DE3016760A1 - LIQUID FORMULATIONS OF PHOSPHORIC AND THIOPHOSPHORIC PESTICIDES - Google Patents

Description

1 SUBMITTED

PATENT LAWYERS

Dlpl.-lng. P. WIRTH Dr. V. SCH MIED-KOWARZIK Dlpl.-Ing. G. DANNENBERG Dr. P. WEINHOLD Dr. D. GUDEL

335024 SIEGFRIEDSTRASSE

TELEPHONE: C089, _{8 {) 00}

SK / SK

Case K.2729

Montedison S.p.A. Foro Buonaparte Milan / Italy

Liquid formulations of phosphorus and thiophosphorus pesticides

03 0 046/0826

The present invention relates to liquid formulations of phosphorus and thiophosphorus pesticides which over long Time are stable; it relates in particular to liquid pesticide formulations that are resistant to high and low temperatures are persistent.

Phosphorus and thiophosphorus pesticides have been known for some time, such as ROGOR ^ (trademark of Montedison S.p.A.

ι. for 0,0-dimethyl-S- (N-methylcarbamylmethyl) -phosphorodithiate ), CIDIAL ^ (Trademark of Soc.Montedison for 0,0-dimethyl-S- (o (-ethoxycarbonylben2yl) -phosphorodithioate), MALATHION ^ (trademark of the American Cyanamide for S- £ i, 2-di- (ethoxycarbonyl) -ethyl7-phosphorothiolthionate),

PARATHION ® (trademark of American Cyanmide for 0,0-dimethyl-O-p-nitrophenyl phosphorothioate) etc. Of these substances, PARATHION, MALATHION and many others are liquid; ROGOR, FAC ^ (trademark of Montedison S.p.A. for 0,0-diethyl-S- (N-isopropylcarbamoylmethyl) -phosphorodithioate)

·> “ Are solids.

Liquid solutions of these compounds are particularly useful for easy handling and making emulsifiable Formulates and concentrates that are used in very small volumes.

These liquid solutions are, however, in terms of their physical resistance to low and high temperatures and with respect to their chemical resistance difficult fro _{t (i} observed. Without special precautions they readily undergo a decrease of their biological activity.

Pesticide phosphates or thiophosphates either show poor solubility in most common organic Solvents, especially at low temperatures, or a solvent that is insufficient to guarantee their activity, Chemical resistance. In order to circumvent these disadvantages, various suggestions have been made in this way

10-1 6760

e.g., according to US Pat. No. 3,444,273, the thiophosphoric acid esters are mixed with dialkylphenols and this mixture is then mixed with diluted with an aromatic hydrocarbon. This achieves sufficient chemical resistance and good resistance to low temperatures. However, the alkylphenols are quite expensive and difficult to handle, and often they impart some phytotoxicity to the formulations so obtained.

It is also known that phosphorus or thiophosphorus pesticides often difficult to dissolve in many of the organic solvents, such as xylene, Shellsol A and Shellsol AB (mixture aromatic and aliphatic hydrocarbons from Shell f., Comp.), while in solvents such as alcohols, glycols, Ketones, dimethylformamide, dimethyl sulfoxide, etc. often one The active compound decomposes.

The aim of the present invention are formulations of 20 phosphorus or thiophosphorus pesticides which are stable at low and high temperatures and from solutions of A) phosphorus or thiophosphorus pesticides 0.5 to 90 % b) one or more organic acids 99.5 to 10 % to which one or more of the following diluents have been added:

1) Xylene type aromatic solvents or aromatic aliphatic solvents Solvents such as Shellsol, A, Shellsol AB (Mixtures of dimethyl, ethyl and tetramethylbenzene) etc., Solvesso 100-150 or 20 (mixtures of dimethyl,

30 ethyl and tetramethylbenzene; Trademark of Esso Comp.)}

2) dimethylformamide, dimethyl sulfoxide, C ₁ -C 6 alcohols and C ₂ -C ₂₀ glycols;

3) Amyl acetate type, methyl benzoate type esters, etc.

4) ketones of the cyclohexene type, ethyl amyl ketone, acetophenone; • ^ 5) surfactants, such as SETROLONE ^ (trademark '

the ROL-ME Comp .; consisting of polyoxyethylene sorbitan oleate), EMULSION 10B ^ * (trademark of ROL-Comp., consisting of alkylphenol polyoxyethylate), EMULSION ^

030046/0826

(Trademark of ROL-ME Comp., Consisting of alkylbenzenesulfonate).

Group A compounds are ROGOR, methyl parathion (0,0-dimethyl-O-p-nitrophenyl phosphorothioate), monocrotophos / T-Methyl-3- (methylaraino) -3-oxo-1-propenyl phosphate 7, M G174 (idinphos, trademark of Montedison for O, O-diethyl-O- / T-methyl-3- (ß, ß-dichlorovinyl) -1,2,4-triazol-5-yl7-thiophosphate), Fee, azinphos-methyl (0,0-dimethyl-S ~ / T4-oxo-1,2,3-benzotriazin-3 (AH) -yl) -methyl7-phosphorodithioa '' /).

The compounds of group B (organic acids) can be: acetic acid, propionic acid, butyric acid, caprylic acid, Oleic acid, phenylacetic acid, formic acid, caproic acid, stearic acid and generally all organic, with the diluents the pesticidal phosphorus / organic acid mixture miscible acids.

Under these conditions, the resistance to high and / or low temperatures and / or the solubility increases the phosphorus or thiophosphorus pesticides considerably. As can be seen from Table 1, the solubility of ROGOR in various organic solvents, especially at low temperatures, are often not very high.

Table 1

Percent solubility of Rogor / 0,0-dimethyl-S- (N-methylcarbamoylmethyl) phosphorodithioate / 2C at ^<Q C and 0 C ⁰

solvent 2O ⁰ C O ⁰ C Xylene 12 % 3 % Shellsol AB 8th % 2 % Butyl alcohol 50 % 10 % Amyl acetate 30 % 8 % , Dimethylformamide 75 % 50 % Diet hyloxalate 60 % 35 % Cyclohexanone 60 % 50 %

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Venn the solubility is good (dimethylformamide, cyclohexanone), then particularly at high temperature (ie, above 5O ⁰ C) of the pesticidal solutions is the chemical resistance is unsatisfactory. The following Table 2 z & gt dai high stability loss (calculated as the percentage decrease in the active substance) in solvents in which Rogor is quite soluble.

Table 2

Stability of Rogor in various solvents after 5 days at 60 ⁰ C.

Mixture - Loss in %

40:60 ROGOR: dimethylformamide - 90

40:60 ROGOR: dimethyl sulfoxide 90

.40: 60 ROGOR: Butyl alcohol 50

40:60 ROGOR: propylene glycol 70

40:60 ROGOR: Me ^J jhylcellosolve 50

40:60 ROGOR: cyclohexanone 6.3

From Tables 1 and 2 it can be seen that ROGOR can be used in solvents, in which it is stable, like aromatic solvents, is sparingly soluble, while it is in solvents, in which it is very soluble, is unstable. (Cyclohexanone is an exception, but it is very expensive.)

With the mixtures according to the invention you can have both a Avoid decomposing as well as increasing the solubility of the pesticide in solvents in which it is usually not very soluble is.

The following tables and examples illustrate the present Invention.

030046/0826

Table 3

Stability of ROGOR in a mixture of different organic acids after dilution with xylene and surfactants; after 5 days

at 60 ⁰ C

techn. ROGOR 95 formic acid acetic acid propionic acid

° butyric acid

cn oleic acid

Phenylacetic acid caprylic acid

Linolenic acid

Xylene
Setrolene 0

loss

40 40 40 40 40 40 40 40 40 40 40 10 10 10 15th 15th 15th 15th S. 25th 20th 25th 25th ..5O. 50 40. . 45. ..35. .4.5. . .35. . 25th 30th 25th 10 10 10 10 10 10 10 3.4% 2.0% 2.1% 0.0% 0.0% 1.0% 0, SS 3, 0>; 3.0% 0.3 % 2, σ ;;

• Si

O 1 line - ^ O CO X 3 m CO O rc Q

Table 5a

rmulation 65 % 1) techn. ROGOR 95 % ± p 24 % acetic acid 11 % Stellsol AB 65 % 2) techn. ROGOR 95% 30 % Propionic acid C Oi
J jQ Shellsol AB 65 % 3) * techn. ROGOR 95 #ig 30 % phenol 5% Shellsol AB * Usual formulation Table 4

Loss after days at 60 ° C; %

4.6

4.1

12.6

mixture

Stability test at different temperatures of ROGOR formulations with acetic acid (1, 2) in comparison to common ROGOR formulations (3,4)

% Loss after '

Tage14 days1 month 1 month at 60 ⁰ C at 54 ° C at 50 C. at 40 ^Q C

40:10:50 tech. ROGOR acetic acid: xylene

2.0

40: 10: 40: 7: 3 technical ROGOR: acetic acid: xylene: 2.1 SEl ¹ ROLENE 0: emulsion 255 *

40:10:50 technical ROGOR: xylene: cyclohexanone

3.9 4.5 2.8 3.9

6.6 6.3

4.7 0.5 6.8 1.0 7.6 3.1 7.1. 2.9

40:42:18 Tech ROGOR: xylene: phenol

* = Emulsion 255 = trademark of ROL-Me for alkylbenzenesulfonate

0300A6 / 0826

Table 5

Stability of various pesticide compounds in formulations based on acetic acid and Xylene, after 5 days at 60 ° C

mixture _i Loss in %

40:10:50 tech. M 8174: ßssig- ₂ ,

acid: xylene '

40:10:50 tech. Methyl parathion: acetic acid: xylene 0.8

40:10:50 Monocrotophos: vinegar- ■? _n

acid: xylene '^' ^u

example Λ_

A solution of 0.5 g ROGOR, 0.1 g acetic acid and 99.4 g

■ · Xybl was made by mixing the pesticide with the acetic acid and then with the xylene at room temperature. 50 g of this solution for 48 hours at 0 ⁰ C and 5 days were maintained at 6O ⁰ C, showed no change, wherein the liquid / gas Chrornatographieanalyse no

■ i indicated noticeable decomposition.

Example 2

A solution was prepared by adding 72 g of ROGOR, 18 g of acetic acid, 10 g of Shellsol AB (V / nrenzeichen der Shell Comp, for a mixture of aromatic

• Table and aliphatic solvents made from dimethyl, ethyl and tetramethylbenzene) .mixed. 50 g of this mixture, which ^{had been kept at 0} ° C. for 48 hours or at 60 ° C. for 5 days, showed no change at all; no noticeable decomposition had occurred according to liquid / gas chromatography.

, · ■ Example 3_

From 40 g of ROGOR, 10 g of acetic acid and 50 g of xylene, a solution was prepared at room temperature which showed the same stability as in the previous examples. Example 4

ü, The same results were obtained with the following mixtures: 40 g ROGOR, 5 g acetic acid, 5 g dimethylformamide and 50 g Xylene; 40 g ROGOR, 5 g acetic acid, 25 g cyclohexanone and 30 g xylene; 72 g ROGOR, 18 g acetic acid and 10 g Setrolene

030046/0826

(Trademark of ROL-Me Comp, for a surface-active Polyoxyethylene sorbitan oleate); 40 g ROGOR, 10 g acetic acid, 40 g xylene and 10 g of a hybrid of NonylphenOlpolyoxyäthylat ■ and dodecylbenzenesulfonate; 40 g ROGOR, 5 g acetic acid, 5 g Dimethylformamide, 40 g xylene and 10 g setrolene.

The mixtures of Examples 3 and 4 showed no 'phytotoxicity in doses of 0.05 and 0.1% compared to ₀ cucumbers,

^: - Beets, vines, apples, cabbage and cotton. Example 5

It was a formulation by mixing 40 g of techn. ROGOR, 15 g propionic acid, 35 g xylene and 10 g Setrolene 0 prepared with stirring. Then there was 50 g of this mixture

■ '. Leave 48 hours at ⁰ ° C and a further 50 g for 5 days at 60 ° C. After both tests, liquid: gas chromatographic analysis showed no noticeable degradation.

Example (p

A formulation was made by mixing 40 g

■ "ι techn. Rogor, 20 g of phenylacetic acid, 25 g of xylene and 10 g Setrolone 0 under stirring. 50 g of this mixture were incubated for 48 hours at O ⁰ C and g more 50 5 days at 6O ⁰ C. After two tests showed liquid / gas chromatography did not show any noticeable decomposition.

- ··. Example 7

40 g tech. M 8174 are mixed with 10 g acetic acid, 40 g xylene and 10 g EMULSION 10B at room temperature. 50 g of this mixture were incubated for 48 hours at O ⁰ C and another 50 · S were held 5 Tege at 60 ° C. After these tests could

V ₁₁ no separation can be found, and according to liquid / gas chromatography no decomposition had occurred.

Example 8

40 g tech. Methyl parathion were mixed with 10 g of acetic acid, 40 g of xylene and 10 g of EMULSION 1ΌΒ at room temperature. ·., 50 g of this mixture was 48 hours at O ⁰ C and a further 50 g kept for 5 days at 6O ⁰ C. No separation was observed after these tests and no noticeable decomposition had occurred by liquid / gas chromatography.

030046/0826

301676Q

Be j, game 9

40 g tech. Monocrotophos were mixed with 10 g acetic acid and 50 g xylene. 50 g of this mixture were kept at ⁰ ° C. for 48 hours and a further 50 g were ^{kept at 60 °} C. for 5 days. No change was found after these tests and no noticeable decomposition had occurred according to liquid / gas chromatography.

Among organic acids that can be used as compounds B. are, in particular, aliphatic acids (fatty acids) with about 1 to 20 carbon atoms, optionally 1, 2 or 3 ethylenic bonds can be understood. Particularly unsaturated acids are those of natural origin used.

In particular, aromatic solvents are used Question that consists of xylenes, ethylbenzene, tri- or tetramethylbenzenes, possibly mixed with a smaller one Amount of aliphatic hydrocarbons with an approximately similar boiling range exist.

Usable alcohols are, for example, methanol, ethanol, n- or i-propanol, n- or i-butanol, pentanols, hexanols. Usable glycols are, for example, ethylene glycol, 1,3- or 1,2-propylene glycol, 1,4-butylene glycol and other « ^{I, iO 1} glycols and corresponding ether glycols, such as diethylene, dipropylene

20 and dibutylene glycol, tri- or tetraethylene glycol or -propylene glycol.

Useful surfactants include the known nonionic agents, particularly ethylene oxide adducts of Sorbites and its esters, the ethylene oxide adducts of the various alkylphenols or the known anionic agents, like the sulfates or sulfonates of the various alkylbenzenes or naphthalenes. Ethylene oxide adducts of castor oil are also sine useful.

Claims (1)

NAOHC ΐΐ .'- \. Claims 1.- Liquid formulations of phosphorus, stable for a long time and resistant to low and high temperatures and thiophosphorus pesticides, characterized in that the 5 formulation of a mixture of 0.05 to 90 % phosphorus or thiophosphorus pesticide 99.5 to 10% of an organic acid or mixture the same
consists, the mixture then with stirring one or ό more than one of the following solvents is added: a) Xylene type aromatic solvents or aromatic solvents Solvents such as Shellsol A, AB or Sovesso 100, 150 or 200; b) dimethylformamide, dimethyl sulfoxide, C ₁ -Cg alcohols or is ^C 2 ~ ^C 20 ^glycols c) ketones of the cyclohexanone type, ethylamyl ketone; d) esters of the amyl acetate type, methyl benzoate, etc. and optionally e) common surfactants. 2. - Formulations according to claim 1, characterized in that that the organic acids acetic acid, propionic acid, butyric acid, caproic acid, capryic acid, oleic acid, ricinoleic acid, Is stearic acid, formic acid or phenylacetic acid. ? ■ ") 3.- Formulations according to claim 1, characterized in that ■ that the phosphorus or thiophosphorus pesticide is ROGOR, M 817 ^, methyl parathlon, Monocrotophos or FAC. so k. ~ Formulations according to claim 1, characterized in that they have been obtained by adding xylene to the mixture of phosphorus or thiophosphorus pesticide and the organic acid. 5.- Formulations according to claim 1, characterized in that they have been obtained by mixing the mixture Phosphorus or thiophorophosphorus pesticide, organic acid and Xylene adds a surfactant. The Pn ~ '"" "030048/0826 ORIGINAL INSPECTEO