DK174127B1 - New aqueous emulsions of plant protection products - Google Patents

Description

DK 174127 B1

The preparation of stock stable concentrated emulsions of herbicide-acting phenoxyalkanecarboxylic acid esters using aqueous solvents using ester-soluble emulsifiers and water-soluble dispersants is known and described in European Patent Application No. 47,396. For ester-soluble emulsifiers, optionally in admixture with alkylarylsulfonates, fatty acid polyethylene glycol esters, polyethylene glycol ethers of fatty alcohols, of glycerides or of alkylphenols and polyoxyethylene and polyoxy propylene block polymers. For dispersants, phosphated alkylaryl polyethylene oxides, the ammonium, sodium or potassium salts of phosphorylated polystyrylphenylpolyethylene oxide or ethylene oxide condensates of fatty amines.

The amounts of the oil-soluble emulsifiers added are between 1.01 and 11.1 parts by weight. 100 parts by weight of phenoxyalkanecarboxylic acid ester. The amounts of dispersants are from 0.5 to 5 parts by weight per minute. 100 parts by weight of aqueous solution. To avoid the resulting foam formation, antifoaming agents are added based on 15 long chain alcohols and silicones.

Attempts to extend the use of the above water-soluble ammonium, sodium or potassium salts of the phosphorylated alkylaryipolyglycol oxides to other than the active substances mentioned in European Patent Application No. 47,396 lead to significant application problems. In experiments with storage for 3 months at 50 ° C, a variety of preparations occur which are reversible to a certain extent only.

Similar problems are observed with the phosphorylated polystyrylphenyl polyethylene oxides described in European Patent Application No. 33,291; likewise, with alkylaryl polyglycol ether compounds described in DE-A No. 3,111,934, only to a certain degree heat-stable colloidal emulsions can be obtained.

EP-A-118,759 also discloses that end-positioned monophosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymers or salts thereof can be used as dispersing agents to prepare aqueous pesticide compositions.

US-A No. 4,220,611 discloses surfactant and emulsifying compounds containing at least two phosphate ester groups 35 linked through a polyoxyalkylene chain with C (8-13) fatty alkyl groups in the alcohol component of the phosphate ester groups. These DK 174127 B1 compounds include. described as possible emulsifiers for organic solvents in aqueous systems or for DDT preparations.

It has now surprisingly been found that it is advantageous to use certain water-soluble wetting and dispersing solvents in water and organic solvents in comparison with the water-soluble dispersers described in EP-A-47,396 of the type with phosphorylated alkylaryl polyethylene oxides and in comparison with those in EP-A no.

118,759 described once phosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymers once described.

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Thus, the present invention relates to plant protection agents based on aqueous emulsions containing one or more active substances which are characterized in that they contain as a dispersing agent a block copolymer of formula 15

ISLAND

II

(K0) 2? - [0 (CH2-CK2-0) x- (CT-CH2-0) y- (CH2-CH2-0) z]. ISLAND

Wherein CH and Z are independently of a number from 30 to 100, y is a number from 2 to 200, and n and m are equal to 0, 1 or 2, where the sum of n + m must be 2.

In particular salts are the alkali metal, alkaline earth metal, ammonium, mono, or trialkylammonium or mono, di or trialkanolammonium salts. In particular, these have from 1 to 5 C atoms in the alkyl moiety or alkanol moiety.

The compositions of the invention are largely free of organic solvents and inorganic salts. Consequently, they are harmless to handle, especially when transported and stored. By varying the proportion of polyethylene glycol, the desired viscosity of the finished composition can be easily adjusted so that the otherwise common dispersing and thickening agents can be dispensed with.

x and y preferably have the same meaning; y is in particular a number from 20 to 100 and n is especially 0.

These block polymers can be used as mixtures. Their preparation is disclosed in JP-A No. 7,247,982 or DE-A No. 3,542,441.

3 DK 174127 B1

In addition, the compositions of the invention may further contain antifreeze agents. For example, ethylene glycol, propylene glycol, butanediol, urea, glycerol, polyethylene glycols or polypropylene glycols are included. Furthermore, they may contain an additional 5 preparation aids such as conventional dispersants, emulsifiers, thickeners and - especially for solid active substances - also minor constituents of organic solvents.

In particular, such active substances can be used for those active substances which, on the basis of their low melting points by means of grinding devices, can only poorly or not at all be converted into an aqueous phase of a fine disperser, or even such active substances, whereby the grinding process requires special precautionary measures.

In view of the active substances used for plant protection products to be used, herbicides, insecticides, acarlcides, nematodicides, pheromones or repellants will be present, as these must not or only be insoluble in water. However, solid active substances must have a good to very good solubility of one of the organic solvents listed below.

Suitable herbicidal active substances are, for example, phenoxyphenoxy or heteroaryloxy-phenoxy-propionic acid alkyl esters such as α-4- (2 ', 4'-dichlorophenoxy) -phenoxy-propionic acid methyl ester [trivial name: dichlofopmethyl] (A), ethyl 2- [ 4- (6-chloro-2-benzothiazolyl-oxy) phenoxy] propionate (B) or ethyl 2- [4- (6-chloro-2-benzoxazolyl-oxy) phenoxy] propionate (common name: phenoxaprop -ethyl) (C), dinitroaniline compounds such as 2,6-dinitro-4-25 trifluoromethyl-N, N-dipropylaniline [trivial name: trifluralin] (D) or 2,6-dinitro-4-isopropyl-Ν, Ν-dipropylaniline [trivial name: Isopropaline] (E), hydroxybenzonitrile derivatives such as 2,6-dibromo-4-hydroxybenzonitrile octanoate (F), dinitrophenol compounds such as 2-sec-butyl-4,6-dinitrophenol [trivial name: dinoterb] (G).

Suitable insecticides are, for example, 1,4,5,6,7,7-hexachloro-8,9,10-trinorborn-5-ene-2,3-ylendimethylsulfite [trivial name: endosulfan], 2- (1-methyl -n-propyl) -4,6-dinitro-phenyl-2-methylcrotonate [common name: binapacryl], phosphoric acid esters such as 0,0-diethyl-0-1-phenyl-1H-1,2,4-triazol-3-yl phosphorus thioates [common name: triazophos] or pyrethroids such as (S) -α-cyano-3-phenoxybenzyl- (1R, 3R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane carboxylate [trivial name: deltamethrinj.

DK 174127 B1 4

Suitable fungicides may be mentioned, for example, ethyl 2-diethoxythiophosphoryloxy-5-methylpyrazolo [1,5-a] pyrimidine-6-carboxylate [common name: pyrazophos], as well as the pheromone compounds (E) -8- (E) -10-dodecadienol or (Z) -7,8-epoxy-2-methyl-octadecane, and as a repellant phthalic acid dimethyl ester.

5

With the exception of compounds (B) and (C), the insecticides and the repellant known from H. Martin, Pesticide Manual 6th edition 1979. The herbicides (B) and (C) are described in German Publication No. 2,640. 730, the two pheromones in M. Beroza, Chem. Controlling Insect Behavior, Academic Press, N.Y. 1970th

Typical dispersants to be used are preferably lignosulfonates, sodium salts of dinaphthylmethanedisulfonic acids, the sodium salt of a sulfonic acid of cresol, formaldehyde, sodium sulfite and oxynaphthylene sulfonic acid, the sodium salt of a sulfonic acid of m-cresol, , condensation products of aryl sulfonic acids and formaldehyde sodium salts, triethanolamine salts of phosphorylated polystyrene polyphenol polyethylene oxides, polyvinyl alcohol, dodecylbenzenesulfonic acid calcium and alkyl naphthalenesulfonates of varying alkyl chain length.

Suitable emulsifiers are nonionic, anionic or cationic surfactants, using mixtures of nonionic components with anionic components predominantly. However, combinations of nonionic and cationic surfactants can also be used. Preferred emulsifiers include phenylsulfonate calcium, ethoxylated nonylphenols, ethoxylated aliphatic alcohols, ethoxylated castor oil, fatty acid polyglycol esters, propylene glycol-ethylene glycol block polymers and mixtures thereof.

Water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone and cellulose derivatives can be used as thickeners.

As organic solvents, all water-immiscible solvents, e.g., aromatic compounds such as toluene, xylenes, 1/2 methyl naphthalene, dimethyl naphthalenes, aliphatic compounds such as paraffin oils, vegetable oils, alicyclic compounds such as cyclohexane, alkanols such as cyclohexanone, alcohol, ethers such as diethyl ether, ketones such as cyclohexanone, 4-methyl-cyclohexanone, isophorone, esters such as ethyl acetate and tri-n-butyl phosphate are suitable.

5 DK 174127 B1

In particular, the plant protection agents of the invention contain from 5 to 60% by weight of active substance, from 10 to 90% by weight, preferably from 15 to 40% by weight of water and from 0.5 to 20% by weight, preferably from 1 to 10% by weight of a compound having the formula I or salts thereof and conventional additives, optionally from 5 to 50% by weight of an antifreeze and / or from 1 to 10% by weight of a dispersant and / or from 1 to 15% by weight of an emulsifier and / or from 1 to 10%. 10% by weight of a thickener and / or from 1 to 30% by weight of an organic solvent.

The compositions of the invention are prepared by stirring the aforementioned components 10 or also shaking in the required amounts at temperatures between 0 and 60 ° C, conveniently at room temperature, in a high turbulence zone until the desired stable emulsion is formed; in this connection, particle diameters of preferably 1 to 15 microns must be set.

For the practical implementation of the process, the aqueous phase (carrier phase) is first prepared by stirring the di or polyols and dispersant together in water. The emulsifier portion is then added to the active substance to be emulsified and dispersed in the aqueous phase. For active substances with a melting point of approx. 0 ° C and above, it may be necessary to prepare concentrated solutions thereof in one or more of the above organic solvents and to disperse them in the aqueous phase after the addition of emulsifiers and optionally stabilizers.

However, one can also first mix the dispersant with the active substance and then with it disperse it in the aqueous phase.

The dispersion can be effected by a stirring or possibly also shaking process and it is conveniently continued until the organic phase corresponds to the desired size of the small droplets. A diameter of the small droplets from 1 to 15 micrometers is recommended.

The dispersion process may conveniently be carried out at room temperature, but may also be carried out in the cold or at elevated temperatures.

The following examples will illustrate the present invention in more detail.

DK 174127 B1 6

Example Examples Example 1 36% by weight of 2- (4- (2 ', 4'-dichlorophenoxy) -phenoxy) -propionic acid methyl ester is dissolved with stirring in 18% by weight xylene at from 20 to 25 ° C and 6% by weight of fatty acid polyglycol ester ( with 40 EO). Also dissolved at room temperature in 28% by weight water 2% by weight of the potassium salt of the phosphorylated ethylene oxide-propylene oxide-ethylene oxide block polymerate of the above formula I, n = 0 (with a proportion of 68% ethylene oxide in the final product) and then added. there 10% by weight ethylene glycol.

The above organic phase is slowly allowed to flow to this aqueous phase with vigorous stirring with a wing stirrer and stir the resulting white emulsion for another 15 minutes. One sample is stored for 3 months at 50 ° C, another for the same period of time at -10 ° C. The preparation is both chemically and technically stable.

15

Example 2 32.3 wt% endosulfan techn. is dissolved under stirring in 21% by weight of a mixture of aromatic compounds (boiling range from 219 ° C to 282 ° C) and 4% 20% by weight of the diethanolamine salt of the phosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymer of the above Formula I (with a 55% ethylene oxide content in the final product). At room temperature, 8 wt% glycerol is dissolved in 34.7 wt% water. The organic phase is allowed to run slowly with vigorous stirring and the resulting beige-colored emulsion is stirred for a further from ca. 15 to approx. 20 mi-25 nuts.

The preparation is chemically and technically stable.

EXAMPLE 3 30% by weight ethyl 2-diethoxythiophosphoryloxy-5-methylpyrazolo [1,5-apyrimidine-6-carb oxylate (pyrazophos) is dissolved in stirring in 18% by weight xylene at 20 to 25 ° C and 6 % by weight of solid acid polyglycol ester (with 40 EO). Also at room temperature, in 32% by weight water, 4% by weight of the potassium salt of the phosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymer of the above formula I, n = 0 (with a proportion of 50% ethylene oxide in the final product) is dissolved and then added. male 7 DK 174127 B1 10% by weight ethylene glycol. The above organic phase is allowed to run slowly to this aqueous phase with vigorous stirring with a wing stirrer and stir the resulting white emulsion for another 15 minutes. One sample is stored for 3 months at 50 ° C, another for the same period of time at -10 ° C. The preparation is both chemically and technically stable.

Example 4 In 49 wt% water, 6 wt% fatty acid polyglycol ester (36 EO), 3 wt% of the free acid of the phosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymer of the above Formula I (with a total proportion of 40%) are dissolved. % ethylene oxide) and 10% by weight glycerol. 32.0% by weight (E) -8- (E) -10-dodecadienol is allowed to stir thereto with vigorous stirring. The resulting white emulsion is stirred for another 15 from 15 to 20 minutes.

The preparation is chemically and technically stable.

Example 5 30% by weight endosulfan techn. is dissolved under stirring in 21% by weight of a mixture of aromatic compounds (boiling range from 219 ° C to 282 ° C) and 3% by weight of the free acid of the phosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymer of the above Formula I (with a proportion of 55% ethylene oxide in the final product). At room temperature, in 34.0 wt% water, 12 wt% polyethylene glycol (molecular weight 1000) is dissolved. The organic phase is slowly allowed to stir under vigorous stirring and the resulting beige colored emulsion is stirred for a further period of approx. 15 to approx. 20 minutes.

The composition is chemically and technically stable.

Example 6 20% by weight ethyl 2- (4- (6-chloro-2-benzthiazoyloxy) phenoxypropanoate is dissolved under stirring at 40 to 45 ° C in 36% by weight xylene and 4% by weight of the potassium salt of the phosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymers of formula I, n = 0 with a total proportion of 60% ethylene oxide and 2% by weight of the triethanolamine min salt of a phosphorylated polystyrylphenyl polyethylene oxide and 4% by weight of dodecylbenzene sulfone sulfone calcium.

5 At room temperature, dissolve in 25 wt% water 9 wt% ethylene glycol. Under vigorous stirring with a wing stirrer, the above organic phase is allowed to run to this aqueous solution and stir the resulting white emulsion for approx. 15 minutes at room temperature. One sample is stored for 3 months at 50 ° C. The preparation is chemically and technically stable.

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Example 7 35% by weight 2,6-dinitro-4-trifluoromethyl-NpN-dipropylaniline (trifluralin) is dissolved with stirring at 20 to 25 ° C in 20% by weight xylene and 3% by weight of the triethanolamine salt is added. phosphorylated ethylene oxide-propylene oxide-ethylene oxide block copolymer of formula I (with 55% ethylene oxide) and 2% by weight of the triethanolamine salt of a phosphorylated polystyrylphenyl-polyethylene oxide and 3% by weight of fatty acid polyglycol ester (36 EO). At room temperature, dissolve in 31 wt% water 6 wt% polypropylene glycol (molecular weight 500). With vigorous stirring, the organic phase 20 is slowly allowed to run to this aqueous solution and stirred to form the yellow emulsion formed for a further from ca. 20 to approx. 25 minutes until the light yellow hue of the emulsion no longer changes. The product is also technically and chemically stable after storage at various temperatures.

Claims (6)

Plant protection products based on aqueous emulsions containing one or more active substances, characterized in that they contain as a dispersing agent a 5 block copolymer of the formula O II <KC) 2 - - [O (CH 2 -CH 2 -O) x- ( CH-CH2-O) γ- (CH2-CH2-O) z] O f CH3-c (H02P-O- (CH2-CK2-O) x- (CH-CH2-O) y- (CH2-CH 0) z] S ch 3 (I) wherein x and z are independently of a number from 30 to 100, y is a number from 2 to 200, and n 15 and m are equal to 0.1 or 2, the sum of n + m must be 2. Means according to claim 1, characterized in that x and z in formula I have the same meaning, y is a number from 20 to 100 and n is the number 0. A composition according to any one of claims 1 or 2, characterized in that they contain from 5 to 60% by weight of active substance, from 10 to 90% by weight of water, and from 0.5 to 20% by weight of a compound of formula I and common additives. Agents according to one or more of claims 1 to 3, characterized in that they further contain one or more of the following additives: from 5 to 50% by weight of antifreeze, from 1 to 10% by weight of dispersant, from 1 to 15% by weight % emulsifier, 30 from 1 to 10% by weight of thickener, or from 1 to 30% by weight of organic solvent. Compositions according to one or more of claims 1 to 4, characterized in that they contain as an active substance a herbicide selected from phenoxyphenoxy or heteroaryloxyphenoxy-propionic acid alkyl esters, dinitroaniline compounds, hydroxybenzonitrile derivatives or dinitrophenyl compounds, or an insecticide, or an insecticide selected from The phosphoric acid esters or pyrethroids or a fungicide such as pyrazophos or a pheromone or a repellant. Compositions according to one or more of claims 1 to 5, characterized in that they contain as active substance 5 a compound selected from diclofopmethyl, phenoxapropethyl, trifluralin, iso-propaline, 2,6-dibromo-4-hydroxybenzonitrile-octanate, dinoterb. , endosulfate, binapacryl, triazophos, deltamethrin, pyrazophos, phthalic acid dimethyl ester, (E) -8- (E) -10-dodecadienol or (Z) -7,8-epoxy-2-methyl-octadecane.