CS254963B2 - Herbicide mixture - Google Patents

Abstract

This herbicidal compsn. comprises (a) liq. thiolcarbamate(s) of formula (I); R1R2N-CO-S-R3 (I); (b) solid s-triazine(s) of formula (II) of particle size 2-5 microns; (c) opt. an antidotally effective amt. of a (thio)acyl-oxazolidine or -thiazolidine of formula (III), or amide (IVa) of a 2 - 7C haloalkanoic acid or amide of formula (IVb) R13-CO-NR14R15(IVb); (d) Ca 10 - 15C-alkyl benzene sulfonate anionic emulsifier(V); (e) (modified) nonionic emulsifier of formula(VIa) or (VIb); (f) (I)-insoluble, watersoluble ethoxylated phenol wetting agent of formula(VII); (g) Ca lignin sulfonate as dispersant; (h) antifoam; (i) fumed silica; and (j) water.

Description

These thiolcarbamates have been shown to be particularly effective in controlling grass weeds which interfere with the production of various crops such as barley, corn, lentils, peanuts, peas, potatoes, soybeans, spinach, tobacco and tomatoes.

Also known are the following s-triazine herbicides of the formula wherein

R1 is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms and alkynyl of 2 to 6 carbon atoms, R2 is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, cyclohexyl and phenyl; or R 1 and R 2 together with the nitrogen atom to which they are attached form a ring structure having 4 to 10 carbon atoms, preferably piperidino, hexamethylenimino, decahydroquinolino, 2,5-dimethylpiperidino, or 5-ethyl-2-methylpiperidino;

R ₃ is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 4 carbon atoms, benzyl, phenyl, halophenyl, and methyl-substituted phenyl or benzyl and haloalkyl of 1 to 6 carbon atoms.

These thiolcarbamate compounds are described in U.S. Patent No. 2,913,327;

198 786; 185 720; 2,913,324 and 3,846,115.

where

A is chloro, methoxy and methylthio, and

R 1, and R ₅ are independently C 1 -C 4 alkyl, C 2 -C 8 alkoxyalkyl and C 1 -C 4 yanoalkyl.

These compounds are described in U.S. Patent Nos. 289,155 and 2,909,420.

Previously, various s-triazines were combined with various tholocarbamates to form herbicidal mixtures. (See U.S. Patent Nos. 3,037,853 and 3,682,616).

Some prior patents disclose liquid formulations comprising liquid thiolcarbamate and solid s-triazine. (See Belgian Patent No. 889,274 and South African Patent Application No. 77 (3478). None of the formulations described in these publications have been commercially successful. The solid s-triazine portion of the formulation separates on standing from liquid thiocarbamate and is therefore commercially inappropriate. earlier compositions have poor dilution properties in hard water and in nitrogen fertilizer solutions.

The subject of the invention is a herbicidal mixture, characterized in that it contains by weight

5.0 to 85% of S-ethyl Ν, Ν-diisobutyl thiolcarbamate,

5.0 to 85% of 2-chloro-4-ethylamino-4-isopropylamino-1,3,5-triazine (atrazine), up to 20% calcium dodecylbenzenesulfonate calcium as an anionic emulsifier, up to 20% nonionic emulsifier of structural formula

0 (СН ^ Сн _г ) ₃ -СН £

2.0 to 5.0% of a surfactant of structural formula с ₃ н, гСУ ° ' ^Ch 2 ^Ch z ° V ^CH 2 ^C í ^CH '

0.5 to 5.0% of lignin sulphonate calcium as dispersant,

0.01 to 0.5% of dimethylpolysiloxane as an antifoam; and

0.5 to 5.0% silica as a thickening agent.

The herbicidal mixture may further comprise 0 to 15% Ν, Ν-dlallyl dlchloroacetamide and 0 to 35.0% water.

The formulation is diluted with water or a water-containing liquid prior to application to the field. It has the advantage that it can contain a large amount (50 to 85% by weight) of the active ingredient, i.e. liquid thiolcarbamate and solid s-triazine as a herbicide. The composition is thermally stable over a wide temperature range. It is compatible and dilutable with hard or soft water and nitrogen fertilizer solution.

Most importantly, neither the solid s-trlazine component nor the water of the herbicidal compositions of the invention separates from aging during a several-month storage over a wide temperature range from the liquid thiolcarbamate component. The formulation has been found to be stable over several months of storage over a wide temperature range.

Any liquid water insoluble pesticide (or a solution thereof in a water insoluble solvent) may be used in place of said liquid thiocarbamate.

Any water-insoluble solid pesticide that is substantially insoluble (less than 5%) in the liquid pesticide may also be used in place of said s-triazine.

The ratio of liquid thiolcarbamate to solid s-triazine may range from 1: 1 to 12: 1 for a total amount of active ingredients ranging from 50 to 85% total weight at a ratio of 1: 1 to between 71.5 and 80.5% total weight. at a 12: 1 ratio,

Optionally, said anti-toxin compound may be used. Therefore, the amount of the antidote compound in the mixture may be zero. In the presence of an antidote compound, the amount may be close to the herbicidal amount. This amount is called the "antidote amount".

The preferred amount of the antidote compound is in the range of 3 to 5% by weight based on the weight of the thiolcarbamate.

The preferred amount of anionic emulsifier is in the range of 15 to 65% by weight of the total amount of both emulsifiers. Accordingly, the amount of nonionic emulsifier may be in the range of 85 to 35% by weight of the total amount of both emulsifiers.

The herbicidal composition of the invention may be prepared by separately preparing an oil portion and an aqueous portion and then combining the two portions together with a thickener.

In preparing the aqueous portion, the solid s-triazine herbicide is comminuted to a particle size

From 3 4 9 6 3 in the range of 2 to 5 microns. Preferably, the comminution is carried out in water in a conventional comminution apparatus, such as a ball mill. The water-soluble surfactant and dispersant may be combined with the s-triazine either before, during, or after comminution. The antifoam is used during comminution to reduce foaming. When water is used in the grinding of s-triazine, an aqueous slurry of s-triazine in water is obtained from the comminution step.

The oily portion is prepared by dissolving an anionic and a nonionic emulsifier with an iprotide compound in liquid thiocarbamate. The solution can be prepared in any conventional container. Any stirring apparatus, such as a paddle mixer, can be used to facilitate dissolution.

The part and the oil part are joined together. Simply, the aqueous portion can be poured into the oil portion using a conventional device. Simple mixing can be used to form a homogeneous mixture.

A thickener is then added to the combined portions to increase the viscosity of the mixture and to provide a s-triazine suspension.

The following are examples of herbicidal mixtures according to the invention.

Example 1

The following ingredients are used in this formulation;

Component Weight (g) (a) S-ethyl-N, N-diisobutyl- thiolcarbamate 460.8 b) 2-chloro-4-ethylamino-4- -isopropylamino-1,3,5-tri- azine (atrazine) 392.0 c) N, N-diallyl-dichlorisation- tamid (antidote) substance) 19.2 d) dodecyl calcium salt benzenesulfonate (anion- computer emulsifier) 156.1 θ)

® (Сн ^ сн ^ о с -Онi)

164.0 (non-ionic emulsifier)

f) ^c a ^Η ιί0 ”> мСН _г ^С Нг. ^СН '

44.0 (surfactant)

lignin sulphonate calcium (dispersing agent) 24.0 dimethyl polysiloxane (defoamer) 0.8 silicon dioxide (dispersing agent) 10.0 water 339.2

254983

The liquid portion of the formulation is prepared by weighing the liquid thiolcarbamate, an anti-antidote, anionic and non-ionic emulsifier into a 1.14 L glass flask. Cover the flask with a lid, warm and shake to obtain a clear, homogeneous solution.

The aqueous portion of the formulation is prepared by weighing a wetting agent, dispersant, antifoam, water and atrazine (pre-ground in air to an average particle size of 3-4 microns) in a 2 L glass beaker. The beaker is fitted with a flexible plastic lid. A high-speed stirrer extending through the opening in the lid to the bottom of the beaker is used to mix the particles to the aqueous slurry.

Weigh the liquid portion (455.0 g) into a 4 L glass beaker. 535.0 g of the resulting aqueous atrasine slurry was then added to the liquid portion of the formulation and 10.0 g of silica was added as a thickening agent. The mixture is covered with a lid and vortexed to moisten the ingredients. Finally, a high speed stirrer is used for 10 minutes to completely mix all components.

The resulting product is a homogeneous, liquid mixture that is stable and does not separate. The product can be diluted with hard and soft water or a nitrogen fertilizer solution.

Example 2

The following ingredients are used in this preparation:

Component

Weight (g)

a) S-ethyl-N, N-diisobutyl thiolcarbamate

b) 2-chloro-4-ethylamino-4-

-isopropylamino-1,3,5-triazine (atrazine)

c) Ν, Ν-diallyl dichloroacetamide (antidote)

d) dodecyl benzene sulphonate calcium (anionic emulsifier)

e) _ Q ⁰ у-сн _г - С-0Ц, (non-it rite emulsifier)

f) g ° ^{C {CHjgHzO} _3g) CHgCH CH ^ _t

678.40

550,00

29.04

45.12

47.44

12.10

(wetting agent) g) calcium salt of lignin sulphonate (dispersing agent) 12.60 h) dimethyl polysiloxane (defoamer) 0.30 (i) silica (dispersing agent) 61,00 (j) water 425,00

The liquid portion of the formulation is prepared by weighing a liquid thiolcarbamate, an anticancer agent, anionic and nonionic or modified nonionic emulsifier into a 1.14 L glass flask. Cover the flask with the lid and shake until a clear, homogeneous solution is obtained.

The aqueous portion of the formulation is prepared by weighing a wetting agent, dispersant, antifoam, water and atrazine into a 2.28 liter ceramic ring mill containing 0.27 cm ceramic beads. The mill is covered and ground for 3 days. The average particle size of the atrazine in the slurry is reduced to 3-4 microns. (Measured on a Coulter computer).

The ground slurry (900 g) is poured into a glass bowl (31.75 x 21.60 x 5.08 cm). The partially dry material was placed in an oven at 32.2-37.8 ° C overnight to completely remove residual water. 517.5 g of solid are obtained.

Then, 372 g of dry matter and 420 g of liquid part and 8.0 g of silica are placed in a 2.28 liter ceramic ball mill. It is milled for 3 hours to obtain a homogeneous suspension of solid atrazine in liquid thiolcarbamate.

The resulting liquid mixture remains stable and does not separate. The product can be diluted with hard and soft water and a nitrogen fertilizer solution.

The composition of the invention may be applied by standard tank mixing technique using water to dilute the concentrate, or may be applied by adding to field irrigation water. These application methods allow pexetration of the active mixture into the soil upon absorption of water. It is not necessary to mix the mixture with the soil particles. After application by the above methods, the top wetted soil portion can be brought to the ipod surface to a depth of at least 1.27 cm by conventional methods such as scouring, dragging or mixing.

A herbicide is a compound that regulates or modifies plant growth, e.g., by damage, growth retardation, defoliation, desiccation, stunting, offshooting, stimulation, leaf yellowing, miniature growth. The term "plant" refers to all physical parts, including seeds, seedlings, young trees, roots, tubers, stalks, stems, foliage and fruits. The term 'plant growth' covers all stages of development, from seed germination to natural or induced cessation of life.

The manufacturer of a particular herbicide proposes a range of doses and concentrations calculated for maximum weed control. The dosage range is from about 0.0112 to 56 kg / h, usually from 0.112 to 28 kg / h. The actual amount used depends on a variety of factors including some weed sensitivity and total cost.

However, at these rates, weeds and crops can be damaged. Therefore, the harmful effect of the herbicide used on the useful plants must be reduced.

In order to maintain the herbicidal effect of the herbicide used and to alleviate crop damage, herbicidal antidote agents have been developed. These antidote agents reduce or eliminate the deleterious effect on the useful plants without substantially reducing the herbicidal effect of the herbicide used. They are described in U.S. Patent Nos. 3,989,502; 4,072,688 and 4,112,372, 4,021,224.

Although various theories have been put forward, the exact mechanism by which antidote agents would reduce herbicidal deleterious effects has not been empirically confirmed. In fact, the antidote compound may be a therapeutic agent, an interference agent, a preservative, or an antagonist. The antidote does not affect weed herbicidal phytotoxicity and reduces or eliminates phytotoxicity to useful plants.

5 4 95 3

A new or higher effect is obtained with the following components:

Performance tests by percentage range

and) S-ethyl N, N-diisobutyl thiolcarbamate 5,0—85 (b) 2-chloro-4-ethylamino-4-isopropylamino-1,3,5-triazine (atrazine) 5,0—85 C) N, N-dialkyldichloracemid (antidote) 0 —15 (d) calcium salt of dodecyl benzene sulfonate (anionic emulsifier) 5 —20

θ)

O {C H „C Μ, Ο С H- C - 0 и I –20 (non-emulsifier emulsifier)

F)

2.0— 5.0 (wetting agent)

g) calcium salt of lignin sulphonate (dispersing agent)

h) dimethyl polysiloxane (defoamer)

(i) silica (dispersing agent)

(j) water

0,5- 5,0

0.01—0.5

0.5- 5.0 —35.0

The advantages of the composition of the invention are shown in the following test.

The formulation of Example 1 was stored for 4 weeks at 51.66 ° C. Only 0.6% of the atrazine decomposes and only 7.7% of the clear layer remains at the top. 92.3% will remain in the original mixture. The composition is again dispersed by shaking the mixture.

The water is adjusted to contain 34.342 and 1000 ppm CaCO 3 _and hardness. A fertilizer solution containing 28 wt% nitrogen is also prepared. 5 ml of the preparation according to Example 1 were added to 95 ml of water having a hardness value of 3 and a fertilizer solution in a 100 ml glass cylinder at 20 ° C.

The formulations are easily wetted and dispersed in all tests: The cylinders are inverted 20 times to form a uniform suspension. No separation was observed after 2 hours.

The herbicidal mixture according to the invention exhibits 90% of the control of the weed under test. In addition, the solid s-triazine moiety does not separate from the liquid thiol carbamate on standing. The formulations also have good properties for dilution in hard water and in nitrogen fertilizer solutions.

Claims (2)

SUBJECT A herbicidal mixture comprising 5.0 to 85% by weight of S-ethyl Ν, Ν-diisobutyl thiolcarbamate, 5.0 to 85% of 2-chloro-4-ethylamino-4-isopropylamino-aminolysis -1,3,5-triazine, 5 to 20% dodecylbenzenesulfonate calcium salt as an anionic emulsifier, 5 to 20% nonionic emulsifier of structural formula 2.0 to 5.0% of a surfactant of the structural formula 0.5 to 5.0% of lysine sulfonate calcium salt as a dispersant, 0.01 to 0.5% of dimethylpolysiloxane as an antifoaming agent and 0.5 to 5.0% of silica as a thickening agent. 2. A herbicidal mixture as claimed in claim 1 comprising 0 to 15% N, N-diallyl dichloroacetamide as an anti-drug and 0 to 35.0% water.