RU2192131C1 - Herbicide composition - Google Patents

Abstract

FIELD: herbicides. SUBSTANCE: invention describes herbicide composition based on N-phosphono-methylglycine isopropylamine salt aqueous solution that comprises mixed emulsifier Geronol CF/AR as surface-active substance in the following ratio of components, wt.-%: N-phosphonomethylglycine isopropylamine salt, 41-43; emulsifier, 9.4-11.0; water up to 100%. Obtained preparation shows effectiveness that is equal to that of the preparation "Raundapu" and exceeding its by indices of toxicity and rain resistance. EFFECT: improved properties of composition. 10 tbl

Description

 The invention relates to a herbicidal composition, more specifically to an aqueous herbicidal composition containing, as an active ingredient, the isopropylamine salt of N-phosphonomethylglycine and a surfactant. N-phosphonomethylglycine, known by the common name glyphosate, is a very effective non-selective herbicide introduced into the commercial market by Monsanto (USA) back in 1974. The drug acts on herbaceous woody and aquatic plants at various stages of development and is widely used as a post-emergence herbicide. Glyphosate is highly active when used in the form of aqueous solutions of alkaline, ammonium, trimethylsulfonium and other water-soluble salts, but its activity can be significantly increased by the addition of surfactants and other additives, such as antifreeze agents, antifoams, adhesives, etc. commercial preparations use an aqueous solution of the monoisopropylamine salt of N-phosphonomethylglycine, to which the surfactant is added to increase the effectiveness.

 As surface-active substances in aqueous solutions of the monoisopropylamine salt of N-phosphonomethylglycine, substances of various classes can be used, ionic, nonionic, etc. (Weed Science, Vol. 25, 1977, pp. 275-288).

 The most widely used for commercial purposes is a composition based on the isopropylamine salt of N-phosphonomethylglycine with ethoxylated fatty amines (W0 94/02021).

 International application WO 92/11764 states that a preferred surfactant for N-phosphonomethylglycine salts is ethoxylated tall amine having an ethoxylation degree of from 15 to 18, as well as a mixture of such substances. One of these surfactants has the brand name Entry II (Monsanto). Another such substance, MON 0818, is part of the commercial drug Roundup, which Monsanto sells in Russia.

MON 0818 is a composition containing 69-73% ethoxylated tall amine (693-734 g / l), 21-29.5 wt.% Antifreeze, including 6% ethylene glycol and 3.5-4% water (Monsanto Safety proprietary materials Data Sheet dated 1/30/01). Roundup itself has the following composition, wt.%:
Glyphosate isopropylamine salt - 41
MON 0818 - 8
Water - 51
Along with high efficiency and undoubted commercial advantages over many other herbicides, Roundup has some disadvantages, among which a low degree of penetration of the drug into the plant from the leaf surface can be noted. Therefore, the drug can be easily washed off by rain if it goes 1-2 hours after the treatment of plants, which will lead to a decrease or complete loss of herbicidal activity.

In addition, Roundup is irritating to the eyes and skin, and also has potential toxicity to beneficial aquatic organisms: MON 0818 has an LC _{50 of} 6.5 mg / L for aquatic animals, which is the toxicity limit for surfactants (Rev / Environ Contam. Toxicol. 167: 35-120. Springer-Verlag 2000).

 A large number of studies, the appearance of numerous publications, including patent ones, which report partial or complete solution of the problem through the use of new surfactants and other additives, the creation of new formulations to improve efficiency, reduce toxicity, or improve either the characteristics of the drug.

EP 0274369 B1 proposes a formulation comprising the isopropylamine salt of N-phosphonomethylglycine, ammonium sulfate and quaternary ammonium salts containing long alkyl or polyoxyethylated residues, for example, alkyl tri (polyoxyethylene) ammonium phosphate. The composition is stable at low temperatures (below 0 ^o C) and shows good effectiveness when tested on some plants.

A⁺ - прототип, щелочной металл или триэтаноламмоний-катион.In European application EP 0357553 A2 a herbicidal composition in the form of a fluid suspension is described containing an IPA salt of glyphosate, a triazine herbicide and a mixture of anionic and cationic surfactants. Among the anionic surfactants mentioned compound

A ⁺ is a prototype, alkali metal or triethanolammonium cation.

S=1-4, t=2-40, R¹⁰=водород, стирил или С₃-С₁₀ алкил.R ⁸ represents

S = 1-4, t = 2-40, R ¹⁰ = hydrogen, styryl or C ₃ -C ₁₀ alkyl.

R ^{9 is} the same as R ⁸ or hydrogen
European application EP 0526443 A1 describes a N-phosphonomethylglycine herbicidal composition containing alkyl polyglycosides as a surfactant and symmetrically substituted acetylene diols as an antifoam agent.

A - алкиленовая группа
R¹ и R - алкил или алканол с 1 - 3 атомами С
R³ - алкил C₁-C₃
и гликоль - пропиленгликоль или полипропиленгликоль с м.в. >1000. Композиция не раздражает глаза и кожу.In European patent EP 0526444 B1, quaternary ammonium compounds of the formula are proposed as surfactants for an aqueous solution of an N-phosphonomethylglycine salt

A is alkylene group
R ¹ and R are alkyl or alkanol with 1 to 3 C atoms
R ³ is alkyl C ₁ -C ₃
and glycol - propylene glycol or polypropylene glycol with m.v. > 1000. The composition does not irritate the eyes and skin.

R - алкил 6 - 20 атомов C
R' - этил, пропил
n m=20-40 и сумма n+m=5-50
R² - алкил C₁-C₄
X^- - Cl^- или фосфат
ETHOQAD/25 (Akzo Chemical Inc.)
Без добавления гликоля он равен по активности Раундапу, меньше раздражает глаза и менее токсичен для рыб.EP 0 650 326 describes a stable aqueous composition comprising a salt of N-phosphonomethylglycine and a surfactant having the formula

R is alkyl of 6 to 20 C atoms
R '- ethyl, propyl
nm = 20-40 and the sum n + m = 5-50
R ² is alkyl C ₁ -C ₄
X ^- - Cl ^- or phosphate
ETHOQAD / 25 (Akzo Chemical Inc.)
Without glycol addition, it is equal in activity to Roundup, it is less irritating to the eyes and less toxic to fish.

 International application W0 96/00010 describes an effective rain-resistant herbicidal composition based on N-phosphonomethylglycine salts, containing a complex surfactant mixture including alkyl polyglycosides, ethoxylated alcohols, as well as cationic or nonionic surfactants containing amine, ammonium or aminokide groups. Examples confirming the properties of the composition are not described.

где R¹ и R² C₆-C₂₂ - алкил или алкенил
R³ - полигидроксиуглеводородный радикал
R⁴ - C₆-C₂₂ углеводородный радикал
R⁵ - O(AO)nR⁶, где AO алкиленоксид
n=1-200
Один из примеров: тетрадецилглюкамид полиэтиленгликолиевого (ПЭГ-600) эфира янтарной кислоты +30% монопропиленгликоля. Композиция эффективна против трудноискореняемых сорняков.International application W0 97/47199 describes a herbicidal composition based on a water-soluble salt of N-phosphonomethylglycine and an adjuvant-surfactant, which is a derivative of succinic acid of the formula:

where R ¹ and R ² C ₆ -C ₂₂ is alkyl or alkenyl
R ³ - polyhydroxyhydrocarbon radical
R ⁴ - C ₆ -C ₂₂ hydrocarbon radical
R ⁵ - O (AO) nR ⁶ , where AO alkylene oxide
n = 1-200
One example: tetradecyl glucamide polyethylene glycol (PEG-600) succinic acid ester + 30% monopropylene glycol. The composition is effective against hardly eradicated weeds.

 International application W0 98/15181 describes a low-foaming composition based on water-soluble salts of N-phosphonomethylglycine and a mixture of surfactants, including alkyl glycosides and quaternary ammonium salts.

 International application W0 98/35561 provides a herbicidal composition based on water-soluble salts of N-phosphonomethylglycine and a surfactant mixture comprising polyoxyalkylene trisiloxane and glycols or glycol ethers. Recommended for the destruction of wood and shrubbery.

R-C₄-C₁₀ алкил
n=2-10
В материалах фирмы Rhodia этот эмульгатор назван изопропиламинной солью алкилэтоксифосфата, поэтому в таблицах присутствует именно это название, хотя оно не вполне соответствует вышеприведенной формуле (См. инфомацию Rhone-Poulenc Geronazzo Spa "Surfactants and Specialitis for Plant Protection"). Наиболее близким аналогом этого соединения является диспергатор Soprophor (Rhone Poulenk), представляющий собой триэтаноламмонийную соль тристирилфенолполиэтиленоксифосфата с количеством этиленоксидных групп, равным 16-20 (см. WO 98/00009, патент РФ 2093986 и патент РФ 2167522, см. также цитированную выше заявку ЕР 0357553 А2).An object of the present invention is a herbicidal composition comprising an aqueous solution of N-phosphonomethylglycine and a mixed emulsifier Geronol CF / AR (Rhodia Geronazzo), which is an isopropylamine salt of a mixture of polyethoxylated alkyl phosphates of the formula

RC ₄ -C ₁₀ alkyl
n = 2-10
In the materials of the company Rhodia, this emulsifier is called the isopropylamine salt of alkyl ethoxyphosphate, so this name is given in the tables, although it does not completely correspond to the above formula (See the Rhone-Poulenc Geronazzo Spa "Surfactants and Specialitis for Plant Protection" information). The closest analogue of this compound is the Soprophor dispersant (Rhone Poulenk), which is a triethanolammonium salt of tristyrylphenolpolyethyleneoxyphosphate with an amount of ethylene oxide groups of 16-20 (see WO 98/00009, RF patent 2093986 and RF patent 2167522, see also cited above E 0357553 A2).

 An attempt to use Soprophor for glyphosate was unsuccessful.

The use of the isopropylamine salt of alkyl ethoxyphosphate made it possible to obtain a preparation with an efficiency equal to Roundup, and superior to it in terms of toxicity and rain resistance. The applicant named his drug Tornado. / An application for registration as a trademark has been filed. /
The study of toxicity in laboratory animals was carried out at the Research Institute of Occupational Medicine RAMS.

 In an experiment on laboratory animals, the main toxicity parameters were established when mice and rats were introduced into the stomach when rabbits were applied to the skin.

It is shown that the drug does not have skin-resorptive properties. Irritant effect on the skin is not expressed (does not irritate in acute experiments and weakly in repeated ones), moderately irritates the mucous membranes of the eyes in their native form. Irritating properties in the working concentration (1%) are not expressed. According to most indicators (LD ₅₀ when mice and rats are introduced into the stomach, LD _{50 is} acute cutaneous for rabbits, sensitizing properties, inhalation toxicity), Tornado belongs to the 4th hazard class according to the hygienic classification of pesticides.

 Table 1 presents comparative data on the toxicology of Tornado and Roundup preparations.

 Table 2 shows the comparative toxicological characteristics of the surfactant preparations Tornado and Roundup.

 The following are examples illustrating the invention.

 Example 1. Getting the drug Tornado. Options 1-9.

 1. To 580 g of tap water add 110 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. 480 g of the isopropylamine salt of N- (phosphonomethyl) glycine are gradually added to the resulting mixture and stirred until a homogeneous solution is obtained.

 2. To 580 g of tap water add 120 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. 480 g of the isopropylamine salt of N- (phosphonomethyl) glycine are gradually added to the resulting mixture and stirred until a homogeneous solution is obtained.

 3. To 580 g of tap water add 130 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. 480 g of the isopropylamine salt of N- (phosphonomethyl) glycine are gradually added to the resulting mixture and stirred until a homogeneous solution is obtained.

 4. To 564 g of tap water add 110 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. To the resulting mixture, 486 g of the isopropylamine salt of N- (phosphonomethyl) glycine are gradually added and stirred until a homogeneous solution is obtained.

 5. To 564 g of tap water add 120 g of the amine salt of alkyl ethoxyphosphate, mix until complete dissolution. To the resulting mixture, 486 g of the isopropylamine salt of N- (phosphonomethyl) glycine are gradually added and stirred until a homogeneous solution is obtained.

 6. To 564 g of tap water add 130 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. To the resulting mixture, 486 g of the isopropylamine salt of N- (phosphonomethyl) glycine are gradually added and stirred until a homogeneous solution is obtained.

 7. To 536 g of tap water add 110 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. To the resulting mixture, 504 g of the isopropylamine salt of N- (phosphonomethyl) glycine is gradually added and stirred until a homogeneous solution is obtained.

 8. To 536 g of tap water add 120 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. To the resulting mixture, 504 g of the isopropylamine salt of N- (phosphonomethyl) glycine is gradually added and stirred until a homogeneous solution is obtained.

 9. To 536 g of tap water add 130 g of the amine salt of alkyl ethoxyphosphate, mix until completely dissolved. To the resulting mixture, 504 g of the isopropylamine salt of N- (phosphonomethyl) glycine is gradually added and stirred until a homogeneous solution is obtained.

 Example 2. Getting the drug Tornado. Options 10-18. The results are presented in tables 3,4,5.

 10. To 250 g of tap water add 110 g of the amine salt of alkyl ethoxyphosphate, 356 g of N- (phosphonomethyl) glycine, then monoisopropylamine (152 g) is gradually added with constant stirring until the solution is completely (solution pH 4.4-4.9). To the resulting mixture add tap water to a total volume of 1 liter, mix.

 11. To 250 g of tap water add 120 g of the amine salt of alkyl ethoxyphosphate, 356 g of N- (phosphonomethyl) glycine, then monoisopropylamine (152 g) is gradually added with constant stirring until the solution is completely (solution pH 4.4-4.9). To the resulting mixture add tap water to a total volume of 1 liter, mix.

 12. To 250 g of tap water add 130 g of the amine salt of alkyl ethoxyphosphate, 356 g of N- (phosphonomethyl) glycine, then monoisopropylamine (152 g) is gradually added with constant stirring until the solution is completely (solution pH 4.4-4.9). To the resulting mixture add tap water to a total volume of 1 liter, mix.

 13. To 250 g of tap water add 110 g of the amine salt of alkyl ethoxyphosphate, 360 g of N- (phosphonomethyl) glycine, then monoisopropylamine (153.5 g) is gradually added with constant stirring until completely dissolved (solution pH 4.4-4.9) . To the resulting mixture add tap water to a total volume of 1 liter, mix.

 14. To 250 g of tap water add 120 g of the amine salt of alkyl ethoxyphosphate, 360 g of N- (phosphonomethyl) glycine, then monoisopropylamine (153.5 g) is gradually added with constant stirring until completely dissolved (solution pH 4.4-4.9) . To the resulting mixture add tap water to a total volume of 1 liter, mix.

 15. To 250 g of tap water add 130 g of the amine salt of alkyl ethoxyphosphate, 360 g of N- (phosphonomethyl) glycine, then monoisopropylamine (153.5 g) is gradually added with constant stirring until completely dissolved (solution pH 4.4-4.9) . To the resulting mixture add tap water to a total volume of 1 liter, mix.

 16. To 250 g of tap water add 110 g of the amine salt of alkyl ethoxyphosphate, 374 g of N- (phosphonomethyl) glycine, then monoisopropylamine (159.5 g) is gradually added with constant stirring until it is completely dissolved (solution pH 4.4-4.9) . To the resulting mixture add tap water to a total volume of 1 liter, mix.

 17. To 250 g of tap water add 120 g of the amine salt of alkyl ethoxyphosphate, 374 g of N- (phosphonomethyl) glycine, then monoisopropylamine (159.5 g) is gradually added with constant stirring until it is completely dissolved (solution pH 4.4-4.9) . To the resulting mixture add tap water to a total volume of 1 liter, mix.

 18. To 250 g of tap water add 130 g of the amine salt of alkyl ethoxyphosphate, 374 g of N- (phosphonomethyl) glycine, then monoisopropylamine (159.5 g) is gradually added with constant stirring until completely dissolved (solution pH 4.4-4.9) . To the resulting mixture add tap water to a total volume of 1 liter, mix.

 Example 3. The study of the stability of the drug during storage and at low temperatures.

 Assessment of storage stability was carried out according to the CIPAC MT 46 method, and at low temperatures according to the CIPAC MT 39 method.

 The results are presented in table 6.

 As follows from the table, both drugs are equally resistant to cooling, however, MOS 0818 (unlike the isopropylamine salt of alkyl ethoxyphosphate) contains antifreeze (21-29.5%), including 6% ethylene glycol.

 Ethylene glycol is toxic to animals by inhalation of vapors and by ingestion by the oral route (causes kidney defects that may be inherited).

 The isopropylamine salt of alkyl ethoxyphosphate is presented in the form of a 70% aqueous solution without the addition of antifreeze, since due to its structure this surfactant has a lower pour point.

 MON 0818 is a combustible substance, when burning it emits toxic substances, the isopropylamine salt of alkyl ethoxyphosphate - a non-combustible substance.

 Example 4. The study of the herbicidal activity of the drug Tornado.

Test plants were grown in waxed paper cups with a diameter of 600 cm ³ filled with a mixture of sod-podzolic soil, sand and peat (1: 1: 1). When growing test plants in a chamber, a controlled mode was maintained:
- illumination of 20 thousand lux for 16 hours, without lighting 16 hours a day,
- air temperature 20 ^o С at night, 25 ^o С during the day,
- air humidity 70%,
- watering at the level of 60% of the water supply.

 After a careful rejection of plants by height and phase of development, a certain equal number of plants was left in each vessel: 6 plants of wheat, 2 plants of mustard and beets. Processing of monocotyledonous plants was carried out in the phase of the onset of the appearance of the third leaf, dicotyledonous - the first pair of true leaves.

 Herbicides were used in 5 differentiated doses, reducing the weight of the ground mass of test plants from 10 to 90%. The repetition of the experiment is fivefold. The effectiveness of the herbicides was evaluated 14 days after treatment in comparison with the control and the standard by the difference in the wet weight of the terrestrial parts of plants. The results are presented in table 7 and 8.

 Experience shows that the Tornado drug works at the level of the Roundup drug (f. Monsanto), but on wheat there is a slight tendency to increase Tornado activity.

 Example 5. The study of the resistance of the drug Tornado.

The experiment was carried out in an artificial climate laboratory. We studied the rate of penetration of the herbicide Tornado and Roundup herbicide into the grasshopper plants in the first 4 hours after treatment of the plants. As the results of the studies showed, in terms of toxicity for test plants of the cocklebur Tornado and Roundup are at the same level (ED ₅₀ are 0.13 and 0.15 l / ha, respectively). However, the penetration rate (rainfall resistance) of the Tornado was slightly higher than Roundup. This is especially noticeable in the first two terms - 30 minutes and 1 hour.

 In subsequent periods of observation, these differences in the rate of penetration of the active substance of the herbicides Tornado and Roundup into the grasshopper plants do not level. Both drugs almost completely penetrate into the plants of the fruit tree in 4 hours. The results are presented in tables 9 and 10.

Claims (1)

A herbicidal composition comprising an aqueous solution of the isopropylamine salt of N-phosphonomethylglycine and a surfactant, characterized in that it contains a mixed emulsifier Geronol CF / AR, which is an isopropylammonium salt of a mixture of polyoxyethylated alkyl phosphates of the formula

where R is C ₄ -C ₁₀ alkyl;
n = 2-10,
in the following ratio of components, wt. %:
Isopropylamine salt of N-phosphonomethylglycine - 41-43
Emulsifier - 9.4-11.0
Water - Up to 100%

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