OA20952A - A stable agrochemical composition and process for preparation thereof. - Google Patents

Abstract

The present invention relates to a continuous process for preparation of a stable agrochemical composition in microreactor processing system. The present invention also provides a stable agrochemical composition having mean particle size distribution and method of controlling undesired vegetation with said composition

Description

A STABLE AGROCHEMICAL COMPOSITION AND PROCESS FOR

PREPARATION THEREOF

FIELD OF INVENTION

The présent invention relates to a stable agrochemical composition and process for préparation of said composition, More particularly, the présent invention relates to a continuons process of preparing stable agrochemical composition with narrow particle size distribution in the form of an émulsion.

BACKGROUND OF THE INVENTION

An émulsion is a System containing two liquid phases, one of which is dispersed as globules in the other. That liquid which is broken up into globules is termed the dispersed phase or oil phase, whilst the liquid surrounding the globules is known as the continuous phase or aqueous phase. The two liquids, which must be immiscible or nearly so, are frequently referred to as the internai and external phases respectively.

An Emulsion, oil in water (EW) composition consist of a dispersion of oil droplets in a continuous aqueous medium. The EW composition is a convcntional type of formulation in the field of the agrochemical formulations. EW formulations are important in agriculture as a means of formulating oil-based Systems in a more environment friendly form. In the EW formulation, the émulsion is pre-formed as a commercial produel and is conventionally diluted with a carrier, such as water, when making up the spray mixture for the purpose of its agricultural application.

Achieving stable EW composition is always a challenge. The stability of an EW composition refers to its ability to resist change in form and properties over time. There are three types of instability common to EW composition: (i) flocculation, (ii) creaming, and (iii) coalescence. Flocculation occurs when there is an attractive force between the droplets, so they form a flocculant mass (flocs) in the fluid through précipitation or aggregation of suspended partie les. Creaming occurs when the droplets rise to the top of émulsion under the influence of buoyancy. Coalescence occurs when droplets collide and combine to form a larger droplet, so the average droplel size increases over time.

Effective émulsification is the way lo overcome above menüoned instability factors. Emulsification may be regarded as a mixing operation whereby two or more normally immiscible materials are intimately mixed. Emulsification is achieved by dispersing one of the phases in the form of drop tels or globules throughout the second phase. In an émulsification process, a larger droplet of oil is emulsified into large number of small droplets. The interfacial area is greatly încreased as a resuit of the sub-division of the bulk oil into much smaller units. This large interfacial energy is accompanied by a large surface energy that is given by the product of interfacial tension and increase in surface area. This increases the total entropy of émulsion System and facilitate the émulsification process.

Based on energetics, the free energy of émulsification is positive. The first corollary of this is that émulsification is rarely a spontaneous process, and hence requires the input of energy. This energy usually cornes from mechanical shear provided by various types of mixers, and the final droplet size of the émulsion is dépendent on not only the chemistry but also the amount of energy applied.

Simple paddle-type mixers are suitable when the required droplet size is above around 10pm, but to make smaller droplets, higher shear is generally required.

High shear rotor-stator mixers are commonly used. These operate by pumping the émulsion phases through the narrow gap between a perforated cylinder (the stator) and the blades of a rapidly rotating stirrer housed inside it (the rotor) where the forces are sufficient to make droplets as small as around Ιμιη.

To make even smaller droplets, at small scale, ultrasonic devices can be used to make émulsions with nanosized droplets, but they are generally not practical to scale up.

High-prcssure homogcnizcrs are rcadily scaled, and also produce émulsions with nanosized droplets. The émulsion phases are pumped together under high pressure into a small volume or through a small orifice (the interaction chamber) where pressures in the tens of thousands of psi (pound per square inch) create very high shear forces. Emulsions, with an average droplet size as small as 0.2 pm, can be formed this way, which is significant as these are amenable to sterilization by filtration through a 0.2pm filter.

Most often, EW compositions are produced by milling, micronizing or high shear processing. Conventionally, EW émulsion is achieved by dissolving water soluble active ingrédient in aqueous phase and oii soluble active ingrédients in an oil phase and then applying energy to disperse oil phase in aqueous phase. Application of energy is required to achieve partie le size of oil globules dispersed in aqueous phase to bc in range of 20-500 nm. The current methods for manufacturing EW émulsions primarily rely on the réduction of particle size of agrochemically active ingrédients in dry or wet formulations. Such “top-down” processes are generally slow, require répétitive processing cycles, and require substantial energy. Indeed, the targeted particle sizes, usually 1-350 nm are often time consuming and expensive to produce, frequently requiring répétitive processing cycles/passes through the milling/high shear equipment to achieve desired particle size. Moreover, another challenge in formulating EW émulsion is to achieve narrow particle size distribution which is responsible for imparting stability to the EW formulations. Narrow particle size distribution of dispersed phase with smaller particle size (ranging 1-350 nm) is highly désirable for stability of the EW émulsion.

It is very difficult by conventional methods to producc EW émulsions with narrow particle size distribution which are both easily reproducible and controlled.

OBJECT OF THE INVENTION

Il is an object of the présent invention to provide a process of preparing stable agrochemical composition with narrow particle size distribution.

Il is an object of the présent invention to provide a process of preparing stable agrochemical composition with narrow particle size distribution in a microreactor processing System.

It is another object of the invention to provide a rapid, commercially viable process for producing stable agrochemical composition and the process is technically advanced over the conventional process.

It is another object of the présent invention to provide a stable agrochemical composition with narrow particle size distribution in the form of an EW composition.

SUMMARY OF THE INVENTION

In an aspect, présent invention relates to a process of preparing stable agrochemical composition in microreactor processing System.

In another aspect a process for préparation of a stable agrochemicaf composition in microreactor processing system, said composition comprising:

at least one pesticide in oil phase; and at least one more pesticide in aqueous phase;

wherein mean particle size distribution of said stable agrochemical composition is ranging from Inm to 350nm.

In another aspect is disclosed a process for préparation of a stable agrochemical composition in microreactor processing system, said composition comprising:

atleast one pesticide in oil phase selected from the group comprising of triazolinone, N-phenylphthalimide, diphenyl ether, chloroacetanilide, aryloxyphenoxypropionic acid compounds, its agrochemically compatible salts, esters and dérivatives thereof; and atleast another pesticide in aqueous phase selected from the group comprising of pyrimidinyloxybenzoic analogues, organophosphrous based compounds, bipyridinium compounds, aryloxyalkanoic acid compounds, imidazolinones and bicyclic dicarboxylic acid compounds, its agrochemically compatible salts, esters and dérivatives thereof, wherein said stable agrochemical composition having particle size distribution ranging from Inm to 350nm.

In yet another aspect is provided a process for preparing a stable agrochemical composition according to the présent invention in microreactor processing system, said process comprising the steps of:

a) charging a pre-formulated oil phase in a continuous flow to a reaction vessel of microreactor;

b) charging a pre-formulated aqueous phase in a continuous flow to a reaction vessel of microreactor;

c) allowing mixing of oil phase and aqueous phase in the reaction vessel at predetermined température and pressure to obtain stable agrochemical composition;

wherein obtained composition is having particle size distribution ranging from Inm to 350nm.

In another aspect the présent invention provides a stable agrochemical composition comprising:

a) atleast one pesticide in oil phase; and

b) atleast one pesticide in aqueous phase,

c) wherein said stable agrochemical composition has a particle size distribution ranging from Inm to 350nm.

In another aspect the présent invention provides a stable agrochemical composition prepared in microreactor processing System, said composition comprising:

a) atleast one pesticide in oil phase; and

b) atleast one pesticide in aqueous phase, wherein said stable agrochemical composition having particle size distribution ranging from Inm to 350nm.

In another aspect , the présent invention provides a method to control undesired plants or to influence the growth of plants, said method comprising applying to the plants or to their locus an effective amount of the composition prepared according to the présent invention comprising atleast one pesticide in oil phase; and atleast another pesticide in aqueous phase, wherein said stable agrochemical composition having particle size distribution ranging from Inm to 350nm, to the plants or to their locus.

In another aspect présent invention provide use of said stable agrochemical composition having particle size distribution ranging from Inm to 350nm as an herbicide to control growth of undesired plants and végétation.

In another aspect présent invention provides a kit comprising stable agrochemical composition having particle size distribution ranging from Inm to 350nm according to the présent invention as an herbicide.

Additional features and advantages of the présent invention will be apparent from the detailed description that foliows, which illustrâtes by way of example, the most preferred features of the présent invention which are not to be consirued as limiting the scope of the invention described herein.

BRIEF DESCRIPTION OF DRAWINGS

The drawings described herein are for illustrative purposes only of selected embodiments and not ail possible implémentations and are not intended to limit the scope of the présent disclosure.

FIG. 1 represents a diagram of a mîcroreactor arrangement with one microreactor vessel for 10 stable agrochemical formulation, according to one embodiment.

FIG. 2 represents intensity weighted particle size distribution of the stable agrochemical composition prepared by conventional processing System obtained by zetasizer.

FIG. 3 represents intensity weighted particle size distribution of the stable agrochemical composition prepared by microreactor processing System obtained by zetasizer.

DETAILED DESCRIPTION OF THE INVENTION

Unless defined otherwise, ail lechnical and scientific ternis used herein hâve the same 20 meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It must be noted that, as used in this spécification, the singular forms “a,” “an” and “the” include plural referents unless the content clearly dictâtes otherwise.

As used herein, the terms “comprising” “including,” “having,” “containing,” “invol ving,” and 25 the like are to be understood to be open-ended, i.e., to mean including but not liinited to, The terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances.

In an embodiment, the aspects and embodiments described herein shall also be interpreted to 30 replace the clause “comprising” with either “consisting of ’ or with “consisting essentially of ’ or with “consisting substantially of’.

The terms “plants” and “végétation” include, but aie not liinited to, germinant seeds, emerging seedlings, plants emerging from végétative propagules, and established végétation.

The term “undesired plant” or “weed” refers to and includes any plant which grows where it is not wanted, including pesticide résistant plants.

The term “locus” as used herein shall dénoté the vicinity of a desired crop in which weed control. typically sélective weed control is desired. The locus includes the vicinity of desired crop plants wherein the weed infestation has either etnerged or is yet to emerge. The term crop shall include a multitude of desired crop plants or an îndividual crop plant growing at a locus.

The term ‘partiele size’ refers to the partiele size of oil phase which is in the form of dispersed oil globules in the continuons aqueous phase. The term ‘narrow particle size distribution’ refers to a particle size of more than 80% of oil phase which is in the form of dispersed oil globules in the continuous aqueous phase.

With respect to présent invention ihc mcan particle size distribution of the compositions prepared in mîcroreactor processing system has a narrow range from Inm to 350nm, preferably from 200nm to 350nm.

Surprisingly, invenlors of the présent invention found that the émulsion (EW) agrochemical composition obtained by the émulsification of biphasic System in a mîcroreactor processing System resulted into a stable composition with narrow particle size distribution. Also, the composition prepared in mîcroreactor processing System achieved narrow particle size distribution more rapidly than the conventional processes.

Accordingly, ihe present invention also allows hîgh loads of agrochemical iy active ingrédients with good compatibility and good stability profile. The émulsion thus obtained reinained stable during storage at various température conditions e.g. ambient (25°C), AHS (54°C), 0°C and also -5°C (CIPAC MT 46.3 and MT 39.3) as well as upon end use while diluted with water. The stability of the present composition/formulation is demonstrated in the examples.

The present invention résides in the process for preparing said émulsions in mîcroreactor System and the émulsion formulation having narrow particle size distribution with excellent stability and good efficacy.

The stable agrochemîcal composition prepared in microreactor assembly according to the présent invention has a narrow particle size distribution of less than 500 nm preferably in the range from about 1 nm to about 350 nm.

The stable agrochemîcal composition prepared in microreactor assembly according to the présent invention has a narrow particle size distribution in the range from about 100 nm to about 350 nm.

According to most preferred embodiment of the présent invention, the stable agrochemîcal composition prepared in microreactor processing System according to the présent invention has the particle size distribution in the range from about 200 nm to about 300 nm.

In an aspect the présent invention provides a process for preparing a stable agrochemîcal composition in a microreactor processing System.

In another aspect of the présent invention, there is provided a stable agrochemîcal composition in a microreactor processing System, said composition comprising: atleast one pesticide in oil phase; and atleast one pesticide in aqueous phase, wherein said stable agrochemîcal composition has particle size distribution ranging from 200nm to 350nm.

In another aspect of the présent invention, there is provided a process for préparation of an émulsion in a microreactor processing System, said composition comprising:

atleast one pesticide in oil phase; and atleast one pesticide in aqueous phase, wherein said stable agrochemîcal émulsion composition havîng particle size distribution ranging from 200nm to 350nm.

With preferred embodiments of this invention havîng been described in detail below, the design and operation of the process may now be described as follows.

The process according to the invention will be described with reference to figure 1. FIG, 1 is an overall view of a System incorporating an émulsion manufacturing microreactor system according to the présent invention.

Referring to FIG, 1, the process for préparation of stable agrochemical composition according to the présent invention is conducted in continuons flow reactor System. The microreactor system described is a Phig Flow Reactor (PFR) with one mixing vessel unit (6), having 50 ml capacity. The mixing vessel unit (6) is designed to maintaîn required température according to conditions of the reaction in the system. The pressure élément (7) is connected to the mixing vessel (6) to supply pressure adjustment externally. Heating élément (5) is attached to the mixing vessel (6) that allows external setting to control the température and maintaîn required température. Feed containers (1) and (2) are connected to the mixing vessel (6) by tabulai* components known as first mixing line (10) and second mixing line (11). Feed containers (1) and (2) are connected to the mixing line (10) and mixing line (11) respectively and carries disperscd phase and aqueous phase separately to the mixing vessel (6). Pumps (3) and (4) are attached to these mixing lines (10) and (11) such that it drives the dispersed phase and aqueous phase contained in the feed containers (1) and (2) respectively to the mixing vessel (6). First mixing line (10), is connected to the mixing reaction vessel (6) via pump (3) and second mixing line (11), is connected to the mixing vessel (6) via pump (4) by direclional arrow displayed. During operation, a first liquid flow into the process microreactor. The second liquid contacts and mixes with the first liquid flowing from the feed containers (1) and (2) respectively in the mixing vessel (6) to form an émulsion. The second liquid may form a discontinuons phase in the first liquid. The first liquid can form a continuons phase. The mixing vessel (6) is connected to the collectoi* vessel (9) via receiver line (8). The émulsion flows from mixing vessel (6) is collected in the collecter vessel (9).

The émulsion thus formed in the microreactor system is a stable composition.

In one embodiment, émulsion formulations can be produced within a single continuons flow reactor System. The présent system can be scaled up for desired large capacity.

According to an embodiment of the présent invention, the process of preparing stable agrochemical composition in microreactor processing system comprising steps of:

a) charging a pre-formulated oil phase to microreactor System through a first mixing hne in a continuons flow;

b) charging a pre-formulated aqueous phase to microreactor system through a second mixing line in a continuous flow;

c) allowing mixing of oil phase and aqueous phase in the mixing vessel of microreactor system to obtain stable agrochemical composition.

The process of preparing stable agrochemical composition in microreactor processing System comprises at least one agrochemical active in oil phase and at least one another agrochemical active in aqueous phase.

In an embodiment, the composition of the present invention is an émulsion, oil in water formulation (EW) and émulsion, water in oil formulation (EO).

In a prcfcrred embodiment, the composition of the present invention is an émulsion, oil in water formulation (EW).

According to the présent invention the stable agrochemical composition obtained by this process has a particle size distribution ranging from 200nm to 350nm.

According to an embodiment of the present invention, an agrochemical active in oil phase is a herbicide selected from the group comprising triazolinone compounds, N-phenylphthalimide compounds, diphenyl ether compounds, chloroacetanilide compound, aryloxyphenoxypropionic acid compounds their équivalents, salts, esters, isomers and dérivatives or mixtures or combinations thereof.

In an embodiment the oil phase comprises at least one herbicide in a solvent under continuous mixing; non-ionic and/or anionic surfactants and other customary adjuvants, if required to obtain pre-formulated oil phase.

According to preferred embodiment of the present invention, the oil phase is obtained by dissolving at least one herbicide selected from the group comprising of diphenyl ether herbicides, chloroacetanilide herbicide or aryloxyphenoxypropionic acid herbicides, triazolineone herbicides and imidazolinone herbicides.

According ίο an embodiment of the présent invention, the aqueous phase comprises at least one herbicide selected from pyrimidinyloxybenzoic compounds, organophosphrous based compounds, bipyridinium compounds and imidazolinone compounds, their équivalents, salts, esters, isomers and dérivatives or mixtures thereof. Preferably the aqueous phase comprises at least one herbicide in water to obtain pre-formulated aqueous phase.

According to an embodiment of the présent invention, the process comprising préparation of a stable agrochemical composition in microreactor processing System and wherein said process comprising the steps of:

- solubilizing atleast one pesticide and optionally, other oil soluble ingrédients to obtain pre-formulated oil phase;

- dissolving atleast one pesticide and other water-soluble ingrédients to obtain preformulated aqueous phase;

- i'eeding pre-formulated oil phase and pre-formulated aqueous phase in a microrcactor asscmbly;

- allowing the pre-formulated oil phase and pre-formulated aqueous phase to mix at pre-determined pressure and température in a micro-rcactor assembly to obtain stable agrochemical composition wherein said composition is having mean particle size distribution ranging from 200nm to 350nm.

According to an embodiment of the présent invention, a process for préparation of a stable agrochemical composition in microreactor processing System comprising:

- solubilizing S-metolachlor and optionally other oil soluble ingrédients to obtain preformulated oil phase;

- separatcly, dissolving glufosinate-ammonium and other watcr-solubic ingrédients to obtain pre-formulated aqueous phase;

- feeding pre-formulated oil phase and pre-formulated aqueous phase in a microreactor assembly;

- permitting pre-formulated oil phase and pre-formulated aqueous phase to mix at predetermined pressure and température in a micro-reactor assembly to obtain stable agrochemical composition with mean particle size distribution ranging from 200nm to 350nm.

According to an embodiment of the présent invention, a process for préparation of a stable agrochemical composition in microreactor processing System comprising::

- solubilizing oxyiluorfen and optionally other oil soluble ingrédients to obtain preformulated oîi phase;

- separately, dissolving glufosinate-ammonium and other waler-soluble ingrédients to obtain pre-formulated aqueous phase;

- flowing pre-formulated oil phase and pre-formulated aqueous phase in a microreactor assembly;

- allowing pre-formulated oil phase and pre-formulated aqueous phase to mix at predetermined pressure and température in a miciO-reactor assembly to obtain stable agrochemical composition with mean particle size distribution ranging from 200nm to 350nm.

According to an embodiment of the présent invention, a process for préparation of a stable agrochemical composition in microreactor processing System comprising:

- solubilizing haloxyfop-P-methyl and optionally other oil soluble ingrédients to obtain pre-formulated oil phase;

- separately, dissolving glufosinate-ammonium and other water-soluble ingrédients to obtain pre-formulated aqueous phase;

- flowing pre-formulated oil phase and pre-formulated aqueous phase in a microreactor System;

- pennitting pre-formulated oil phase and pre-formulated aqueous phase to mix at predetermined pressure and température in a micro-reactor assembly to obtain stable agrochemical composition with mean particle size distribution ranging from 200nm to 350nm.

According to an embodiment of the présent invention, a process for préparation of a stable agrochemical composition in microreactor processing System/assembly is a continuous process.

According to an embodiment of the présent invention, a process of preparing stable agrochemical composition in microreactor processing System is carried out in a reactor selected from Spinning Disk Reactor (SDR), Plug Flow Reactors (PFR), Micro Channels,

Meso Channel Plates, Continuons Stirring Tank Reactor (CSTR), Shaken Tube or Oscillatory Flow Tubes.

According to an embodiment of the présent invention, a process of preparing stable 5 agrochemical composition in microreactor processing System is carried out in Spinning Disk Reactor (SDR).

According to an embodiment of the présent invention, a process of preparing stable agrochemical composition in microreactor processing System is carried out in Plug Flow Reactors (PFR).

According to an embodiment of the présent invention, the rate of flow of pre-formulated oil phase in first mixing line is ranging from about O.lg/min to about 10g/min.

According to preferred embodiment of the présent invention, the rate of flow of pre15 fonnulated oil phase in first mixing line is ranging from about 2g/niin to about 6 g/min.

According to an embodiment of the présent invention, the rate of flow of pre-formulated aqueous phase in second mixing line is ranging from about O.lg/min to about 4000 g/min.

According to preferred embodiment of the présent invention, the rate of flow of preformulated aqueous phase in second mixing line is ranging from about 2g/min to about 3000g/min.

Choice of mixing vessel capacity dépends on the amount of stable composition to be 25 prepared. According to an embodiment of the présent invention, capacity of mixing vessel varies from 0.1 ml to 1000ml.

According to a preferred embodiment of the présent invention, mixing vessel is a spinning dise type reactor having rotating dise in a collection tank. The surface area availabié for mass 30 transfer is roughly equal to the surface area of the dise, and a moderate amount of shear in the liquid film enhances mass transfer. The résidence lime in the reactor does greatly dépend on the spinning rate of the dise, so that higher shear cornes at the cost of shorter résidence times.

Accordîng to an embodiment of the présent invention, résidence time of pre-formulated oil phase and pre-formulated aqueous phase reactants in the reaction vessel to préparé said stable agrochemical composition is from about 30 seconds to 1 hour.

Accordîng to an embodiment of the présent invention, mixing vessel receives pre-formulated oil phase from first mixing line and pre-formulated aqueous phase from second mixing line simultaneously or sequentially to facilitate mixing of oil phase and aqueous phase under predetermined température and pressure.

Accordîng to an embodiment of the présent invention, température of the mixing vessel is ranging from about 1°C to about 50°C.

Accordîng to preferred embodiment of the présent invention, température of the mixing vessel is ranging from about 10°C to about 40°C.

Accordîng to an embodiment of the présent invention, température of the mixing vessel is ranging from about 20°C to about 30°C.

Accordîng to an embodiment of the présent invention, pressure of the mixing vessel is ranging from about 0.1 to about 20 bar.

Accordîng to preferred embodiment of the présent invention, pressure of the mixing vessel is ranging from about 1 to about 10 bar.

Accordîng to an embodiment of the présent invention, résidence time to facilitate efficient mixing of oil phase and aqueous phase to obtain stable agrochemical composition is less than 30 minutes.

Accordîng to an embodiment of the présent invention, résidence time to facilitate efficient mixing of oil phase and aqueous phase to obtain stable agrochemical composition is less than 10 minutes.

Accordîng to an embodiment of the présent invention, résidence time to facilitate efficient mixing of oil phase and aqueous phase to obtain stable agrochemical composition is less than 1 minute.

In an aspect the présent invention provides a stable agrochemical composition comprising: atleast one pesticide in oil phase; and atleast one pesticide in aqueous phase, wherein said stable agrochemical composition has narrow mean particle size distribution ranging from 200nm to 350nm.

According to an embodiment of the présent invention, the pesticide in oil phase of the stable agrochemical composition is selected from the group comprising of triazolinone, Nphenylphthalimide, diphenyl ether, chloroacetanilide, aryloxyphenoxypropionic acid compounds, its agrochemically compatible salts, esters and dérivatives thereof.

According to an embodiment of the présent invention, the pesticide in oil phase of the stable agrochemical composition is selected from the group comprising of diphenyl ethers, chloroacetanilide compounds, aryloxyphenoxypropionic acid compound, imidazolinones, carbamates, thiocarbamatcs, baloacetanilides, phcnoxycarboxyiic acid dérivatives, triazolinones, N-phenylphthalimide herbicides, heteroaryloxyphenoxy-alkanecarboxylic acid dérivatives such as aryioxyphenoxy, quinolyloxy, quinoxalyloxy, pyridyloxy, benzoxalyloxy and benzothiazoleyloxyphenoxyalkanecarboxylic esters, cyclohexanedione dérivatives, pyrimidyloxypyridinecarboxylic acid dérivatives, pyrimidyloxybenzoic acid dérivatives, sulfonylureas, triazoleopyrimidinesulfonamide dérivatives, and S-(Naryl-Nalkylcarbamoylmethyl)dithiophosphoric ester compounds and salts or mixtures of such pesticides.

According to certain embodiments of the présent invention, the pesticide in oil phase is selected from diphenyl ether compound, chloroacetanilide compound or aryloxyphenoxypropionic acid compound, triazoiineone compound and imidazolinone compound.

According to an embodiment of the présent invention, the pesticide n an oil phase is selected from the group comprising of diphenyl ether compound, chloroacetanilide compound or aryloxyphenoxypropionic acid compounds.

According to an embodiment of the présent invention, the pesticide in an oil phase is selected from diphenyl ether compounds, their équivalents, metaboiites, salts, esters, isomers and dérivatives compounds thereof.

According lo an embodiment of the présent invention, diphenyï ether compound include ethoxyfen, acifluorfen, aclonifen, bifenox, chlomethoxyfen, chlornitrofen. etnipromid, fluorodifen, fluoroglycofen fluoronitrofen, fomesafen, fucaomi, furyloxyfen, halosafen, 5 lactofen ,nitrofen, nitrofluorfen, oxyfluorfen their équivalents, métabolites, salts, esters and dérivative compounds.

According to preferred embodiment of the présent invention the diphenyï ether compound is oxyfluorfen.

According to an embodiment of the présent invention, pesticide in an oil phase selected from chloroacetanilide compounds, their équivalents, métabolites, salts, esters, isomers and dérivatives thereof.

According to an embodiment of the présent invention, chloroacetanilide compounds include 15 acelochlor, alachlor, butachlor, butenachlor, dclachlor, dicthatyl, dimcthachior, cthachlor, ethaprochlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prynachlor, terbuchlor, thenylchlor, xylachlor.

According to preferred embodiment of the présent invention the chloroacetanilide compound 20 is selected from metolachlor or S -metolachlor.

According to an embodiment of the présent invention, pesticide in an oil phase selected from aryloxyphenoxypropionic acid compounds, their équivalents, métabolites, salts, esters, isomers and dérivatives thereof.

According to an embodiment of the présent invention, aryioxyphenoxy propionic acid compounds include chlorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop fenoxaprop-P, fenthiaprop, fluazifop, fluazifop-P, haloxyfop, haloxyfop-P, haloxyfop-P methyl, isoxapyrifop, kuicaoxi, metamifop, propaquizafop, quizalofop, quizalofop-P and 30 trifop.

In certain embodiment of the présent invention the aryloxyphenoxypropionic acid compounds are selected from haloxyfop, and its isomers or its dérivatives such as esters.

In another embodiment of the présent invention the aryloxyphenoxypropionic acid compound is haloxyfop-P methyl.

According to an embodiment of the présent invention, the stable agrochemical composition S comprising from about 0.1% to about 90% w/w and preferably from about 1% to about 70% w/w of pesticide in oil phase of the total weight of the stable agrochemical composition.

According to a preferred embodiment of the présent invention, the stable agrochemical composition comprising from about 10%' to about 50% w/w of pesticide in oil phase of the 10 total weight of the stable agrochemical composition.

According to an embodiment of the présent invention, pesticide in oil phase of the stable agrochemical composition is selected from the group comprising of acetochlor, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, 15 benfuresate, bensulfuron-mcthyl, bcnsulidc, bcnzfendizonc, bcnzofcnap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clomazone, clomeprop, cloransulam-rnelhyl, cyanazine, cycloate, cyclosulfamuron, daimuron, 20 desmedipham, desmetryn, dichlobenil, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, dinoterb, diphenamid, dithiopyr, diuron, EPTC, esprocarb, ethalfiuralin, ethametsulifuron-methyl, ethofumesate, ethoxysulfuron, etobenzanid, ferioxaprop-ethyl, fenuron, flamprop-methyl, flazasulfuron, fluazolate, fhichloralin, flumetsulam, llumiclorac-pentyl, flumioxazin, fluometuron, fluorochloridone, 25 flupoxam, flurenol, fluridone, fluroxypyr-l-methylheplyl, flurtamone, fluthiacet-methyl, halosulfuron, hcxazinonc, imazosulfuron, indanof an, isoproturon, isouron, isoxaben, isoxaiflutole, lenacii, linuron, mefenacet, metamitron, metazachlor, methabenzthiazuron, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, meloxuron, metribuzin, metsulifuron, molinate, monolinuron, naproanilide, napropamide, neburon, 30 nicosulfuron, norfiurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, pebulate, pendimethalin, pcntanochlor, pentoxazone, phenmedipham, piperophos, pretilachlor, primisulfuron, prodi amine, profluazol, prometon. prometryn, propachlor, propanhl, propazine, propham, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyributicarb, pyridate, pyriminobac-methyl, quinclorac, quinmerac, rimsulfuron, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron, sulfosulfuron, tebutam, lebulhiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thenyichlor, thiazopyr, thidiazimin, thifensulfuron, thiobencarb, tiocarbazil, triallate, triasulfuron, tribenuroii, trietazine, trifluralin, triflusuifuron and vernolate and salts or mixtures of such herbicides.

According to an embodiment of the présent invention, the pesticide in aqueous phase of the stable agrochemical composition is selected from the group comprising of pyrimidinyloxybenzoic compounds, organophosphorous based compounds, bipyridinium compounds, aryloxyalkanoic acid compounds, imidazolinones and bicyclic dicarboxylic acid compounds and salts or mixtures of such pesticides, their équivalents, métabolites, salts, esters, isomers and dérivatives thereof.

According to an embodiment of the présent invention, the pesticide in aqueous phase of the stable agrochemical composition is selected from the group comprising of lactofen, fomesafen, pyrithiobac sodium, bispyribac sodium; glyphosate, glufosinate. glufosinate-P, bilanafos, bialaphos, paraquat, diquat, 2,4-D, MC PA, MCPB, triclopyr, pichloram, aminopyralid, dicamba, 2,3,6-TBA, tricamba, clopyralid; imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin. imazelhapyr; endolhal and salts or isomers or mixtures of such pesticides.

According to preferred embodiment of the présent invention, the herbicide in aqueous phase is glufosinate, ail stereoisomers and salis, for example, D,L-2-amino-4-[hydroxy(melhyl)phosphinyl]butanoic acid (DL-glufosinate), glufosinate ammonium sait, glufosinate sodium sait, glufosinate potassium sait, L-glufosinate, L-glufosinate sodium sait, L-glufosinate ammonium sait, L-glufosinate potassium sait.

According to most preferred embodiment of the présent invention, herbicide in aqueous phase is glufosinate ammonium sait, or L-glufosinate ammonium sait, or their mixtures and salis thereof.

According to an embodiment of the présent invention, the stable agrochemical composition comprising from about 0.1% to about 90% w/w and preferably from about 1% to about 70% w/w of pesticide dissolved in aqueous phase of the total weight of the stable agrochemîcal composition.

According to preferred embodiment of the présent invention, the stable agrochemîcal composition comprising from about 10% to about 50% w/w of pesticide dissolved in aqueous phase of the total weight of the stable agrochemîcal composition.

According to an embodiment of the présent invention, the stable agrochemîcal compositions according to the présent invention may oplionally include adjuvants/auxiliary agents commonly used in agricultural formulations and known to those skilled in the art. Examples include surfactants, solvent, fertilizer, pH modifiers, crystaiiization inhibitors, viscosity modifïers, suspending , agents, spray droplet modifiers, pigments, antioxidants, foaming agents, light- blocking agents, antifoam agents, sequestering agents, neutralizing agents, corrosion inhibitors, dyes, odorants, spreading agents, pénétration aids, micronutrients, émollients, lubricants, sticking agents, dispersing agents, wetting agent, thickening agents, freezing point depressants, antimicrobial agents, and the like.

According to an embodiment of the présent invention, stable agrochemîcal composition comprises of one or more organic solvents. With respect to the présent invention the term ’organic solvent’, refers to polar or nonpolar organic solvents.

Examples of polar or non-polar organic solvents are aliphatic or aromatic hydrocarbons for example Aromatic C-9, Solvent naphtha, Solvesso 100, Solvessol50 and Solvesso 200, their dérivatives, halogenated aliphatic or aromatic hydrocarbons, ethers, polyhydric alcohols, alkylene glycols, alkyleneglycol monoalkyl ethers such as propylene glycol monomethyl ether, spicosolve and dialkyl ethers, amides such as Rhodiasolv ADMA 10, ADMA 810, kctoncs for cxample cyclohexanonc or isophorone, glycerol and glycerol esters such as glycerol triacetate, N- methylpyrrolidone, nitriles and sulfoxides and or combinations thereof.

According to another embodiment the solvents are selected from oils of vegetable or animal origin or their dérivatives. Examples of oils include soyabean oil, epoxidized soybean oil, linseed oil, rapeseed oil, canola oil, olive oil or sunflower oil, emulsified vegetable oil, com oil, its concentrâtes and lower alkyl dérivatives thereof.

Alkyl esters of oil s of végétal)le origin such as, for example, the methyl dérivatives, or an oil of animal origin such as fish oil or beef tallow. Esters of plant oils are alkyl esters obtainable from medium chained fatty acids by estérification with alkanols or by transestérification of the corresponding plant oils. Examples of methyl ester of fatty acids and vegetable oil are methyl ester of soyabean oil, methyl ester of canola oil, Sleposol C-65, Steposol C-25 and Steposol C-42.

In a preferred embodiment of the présent invention, the stable agrochemical composition comprises aromatic hydrocarbon solvents selected from Aromatic C-9, ADMA 810, ADMA 10, Xylene, Solvesso 100, Solvesso 150, and Solvesso 200 or combinations thereof.

According to another embodiment of the présent invention, the stable agrochemical composition comprises from about 1% to about 50% and preferably from about 5% to about 40% solvents of the total weight of the stable agrochemical composition.

In a preferred embodiment of the présent invention, the stable agrochemical composition comprises from about 1% to about 30% solvents of the total weight of the stable agrochemical composition.

According to an embodiment of the présent invention, the stable agrochemical composition comprises one or more surfactants selected from the group comprising of anionic and nonionic surfactants.

Non-limiting examples of anionic surfactants include are phosphate esters and sulfate esters of poly (preferably 2 to 30) ethoxylated (preferably Ceto C22) fatty alcohols such as ethoxylated (2 EO (EO means an ethylene oxide unit) oleyl alcohol phosphate ester, ethoxylated oleyl alcohol phosphate esters, ethoxylated (2-10 EO) ccto/stearyl alcohol phosphate esters, ethoxylated (4-6 EO) tridecyl alcohol phosphate esters, ethoxylated fatty alcohol phosphate ester, ethoxylated (3-6 EO) fatty alcohol phosphate esters, free acids of complex organic phosphate esters , phosphate esters of polyethoxylated (8 to 25 EO) such as Stepfac TSP-PE-N, arylphenols (such as pofyelhoxylated di- and tristyrylphenols) (e.g. Soprophor), sulfate esters of polyethoxylated (8 to 25 EO) arylphenols (such as polyethoxylated di- and tristyrylphenols) (e.g. Soprophor DSS/7®, Soprophor 4D384®), inorganic salts of alkylbenzenesulfonate (such as calcium dodecylbenzenesulfonate) or inorganic salts of polycarboxlic acids, such as sodium and potassium salts, Geropon T77® (Rhodia) Rcax 825® (Westvaco) (ethoxylated bgnm sulfonate); Stepfac 8171® (Stepan) (ethoxylated nonylphenol phosphate ester); Ninate 401-A® (Stepan) (calcium alkylbenzene sulfonate); Emphos CS-131® (Witco) (ethoxylated nonylphenol phosphate ester); and Atphos 3226® (Uniqema) (ethoxylated tridecylalcohol phosphate ester) or combinations thereof.

Non-limiting examples of non-ionic surfactants include ethoxylated branched alcohols (e.g. Genapol® X-type) with 2-20 EO units; methyl end-capped, ethoxylated branched alcohols (e.g. Genapol® XM-type) comprising 2-20 EO units; ethoxylated coconut alcohols (e.g. Genapol® C-types) comprising 2-20 EO units; poiyethoxylates, polyether alcohols, branched secondary alcohol ethoxylates (Tergitol™ TMN sériés, Dow Chemical, Midland, Mich.), ethylene oxide/propylene oxide copolymers (Tergitol™ L Sériés, Tergitol™ XD, XH, XJ and Dow Chemical, Midland, Mich.), nonylphenol ethoxylates (Tergitol™ NP Sériés, Dow Chemical, Midland, Mich.), octylphenol ethoxylates (Triton™ X Sériés, Dow Chemical, Midland, Mich ), secondary alcohol ethoxylates (Tergitol™ 15-S Sériés, Dow Chemical, Midland, Mich.), glycol esters, triglycéride ethoxylates, alkanolamides, sorbitan ester ethoxylates, linear and branched alcohol alkoxylates, potyalkyîene oxide block copolymer (Atlox G5000 and G5000L sériés), fatty alcohol ethoxylates, organomodified polysiloxanes, e.g. BreakThru® OE444, BreakThru® S240, Silwett® L77, Silwett® L408, Silwet® L8O6; Vegetable oil ethoxylates (Alkamuls VO/2003®, Alkamuls PSTO 20®, Alkamuls 400DO®, (Alkamuls SML®); polyethoxylated (30 to 40 EO) castor oils, polyethoxylated (6 to 20 EO) fatty (Cg to C22) alcohols, polyethoxylated (8 to 25 EO) arylphenols (such as polyethoxylated di- and tristyrylphenols (Soprophore BSU), tridecyl alcohol polyglycol ethers (such as ethoxylated (6 EO) tridecyl alcohol: Genapol® X-060, Clariant, Germany) polyalkoxylated alkyl ethers (such as polyalkoxylated butyl ether: Witconol® NS 500 K, CK Witco, USA), ethylene oxide propylcnc oxide block copolymers (molecular weight ranging from 4,000 to 20,000 preferably ranging from 6,500 to 15,000) or combinations thereof.

According to another embodiment of the présent invention, the stable agrochemical composition comprises from surfactants from about 0.1% to about 30% and preferably from about 0.5% to about 20% of the total weight of the stable agrochemical composition.

In a preferred embodiment of the présent invention, composition comprises surfactants from about 1% to about 15% of the total weight of the stable agrochemical composition.

According to another embodiment of the présent invention, stable agrochemical composition further comprises one or more film-forming agent/thickener. Ex amples of suitable filmforming agents/thickeners are thermoplastic resins such as polyvinyl pyrrolidone, polyvinyl alcohols, and or vinylpyrrolidone/vinyl acetate copolymers.

According to another embodiment of the présent invention, stable agrochemical composition comprises film-forming agents/thickeners generally added in an amount from about 0.1% to 5.0% w/w, preferably from about 0.5 to about 3.0% w/w.

According to another embodiment of the présent invention, stable agrochemical composition, optionally comprises further additives or auxiliaries, preferably antifreeze agents, stabilizing agents, antifoams and defoamers, preservatives, colouring agents and/or odour masking products.

Examples of suitable antifreeze agents are ethylcnc glycol, monopropylene glycol, glycerol, hexylene glycol, l-methoxy-2-propanol, cyclohexanol, in particular monopropylene glycol.

They are optionally added in an amount, preferably from about 0.1% to about 30% w/w, particularly from about 1% to about 15% w/w of total weight of the stable agrochemical composition.

Stabilizing agents which are optionally added in the formulation are acids, preferably organic acids, such as dodecylbenzene sulfonic acid, acetic acid, propionic acid or citric acid, in particular citric acid and antioxidants, such as butyl hydroxy toluene (BHT), butyl hydroxy anisole (BHA), in particular butyl hydroxy toluene.

The stabilizing agent is optionally added in an amount of generally from about 0.01% to about 2% w/w, particularly from about 0.1% to about 1% w/w of total weight of the stable agrochemical composition.

Preferred antifoams and defoamers are based on silicone, particularly preferred are an aqueous émulsion of dialkylpolysiloxanes commercially available as Rhodorsil® 426R. Wacker SE sériés, and a mixture of dialkylpolysiloxanes as an oil, commercially available as Rhodorsil® 416, Wacker S184 or Wacker SL.

The antifoams/defoamers are optionally added in an amount from about 0.01% to about 2% w/w, preferably from about 0.1% to about 1.5% w/w of total weight of the stable agrochemical composition.

The preservatives are optionally added such as, dérivatives of benzoic acid, sorbic acid, formaldéhyde, in particular a combination of methyl parahydroxybenzoate or propyl parahydroxybenzoate, generally in an amount from about 0.1% to about 1.0% w/w, particularly from about 0.2% to about 0.5% w/w.

Further preferred optional additives are colouring agents such and odour masking products such as a mixture of numerous natural and synthesis perfumes, such as Perfume® TM 4242.

The additives are optionally added in amounts of generally, from about 0.01% to about 1% w/w, particularly from about 0.1% to about 0.5% w/w of colouring agent and from about 0.02% to about 2% by weight, particularly from about 0.1% to about 1% by weight of odour masking products.

The stable agrochemical composition according to the present invention comprises at least 5% by weight, preferably at least 10% by weight and especially preferably at least 15% by weight of water based on the total weight of the stable agrochemical composition.

The stable agrochemical composition according to the invention comprises from about 5% to about 70% w/w, preferably from about 10% to about 60% w/w and especially preferably from about 15% to about 50% w/w of water, based on the total weight of the stable agrochemical composition.

According to an embodiment of the present invention there is provided a stable agrochemical composition prepared in mîcroreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises glufosinate ammonium, oxyfluorfen, solvent and non-ionic and/or anionic surfactants.

Accordingly, the stable agrochemical composition prepared in mîcroreactor processing system with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 0.1% to about 90% by weight of glufosinate ammonium, from about 0.1% to about

90% by weight of oxyfluorfen, from about 1 % to about 50% by weight of solvent and from about 0.1% to about 30% by weight of non-ionic and/or anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 0.1% to about 50% by weight of glufosinate ammonium, from about 0.5% to about 40% by weight of oxyfluorfen, from about 1% to about 30% by weight of solvents and from about 1% to about 10% by weight of non-ionic and anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 0.1% to about 50% by weight of glufosinate ammonium, from about 0.5% to about 40% by weight of oxyfluorfen, from about 1% to about 30% by weight of solvents and from about 1% to about 10% by weight of non-ionic and anionic surfactants is in the form of an Emulsion, oil in water formulation (EW).

According to an embodiment of the présent invention there is provided a stable agrochemical composition prepared in microreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises glufosinate ammonium, Smetolachlor, solvent and non-ionic and/or anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 0.1% to about 90% by weight of glufosinate ammonium, from about 0.1% to about 90% by weight of s-metolachlor, from about 1% to about 50% by weight of solvent and from about 0.1% to about 30% by weight of non-ionic and/or anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 10% to about 50% by weight of glufosinate ammonium, from about 10% to about 50% by weight of s-metolachlor, from about 1% to about 30% by weight of solvents and from about 5% to about 20% by weight of non-ionic and anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 10% to about 50% by weight of glufosinate ammonium, from about 10% to about 50% by weight of s-metolachlor, from about 1% to about 30% by weight of solvents and from about 5% to about 20% by weight of non-ionic and anionic surfactants is in the form of an Emulsion, oil in water formulation (EW).

According to an embodiment of the présent invention there is provided a stable agrochemical composition developed in microreactor processing System having particle size distribution ranging from 200nm to 350nm. comprises glufosinate ammonium, haloxyfop-p-methyl, solvent and non-ionic and/or anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing System with naiTow particle size distribution ranging from 200nm to 350nm, comprises from about 0.1% to about 90% by weight of glufosinate ammonium, from about 0.1% to about 90% by weight of haloxyfop-p-methyl, from about 1% to about 50% by weight of solvent and from about 0.1% to about 30% by weight of non-ionic and/or anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing system with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 10% to about 50% by weight of glufosinate ammonium, from about 1% to about 50% by weight of haloxyfop-p-methyl, frotn about 1% to about 30% by weight of solvents and from about 1% to about 20% by weight of non-ionic and anionic surfactants.

Accordingly, the stable agrochemical composition prepared in microreactor processing System with narrow particle size distribution ranging from 200nm to 350nm, comprises from about 10% to about 50% by weight of glufosinate ammonium, from about 1% to about 50% by weight of haloxyfop-p-methyl, from about 1% to about 30% by weight of solvents and from about 1 % to about 20% by weight of non-ionic and anionic surfactants is in the form of an Emulsion, oil in water formulation (EW).

According to the présent invention the stable agrochemical compositions prepared in a microreactor processing System as described herein hâve particle size distribution ranging from 200nm to 350nm.

Advantageously the present composition is stable during storage at various température conditions e.g. ambient (25°C), AHS (54°C), 0°C and also -5°C (CIPAC MT 46.3 and MT 39.3) as well as upon end use while diluled with water.

According to an embodiment of the present invention, the present invention provides a method for controlling undesired plants or to influence the growth of plants, said method comprising applying to the plants or to their locus an effective amount of the composition prepared according to the present invention comprising atleast one pesticide in oil phase; and atleast another pesticide in aqueous phase, wherein said stable agrochemical composition having mean particle size distribution ranging from 200nm to 350nm, to the plants or to their locus.

According to an embodiment of the présent invention, the method to control undesired plants or to influence the growth of plants, said method comprising applying to the plants or to their locus an effective amount of the composition comprising atleast one herbicide in oil phase; and atleast one herbicide in aqueous phase;

wherein said stable agrochemical composition has narrow particle size distribution ranging from 200nm to 350nm, to the plants or to their locus and wherein said stable agrochemical composition is prepared in microreactor processing System.

In another embodiment, there is provided a method for weed control comprising applying to the plants, a composition according to the present invention comprising atleast one herbicide in oil phase; and atleast one herbicide dissolved in aqueous phase; wherein said stable agrochemical composition has narrow particle size distribution ranging from 200nm to 350nm and; wherein said stable agrochemical composition is prepared in microreactor processing system.

In a preferred embodiment of the present invention, there is provided a method for controlling harmful plants wherein said method comprises applying to the plants or to their locus an effective amount of the composition according to the present invention comprising glufosinate, other herbicide and/or other auxiliary ingrédients, wherein said stable agrochemical composition has narrow particle size distribution ranging from 200nm to 350nm and; wherein said stable agrochemical composition is prepared in microreactor processing System.

In an aspect the présent invention provides use of présent stable agrochemical composition having particle size distribution ranging from 200nm to 350nm, prepared according to the présent invention as herbicide to control harmful plants.

In an embodiment the présent invention provides use of émulsion composition comprising glufosinate and or other herbicide and/or other auxiliary ingrédients, wherein said émulsion is 10 prepared in microreactor processing System having narrow particle size distribution ranging from 200nm to 350nm.

The abovementioned compositions provide effective weed control to keep agricnltural crops free from undesired competing plants and thus to safeguard and/or increase the yields from the qualitative and quantitative point of view.

The compositions of the présent invention maybe used to target weeds among the crops such corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco, etc.; vegetables: solanaceous vegetables such as eggplant, tomato, pimento, pepper, polato, etc., cucurbil vegetables such as cucumber, 20 pumpkin, zucchini, water melon, melon, squash, etc., cruciferous vegetables such as radîsh, white tumip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower, etc., asteraceous vegetables such as burdock, crown daisy, artichoke. lettuce, etc, liliaceous vegetables such as green onion, onion, garlic, and asparagus, ammiaceous vegetables such as carrot, parsley, celery, parsnip, etc., chenopodiaceous vegetables such as 25 spinach, Swiss chard, etc., lamiaceous vegetables such as Perilia frutescens, mint, basil, etc, strawbcrry, sweet potato, Dioscorca japonica, colocasia, etc., flowers, foliage plants, turf grasses, fruits; pome fruits such apple, pear, quince, etc, stone fleshy fruits such as peach, plum, nectarine, Prunus mume, cherry fruit, apricot, prune, etc., citrus fruits such as orange, lemon, rime, grapefruit, etc., nuts such as chestnuts, walnuts, hazelnuts, almond, pistachio, 30 cashew nuts, macadamia nuts, etc. berries such as blueberry, cranberry, blackberry, raspberry, etc., grape, kaki fruit, olive, plum, banana, coffee, date palm, coconuts, etc., tea, nut and vine crops, crops such as coconut, coffee, cocoa trees other than fruit trees; tea, mulberry, flowering plant, trees such as ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple,

Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zeikova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxas cuspidate, etc.

The iarget weeds may be selected from Alopecurus myosuroides Huds. (blackgrass, ALOMY), Amaranthus palmeri (Palmer amaranth, ΑΜΑΡΑ) Amaranthus viridis (slender amaranth, AM A VI), Avena fatua (wild oat, AVEFA), Brachiaria decumbens Stapf. or Urochloa decumbens (Stapf), Brachiaria brizantha or Urochloa brizantha, Brachiaria platyphylla (Groseb.) Nash or Urochloa platyphylla (broadleaf signalgrass, BRAPP), Brachiaria plantaginea. or Urochloa plantaginea (alexandergrass, B RA PL), Cenchrus echinatus (southern sandbur, CENEC), Digitaria horizonialis Willd. (Jamaican crabgrass, DIGHO), Digitaria insularis (sourgrass, TRCIN), Digitaria sanguinalis (large crabgrass, DIGSA), Echinochloa crus-galli (bamyardgrass, ECHCG), Echinochloa colonum (junglerice, ECHCO), Eleusine indica Gaerin. (goosegrass, ELEIN), Lolium multiflorum Lam. (Italian ryegrass, LOLMU), Panicum dichotomiflorum Michx. (fall panicum, PAND1), Panicum miliaceum L. (wild-proso millet, PANM1), Sesbania exaltata (hemp sesbania, SEBEX), Setaria faberi Herrm. (giant foxtail, SETFA), Setaria viridis (green foxtail, SETVI), Sorghum halepense (Johnsongrass, SORHA), Sorghum bicolor, Moench ssp., Arundinaceum (shattercane, SORVU), Cyperus esculentus (yellow nutsedge, CYPES), Cyperus rotundus (purple nutsedge, CYPRO), Abuülon theophrasti (velvetleaf, A B UT H), Amaranthus species (pig weeds and amaranths, AMAS S), Ambrosia artemisiifolia L. (common ragweed, AMBEL), Ambrosia psilostachya DC. (western ragweed, AMBPS), Ambrosia trifida (giant ragweed, AMBTR), Anoda crisiata (spurred anoda, ANVCR), Asclepias syriaca (common milkweed, ASCSY), Bidens pilosa (hairy beggarticks, BIDPI), Borreria species (BOISS), Borreria alata or Spermacoce alata Aubl. or Spermacoce latifolia (broadleaf buttonweed, BO1LF), Chenopodium album L. (common lambsquarters, CHEAL), Cirsium arvense (Canada thistlc, CIRAR), Commelina benghalensis (tropical spiderwort, COMBE), Datura stramonium (jimsonweed, DATST), Daucus carota (wild carrot, DAUCA), Euphorbia heterophylla (wild poinsettia, EPHHL), Euphorbia hirta or Chamaesyce hirîa (garden spurge, EPHHI), Euphorbia dentata Michx. (toothed spurge, EPHDE), Eriger on bonariensis or Conyza bonariensis (hairy fieabane, ER1BO), Erigeron canadensis or Conyza canadensis (horseweed, ERIC A), Conyza sumatrensis (tall fieabane, ERIFL), Helianthus anmius (common sunflower, HELAN), Jacquemontia tamnifolia (smallflower momingglory, IAQTA), Ipomoea hederacea (ivyleaf momingglory, IPOHE), Ipomoea lacunosa (white momingglory, IPOLA), Lactuca serrioia (prickly lettuce, LACSE), Portulaca oleracea (common purslane, POROL), Richardia species (pusley, RCHSS), Salsola tragus (Russian thistle, SASKR), Sida species (sida, SIDSS), Sida spinosa (prickly sida, SIDSP), Sinapis arvensis (wild mustard, SINAR), Soianum ptychanthum (eastern black nîghtshade, SOLPT), Tridax procumbens (coat buttons, TRQPR), Rumex dentatus (RUMDE)or Xanthium strumarium (common cocklebur, XANST).

Tn an embodiment, the formulation of the présent invention may be applied to the locus either simultaneously or sequentially, such that the herbicide may be applied in a tank mix or as a pre-mixed composition.

In an embodiment, the présent invention may be applied either pre or post emergent. The advantage of the combination/composition is surprisingly good residual effects, when applied in pre-emergent as well as quick knockdown when applied post emergent leading to quick control of weeds. In another embodiment, the présent invention may bc applied for quick burndown of weeds. Another advantage is quick knockdown in the case of burndown.

The method of control of the présent invention may be carried out by spraying the suggested tank mixes, or the individua] herbicides may be formulated as a kit-of-parts containing various components that may be mixed as inslructed prior to spraying.

According to an embodiment of the présent invention, there is provided a kit comprising said stable agrochemical composition as an herbicide to control harmful plants.

According to an embodiment of the présent invention, the various components of the stable agrochemical composition can be used individually or already partially or completely mixed with one another to prépare the composition according to the invention. It is also possible to be packaged and used furlher as combination composition such as a kit of parts.

In one embodiment of the invention, the kits may include one or more, including ail, components that may be used to prépare a stable agrochemical composition. E. g., kits may include active ingrédients and/or auxiliary ingrédients. One or more of the components may already bc combined or formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister.

In other embodiments, two or more components of a kit may be packaged separately, i. e., not pre-formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for stable agrochemical composition.

In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition accordîng to the invention for preparing the stable liquid composition accordîng to the invention.

In a preferred embodiment of the présent invention, the stable agrochemical composition comprising atleast one pesticide in oil phase; and atleast one another pesticide in aqueous phase, wherein said stable agrochemical composition has narrow particle size distribution ranging from 200nm to 350nm; is in the form of a kit.

Inventors of the présent invention succeeded in preparing advantageously stable agrochemical compositions comprising glufosinate, other herbicide and optionally other auxiliary ingrédients, having narrow particle size distribution ranging from 200nm to 350nm. The compositions obtained accordîng to the présent invention has narrow particle size distribution are found to be stable at varions température & conditions as well as effective for their intended biological activity.

In one embodiment the microreactor processing System for producing a stable agrochemical composition comprising glufosinate, other herbicide and optionally other auxiliary ingrédients, is technically advanced over the conventional procès s.

The compositions prepared in microreactor processing system accordîng to the présent invention is obtained at a much faster rate than conventional methods and are reproducible.

The instant invention is more specifically explained by below examples. However, it should be understood thaï the scope of the présent invention is not limiled by the examples in any manner. It will be appreciated by any person skilled in this art that the présent invention includes aforesaid examples and further can be modified and altered within the technical scope of the présent invention.

The following examples demonstrate the préparation of stable oil-in-water émulsion compositions in accordance with the présent invention.

Example 1

An oil-in-water émulsion composition of Giufosinate Ammonium and S-Metolachlor was prepared as follows:

In a Vessel-1, 11.8 g S-metolachlor was dissolved in 12g Solvesso 150 under stirring condition to obtain a mixture. Afterward, 0.5g silwet L408, 1.5g alkamul VO/2003 and 13.3g 10 soprophor 4D384 was subsequently added to the mixture under continuons stirring condition to obtain pre-formulated oil phase. In a Vessel-2, 27.6 g Giufosinate was dissolved in 33.3 ml water under stirring condition to obtain pre-formulated aqueous phase. The reaction vessel was set at a température 30±2°C. Pre-formulated oil phase in Vessel-1 (niaintained at 30±2°C) was fed to the réaction vessel by first mixing line al 3.75 ml/min. Pre-formulated 15 aqueous phase in Vessel-2 (niaintained at 30±2°C) was fed to the reaction vessel by second mixing line at 6.25 ml/min. The reaction vessel was set at 1 bar pressure. Fecding pumps connected to mixing lines were switched on and; pre-formulated oil phase and pre-formulated aqueous phase was allowed to pass through first and second mixing lines respectively to the mixing reaction vessel. The reaction vessel was allowed to facilitate mixing of oil phase and 20 aqueous phase in a continuons flow for about 3.84 second. The resulting oil-in-water émulsion composition was collected in vessel-3.

Ingrédients	Amount (%w/w)
Giufosinate Ammonium	27.6
S-metolachlor	11.8
Solvesso 150	12
Silwet L 408	0.5
Alkamul VO/2003	1.5
Soprophor 4D384	13.3
Water	Qs.

Example 2

An oil-in-water émulsion composition of giufosinate ammonium and haloxyfop-p-methyl 25 was prepared as follows:

In a Vessel-1, 4g haloxyfop-p-methyl was dissolved in 25g aromatic C-9 under stirring condition to obtain mixture. Afterwards, 0.5g silwet L408, 0.5g tergitol XD, 3g soprophore 4D3S4, 3.5g soprophore BSU was subsequently added to the mixture under continuons 5 stirring condition to obtain pre-formulated oil phase. In a Vessel-2, 27.6 g Glufosinate was dissolved in 47.5 ml water under stirring condition to obtain pre-formulated aqueous phase. The reaction vessel was set at a température 3O+2°C. Pre-formulated oil phase in Vessel-1 (maintained at 30±2°C) was fed to the reaction vessel by first mixîng line at 3.5 ml/min. Pre-formulated aqueous phase in Vessel-2 (maintained al 3O±2°C) was fed to the reaction 10 vessel by second mixing line at 6.5 ml/min. The reaction vessel was set at 1 bar pressure.

Feeding pumps connected to mixing lines were switched on and; pre-formulated oil phase and pre-formulated aqueous phase were allowed to pass through first and second mixing lines respectively to the reaction vessel. Allow the reaction vessel to facilitate mixing of oil phase and aqueous phase in a continuous flow for about 3.84 second. The resulting oil-in-water 15 émulsion composition was collected in vesseI-3.

Ingrédients	Amount (%w/w)
Glufosinate Ammonium	27.6
Haloxyfop-P-methyl	4.0
Aromatic C-9	25
Silwet L 408	0.5
Tergitol XD	0.5
Soprophor 4D384	3.0
Soprophor BSU	3.5
Water	Qs.

Example 3

An oil-in-water émulsion composition of glufosinate ammonium and oxyfluorfen was prepared as follows:

In a Vessel-1, 5g Oxyfluorfen was dissolved in 20g organic solvent including aromatic C-9 and Rhodiasolve ADMA 810 under stirring condition to obtain homogeneous solution. Afterwards, 0.5g silwet L408, 1g Atlox G-5000, 4g soprophor BSU was subsequently added

to the solution under continuous stirring condition to obtain pre-formulated homogeneous oil phase.

In a Vessel-2, 14 g Giufosinate ammonium was dissolved in 55.5 ml water under stirring 5 condition to obtain pre-formulated aqueous phase. The reaction vessel was set at a température 30+2°C. Pre-formulated oil phase in Vessel-1 (maintained at 3O±2°C) was fed to the reaction vessel by first mixing line at 3.7 ml/min. Pre-formulated aqueous phase in Vessel-2 (maintained at 30+2°C) was fed to the réaction vessel by second mixing line at 6.3 ml/min. The reaction vessel was set at 1 bar pressure. Feeding pumps connected to mixing 10 lines were switched on and pre-formulated oil phase pre-formulated aqueous phase was allowed to pass through First and second mixing lines respectively to the réaction vessel. Allow the reaction vessel to facilitate mixing of oil phase and aqueous phase in a continuous flow for about 3.84 second. The resulting oil-in-water émulsion composition was coilected in vessel-3.

Ingrédients	Amount (%w/w)
Giufosinate Ammonium	27.6
Oxyfluorfen	5
Solvesso 150	4
ADMA810	16
Silwet L 408	0.5
Atlox G5000	1.0
Soprophor 4D384	4
Water	Qs.

Example 4

An oil-in-water émulsion composition of giufosinate ammonium and s-Melolachlor was prepared as follows: (Comparative Example)

A homogenous solution was prepared by mixing 11.8g S-Metolachlor, 12g solvesso 150 under stirring condition. Afterwards, 0.5g silwet L408, 1.5g alkamul VO/2003 and 13.3g soprophor 4D384 was subsequently added to the solution under continuous stirring condition to obtain pre-formulated homogeneous oil phase. Pre-formulated aqueous phase was prepared by dissolving 27.6 g Glufosinate ammonium in water under stimng condition and oil phase was transferred to aqueous phase slowly to get an EW émulsion.

Ingrédients	Amount (%w/w)
Glufosinate Ammonium	27.6
S-metolachlor	11.8
Solvesso 150	12
S ilwet L 408	0.5
Alkamul VO/2003	1.5
Soprophor 4D384	13.3
Water	Qs.

Comparative study of Particle size distribution:

The stability of ail the compositions were assessed after the stated time period at room température (RT) and 54°C. The samples were tested in a particle size analyzer (Malvern’s Zêta Sizer) to measure the particle size of dispersed oil globules in the continuons phase.

The stable agrochemical composition (Example 1) developed in a microreactor processing System according to the présent invention was tested for particle size distribution. Same composition (Example 4) was prepared by a conventional process. It was observed that composition of Example 1 developed in microreactor processing System found to hâve excellent stability profile with respect to uniformity of the dispersion. 91.7% of particles in the composition of Example 1 found to hâve a mean particle diameter of about 201.2 nm which resulted into very stable émulsion (Fig.3).

However, a wider particle size distribution was observed for the composition of Example 4 developed by conventional method. About 54.9% particles were found to hâve mean particle diameter of 119.3 nm and about 45.1% particles were found to hâve mean particle diameter of 407.6 nm (Fig. 2).

Il was concluded that although Z-Average of both the compositions of Example-3 (ZAverage=303.9nm) and Example-4 (Z-Average= 364.5nm) are within similar range but particle size distribution is drastically different being more narrower distribution in case of Example-1 which depicts uniformity of oil globules (dispersed particles); and more broader distribution in case of Example-4. Therefore, the composition developed in microreactor processing System having narrow particle size distribution found to be more stable than the composition prepared in conventional manner. The resuit of particle size distribution is presented below in Table 1.

Table 1

Example(s)	Mean Particle Diameter (nm)	Percent Intensity
Example (3)	201.2	91.70%
Microreactor Process	43.44	8.30%
Ex ample (4)	119.3	54.90%
Conventional Process	407.6	45.10%

Storage stabilîty of the compositions

The stabilîty of the compositions according to the présent invention was tested as per CIP AC Methods 36,3. Table 2 shows the observations on storing the said stable agrochemîcal compositions at various température conditions e.g. ambient (25°C), AHS (54°C), 0°C and also -5°C (CIPAC MT 46.3 and MT 39.3). It has been observed that ail the compositions (Example 1, 2 and 3) prepared in microreactor System remained quite stable throughout the study. The compositions prepared according to the présent invention appeared as viscous stable émulsion with clear and uniform dispersion in ail the four température conditions mentioned above. No creaming, flocculation or other instabilily related changes observed and the composition developed in micro-reactor System remained quite stable.

Table 2

Composition	Active Ingrédients (% w/w)	Appearance at 25°C after 14 days	Appearance at 54°C after 14 days	Appearance at 0°C after 7 days	Appearance at -5°C after 7 days
Ex ample 1	A-27.6 C- 11.8	Viscous stable émulsion	Viscous stable émulsion	Viscous stable émulsion	Viscous stable émulsion

Ex ample 2	A- 16 B-4	Viscous stable émulsion	Viscous stable émulsion	Viscous stable émulsion	Viscous stable émulsion
Examplc 3	A - 14 D-5	Viscous stable émulsion	Viscous stable émulsion	Viscous stable émulsion	Viscous stable émulsion

A- Glufosinate, B=Haloxyfop-p-methyl. C-S-Metolachlor, D=Oxyfluorfen

Emulsion stability on dilution with water

The compositions were further tested for their stability by observing the appearance of the oil-in water émulsions upon dilution (as per CIP AC MT 36.3) and the results are summarized in Table 3. The stability of said compositions were confirmed by observing them after dilution with water. The sample were checked for the stability parameters such as creaming and sédimentation. Ail the compositions prepared according to the présent invention were 10 found to be stable without any creaming or sédimentation when observed after 24 hours.

Table 3

Composition	Cream formation after 24 hrs (ml)	Sédimentation after 24 hrs	Observation
Example 1	Nil	1 ml	Stable émulsion
Ex ample 2	Nil	0.5 ml	Stable émulsion
Example 3	Nil	0.5 ml	Stable émulsion

Therefore, lhe stable agrochemical composition was successfully prepared in the 15 microreactor system. The composition in the form of an oil dispersion prepared according to the présent invention passed stability tests and remained quite stable in various température conditions. Also, the oil dispersion found to be acceptable even upon dilution. It is to be

understood that the invention is not to be limited to the details of the above embodiments, which are described by way of example only.

Claims (19)

1. A process of preparing stable agrochemical composition in a microreactor processing System comprising:

a) charging a pre-formuiated oil phase comprising atleast one pesticide to microreactor;

b) charging a pre-formulated aqueous phase comprising at least one another pesticide to microreactor; and

c) allowing mixing of oil phase and aqueous phase in the reaction vessel of microreactor to obtain an agrochemical composition wherein said composition is having particle size distribution ranging from 200nm to 350nm.

2. The process as claimed in claim 1 wherein atleast one pesticide in oil phase is selected from (he group comprising of triazolinonc, N-phcnylphthalimidc, diphenyl ether, chloroacetanilide, aryloxyphenoxypropionic acid herbicide compounds, their équivalents, salts, esters, isomers, dérivatives or combinations thereof.

3. The process as claimed in claim 2 wherein pesticide is selected from the group comprising of acifluorfen, chlomethoxyfen, fomesafen, oxyfluorfen, acetochlor, butachlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, clodinafop, cyhalofop, fenoxaprop, haloxyfop, haloxyfop-P, haloxyfop-P methyl, quizalofop, quizalofop-P, amicarbazone, carfentrazone, flucarbazone and sulfentrazone, their équivalents, salts, esters, isomers, dérivatives or combinations thereof.

4. The process as claimed in claim 2 wherein said pesticide is selected from the group comprising pyrimidinyloxybenzoic compounds, organophosphrous based compounds, bipyridinium compounds, imidazolinone herbicide compounds, their équivalents, salts, esters, isomers, dérivatives or combinations thereof.

5. The process as claimed in claim 1 wherein said pesticide is selected from the group comprising bispyribac, pyriminobac, anilofos, bensulide, bilanafos, fosamine, glufosinate, L-glufosinate, glyphosate, imazamox, imazapic, imazapyr, imazaquin and imazethapyr, their équivalents, salts, esters, isomers, dérivatives or combinations thereof.

6. The process as claimed in claim 1 wherein pre-formulated oil phase is obtained by dissolving at least one pesticide selected from the group of triazolinone compounds, N-phenylphthalimide compounds, diphenyl ether compounds, chloroacetanilide compound, aryloxyphenoxypropionic acid compounds their équivalents, métabolites, salts, esters, isomers and dérivatives or mixtures thereof in a solvent under continuous mixing; optionally adding non-ionic and anionic surfactant and customary adjuvants.

7. The process as claimed in claim 1 wherein pre-formulated aqueous phase is obtained by dissolving at least one herbicide selected from the group of pyrimîdinyloxybenzoic compounds, organophosphorous based compounds, bipyridinium compounds and imidazolinone compounds, their équivalents, métabolites, salts, esters, isomers and dérivatives or mixtures thereof in water under continuous mixing to obtain preformulated aqueous phase.

8. The process as claimed in claim 1 wherein said process is carried in microreactor selected from the group comprising of Plug Flow Reactor (PFR), Continuous Stirred Tank Reactor (CSTR), Loop reactor, Packed Bed Reactor (PBR) or combinations thereof.

9. The process as claimed in claim 1 wherein the résidence time for mixing oil phase and aqueous phase is in the range from about 10 seconds to 1 hour.

10. The process as claimed in claim 2 wherein the mixing îs carried out at température in the range from about 10°C to about 50°C and pressure in the range from about 0.1 to about 20 bar.

11. The process as claimed in claim 1 wherein the pre-formulated oil phase is charged to the reactor at flow rate in the range from about O.lg/min to about lOg/min.

12, The process as claimed in claim 2 wherein the pre-formulated aqueous phase is charged to the reactor at flow rate in the range from about 0.1 g/min to about 4000 g/min.

13, A stable agrochemical composition comprising: at least one pesticide in oil phase; and at least one another pesticide in aqueous phase;

wherein mean particle size distribution of said composition is ranging from 200nm to 350nm.

14. The composition as claimed in claim 13 wherein at least one pesticide in oil phase is selected from diphenyl ether, chloroacetanilide and aryloxyphenoxypropionic acid herbicide;

at least one another pesticide in aqueous phase is selected from pyrimidinyloxybcnzoic, organophosphorous and imidazoline herbicide,

15. The composition as claimed in daim 13 wherein the pesticide in oil phase is selected from S-Metolachlor, haloxyfop-p-methyl and oxyfluorfen and another pesticide in aqueous phase is glufosinate or glufosinate ammonium or L- glufosinate or L-glufosinate ammonium.

16. The composition as claimed in claim 15 wherein said agrochemical composition is prepared in mîcroreactor processing system.

17. The composition as claimed in claim 15 wherein said composition is formulated as émulsion, oil in water (EW).

18. A method for controlling undesired plants or to influence the growth of plants comprising applying to the plants or to their locus an effective amount of the stable agrochemical composition comprising: atleast one pesticide in oil phase; and atleast another pesticide dissolved in aqueous phase, wherein said composition having particle size distribution ranging from 200nm to 350nm.

19. The method as claimed in claim 19 wherein at least one pesticide in oil phase is selected from diphenyl ether, chloroacetanilide and aryloxyphenoxypropionic acid herbicide;

at least one another pesticide in aqueous phase is selected from pyrimidinyloxybenzoic, organophosphorous and imidazoline herbicide.