out in random or blockwise manner - used in technical coconut or Taigfettalkohole. Particularly preferred is the trade ^® product Plantapon LC7 Cognis Germany GmbH & Co. KG), which is a mono / diester of citric acid with ₂ Ci _/ i ₄ + coconut alcohol 7EO.

Esters of citric acid with Polvslvcolestern

Esters of citric acid with polyglycol esters (b3), ie adducts of alkylene oxides to aliphatic carboxylic acids, which at the end of the polyether chain still have a free

Hydroxylgruppe have, preferably follow the formula (III),

OH

R ¹⁰ OOC-CH ₂ CCH ₂ COOR ¹¹ (IH)

I COOR ¹²

in the R ¹⁰ for an (EO) _{n 2} (PO) _{m 2} (EO) _{p 2} R ¹³ group, R ¹¹ and R ^{12 are} independently of each other R ¹⁰ or hydrogen, R ^{13 is} an acyl radical having 6 to 22, preferably 12 to IS Carbon atoms and O or 1 to 3 double bonds and EO or PO for an ethylene or propylene oxide unit and the numbers n2, m2 and p2 independently for numbers from 1 to 100, preferably 2 to 10, wherein the sum (n2 + m2 + p2) must be different from zero. For the esterification, adducts of 1 to 10 mol of ethylene oxide and 0 to 2 mol of propylene oxide - the distribution of which can be carried out in random or blockwise fashion - are preferably employed for industrial coconut or tallow fatty acids.

Esters of citric acid with ring-opening products of alpha-olefin epoxides

Esters of citric acid with alpha-olefin epoxides, ie alkanes which are substituted in the 1, 2-position by hydroxyl groups. Preferably follows the formula (IV),

OH

R ¹⁴ OOC-CH ₂ CCH ₂ COOR ¹⁵ (IV) I

COOR ¹⁶

in which R ¹⁴ represents a CH ₂ CH (OH) R ¹⁷ group, R is R ¹⁴ or hydrogen, and R ¹⁷ is ¹⁵ and R ¹⁶ independently represent an alkyl group having 4 to 22, preferably 6 to IO Kohlenstoffato- men. Preference is given to the use of esters of citric acid with ring-opening products of 1-decene, 1-dodecene or 1-tetradecene with water. preparations

In a further preferred embodiment of the present invention, the preparations may have the following composition:

(I) 0 to 10, preferably 1 to 5 wt .-% herbicides, insecticides and / or fungicides, (ii) 10 to 90, preferably 50 to 80 wt .-% fatty substances and / or hydrocarbons, and

(iii) 1 to 10, preferably 2 to 8,% by weight hydroxycarboxylic acid ester,

with the proviso that the quantities are optionally supplemented with other auxiliaries and additives to 100 wt .-%. As further ingredients, the formulations may contain nonionic emulsifiers, for example

(1) addition products of 2 to 120 moles of ethylene oxide and / or 0 to 75 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, fatty amines, to fatty acids having 8 to 22 carbon atoms, to alkylphenols having 8 to 15 C. Atoms in the alkyl group and fatty amines having 6 to 22 carbon atoms;

(2) Cnm fatty acid mono-, di and triesters of addition products of 1 to 120 moles of ethylene oxide with glycerine or technical oligoglycerols;

(3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs;

(5) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(6) polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate or polyglycerol poly-12-hydroxy stearate. Also suitable are mixtures of compounds from several of these classes of compounds;

(7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(8) partial esters based on linear, branched, unsaturated or saturated C6 / ₂₂ fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside , Lauryl glucoside) as well as polyglucosides (eg cellulose);

(9) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;

(10) wool wax alcohols; (11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol, (13) polyalkylene glycols and (14) glycerol carbonate.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. ₂ Ci _/ i ₈ fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are as refatting agents for cosmetic prepara- obligations known.

In many cases, the concomitant use of anionic surfactants has proven to stabilize the formulations and spray mixtures. The calcium salt of dodecylbenzenesulfonic acid (Ca-DDBS) as well as soaps and amide soaps are used here, since they have sufficient oil solubility.

Industrial Applicability

As explained above, the hydroxycarboxylic acid esters are distinguished by being oil-soluble, have excellent emulsifying and dispersing properties for agrochemically active compounds and increase their penetration capacity, are completely biodegradable and are toxicologically harmless. Another object of the present invention therefore relates to their use, especially the use of citric acid esters for the preparation of agrochemical formulations in which they can be used, for example, in amounts of 1 to 10 and preferably 2 to 8 wt .-%. Examples

Example 1 Ejection sprayer based on rapeseed oil

Example 2 Ejection spray on the basis of rapeseed oil methyl ester

Example 3 Ejection spray based on white oil

Example 4 Herbicide EC

Claims

claims

1. Agrochemical preparations containing

(a) Active substances and

(b) esters of hydroxycarboxylic acids.

2. Preparations according to claim 1, characterized in that the component (a) is selected from the group formed by herbicides, insecticides, fungicides, fatty substances and hydrocarbons and mixtures thereof.

3. Preparations according to claims 1 and / or 2, characterized in that they contain as component (b) esters of hydroxycarboxylic acids which are selected from the group formed by lactic acid, malic acid, tartaric acid and citric acid.

4. Preparations according to at least one of claims 1 to 3, characterized in that they as component (b) esters of citric acid with

(bl) partial glycerides,

(b2) polyglycol ethers,

(b3) polyglycol esters or

(b4) ring-opening products of alpha-epoxides

contain.

5. Preparations according to at least one of claims 1 to 4, characterized in that they contain as component (bl) citric acid ester of formula (I),

OH

R ¹ OOC-CH ₂ CCH ₂ COOR ² (I) COOR ³

in the R ^{1 is} a -CH ₂ -CH (OR ⁴ ) CH ₂ OR ⁵ -Grupρe, R ² and R ^{3 are} independently R ¹ or hydrogen, R ^{4 is} an acyl radical having 6 to 22 carbon atoms and O or 1 to 3 double bonds and R ^{5 is} R ⁴ or hydrogen.

6. Preparations according to at least one of claims 1 to 5, characterized in that they contain as component (b2) citric acid ester of formula (II),

OH

R ⁶ OOC-CH ₂ CCH ₂ COOR ⁷ (II)

COOR ⁸

R ^{6 is} an (EO) _n i (PO) _ml (EO) _p R ⁹ group, R ⁷ and R ⁸ are each independently R ⁶ or hydrogen, R ^{9 is} an alkyl or alkenyl radical having 6 to 22 carbon atoms , and EO or PO stand for an ethylene or propylene oxide unit and the numbers nl, ml and pl are independently from numbers from 1 to 100, the sum (n 1 + m 1 + p 1) being different from zero got to .

7. Preparations according to at least one of claims 1 to 6, characterized in that they contain as component (b3) citric acid esters of the formula (III),

OH

R ¹⁰ OOC-CH ₂ CCH ₂ COOR ¹¹ (HI)

COOR ¹²

in which R ^{10 is} an (EO) _{n 2} (PO) _{m 2} (EO) _{p 2} R ¹³ group, R ¹¹ and R ¹² are each independently R ¹⁰ or hydrogen, R ^{13 is} an acyl radical having 6 to 22 carbon atoms and O or 1 are up to 3 double bonds and EO or PO stands for an ethylene or propylene oxide unit and the numbers n2, m2 and p2 independently represent numbers from 1 to 100, where the sum (n2 + m2 + p2) must be different from zero ,

8. Preparations according to at least one of claims 1 to 7, characterized in that they contain as component (b4) citric acid esters of formula (IV),

OH

R ¹⁴ OOC-CH ₂ CCH ₂ COOR ¹⁵ (IV)

I

COOR ¹⁶

in which R ^{14 is} a CH ₂ CH (OH) R ¹⁷ group, R ¹⁵ and R ¹⁶ are each independently R ¹⁴ or hydrogen and R ^{17 is} an alkyl radical having 4 to 22 carbon atoms.

9. Preparations according to at least one of claims 1 to 8, characterized in that they

(i) O to 10% by weight of herbicides, insecticides and / or fungicides,

(ii) 10 to 90% by weight of fatty substances and / or hydrocarbons, and (iii) 1 to 10% by weight of hydroxycarboxylic acid ester

with the proviso that the amounts are optionally supplemented with other auxiliaries and additives to 100 wt .-%.

10. Use of hydroxycarboxylic esters for the preparation of agrochemical formulations.