WO2020194164A1 - Stable herbicide formulation of pyrazosulfuron ethyl - Google Patents

Stable herbicide formulation of pyrazosulfuron ethyl Download PDF

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Publication number
WO2020194164A1
WO2020194164A1 PCT/IB2020/052677 IB2020052677W WO2020194164A1 WO 2020194164 A1 WO2020194164 A1 WO 2020194164A1 IB 2020052677 W IB2020052677 W IB 2020052677W WO 2020194164 A1 WO2020194164 A1 WO 2020194164A1
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Prior art keywords
composition
pyrazosulfuron ethyl
silica
china clay
storage stable
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PCT/IB2020/052677
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French (fr)
Inventor
Rajan Ramakant Shirsat
Vikas Vinayak OLTIKAR
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UPL Ltd
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UPL Ltd
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Priority to MYPI2021004895A priority Critical patent/MY205125A/en
Priority to PH1/2021/552040A priority patent/PH12021552040A1/en
Priority to CN202080017900.0A priority patent/CN113573585A/en
Priority to JP2021557225A priority patent/JP2022527159A/en
Priority to BR112021016614A priority patent/BR112021016614A2/en
Publication of WO2020194164A1 publication Critical patent/WO2020194164A1/en
Priority to CONC2021/0010910A priority patent/CO2021010910A2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules

Definitions

  • the present invention relates to a stable herbicide formulation comprising pyrazosulfuron ethyl.
  • the present invention also relates to a stabilising system for formulation comprising pyrazosulfuron ethyl and method of preparation the formulation.
  • Pyrazosulfuron ethyl is a pyrimidinylsulfonylurea herbicide having IUPAC name 5-[(4,6 dimethoxypyrimidin-2-ylcarbamoyl) sulfamoyl]-l -methyl pyrazole-4-carboxylic acid and chemical structure as follows:
  • Pyrazosulfuron ethyl is a systemic herbicide used to control annual and perennial broad-leaved weeds and sedges, pre- or post-emergence, wet sown and transplanted rice crops.
  • compositions comprising pyrazosulfuron ethyl as active ingredient are available in the market, but they are known to be degrading during the shelf life of the product.
  • the degradation of the active ingredient is not suitable for formulation and will result in ineffective dose application when applied in the field thus resulting in poor control of weeds.
  • the present invention provides a storage stable agrochemical composition comprising:
  • the present invention provides a process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and a stabilising system comprising silica and china clay, said process comprising:
  • Step-1 Pre-blending of pyrazosulfuron ethyl and stabilising system comprising silica and china clay optionally with agrochemically acceptable excipients;
  • Step-2 Milling
  • Step-3 Post-blending and/or drying to get a compositionwith predefined % moisture.
  • the present invention provides a method of controlling undesired weeds, said method comprising applying to the weeds or to their locus an herbicidally effective amount of astorage stable agrochemical composition according to the present invention.
  • the present invention provides an agrochemical composition and in particular a storage stable agrochemical composition.
  • the present inventors found a stabilizing system which is effective in increasing stability and shelf life of agrochemical compositions comprising pyrazosulfuron ethyl.
  • astabilising system comprising silicaand china clay.
  • compositions according to the present invention further comprises other agrochemically acceptable surfactants.
  • a storage stable composition comprising:
  • astabilising system comprising silicaand china clay
  • storage stable composition comprises pyrazosulfuron ethyl as anactive ingredient.
  • storage stable composition comprises herbicidally effective amount of pyrazosulfuron ethyl as active ingredient.
  • storage stable composition according to the present invention comprisespyrazosulfuron ethyl in the concertation of from about 0.1% to about 25%.
  • storage stable composition comprises herbicidally effective amount of pyrazosulfuron ethyl in combination with other agrochemically active ingredient.
  • degradation of pyrazosulfuron ethyl is controlled. In another embodiment, according to the present invention, degradation of pyrazosulfuron ethyl is controlled to ⁇ 5% of pyrazosulfuron ethyl present in the composition.
  • storage stable composition of pyrazosulfuron ethyl according to the present invention comprises a stabilising system.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica and china clay.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica selected from precipitated silica and fumed silica.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 0.1% to about 10%.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 0.1% to about 7%.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay.
  • china clay of stabilising system has water holding capacity of up to 75% by weight.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of 10% to 90%.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises precipitated silica and china clay, in a ratio from aboutl:5 to about 1:30.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises precipitated silica and china clay, in a ratio from about 1:7 to about 1:20.
  • the storage stable composition of pyrazosulfuron ethyl according to the present invention comprises an agrochemically acceptable surfactant.
  • a storage stable composition comprising:
  • astabilising system comprising silica and china clay
  • the stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica selected from precipitated silica and fumed silica.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 0.1% to about 10%.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 1% to about 7%.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of from about 10% to about 90%.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of from about 50% to about 90%.
  • stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of from about 60% to about 80%.
  • agrochemically acceptable surfactant may be selected from dispersing agents, wetting agents, fillers and the like.
  • agrochemically accepted excipients may be selected from, but not limited to, following stated agrochemically accepted excipients:
  • Dispersing agents may include lignosulfonate, calcium lignin iodate, sodium lauryl polyoxyethylene ether sulfate, alkyl naphthalene condensate sulfonate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate, Alkyl polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene ether nonylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer , pull-open powder, high molecular carboxylate, sodium methylene biguanide sulfonate, polyvinyl alcohol, modified naphthalene sulfonate, polycarboxylate, alkylnaphthalene
  • Wetting agents may include alkyl sulfates, alkyl sulfonates, naphthalene sulfonates, sodium lignosulfonate, fatty alcohol polyoxyethylene ethers, alkylphenol ethoxylates, short chain EO/PO block polyethers , nonylphenol ethoxylate, nonionic ethoxylate, sodium alkyl sulfate, sodium dodecyl sulfate, TERSPERSE 2700, TERSPERSE 1004, sodium lignosulfonate, NNO, polyoxyethylene polyoxypropylene one or a combination of two or more of an ether block copolymer, an alkylphenol polyoxyethylene ether phosphate, or a water-soluble polymer compound CMC or PVA, etc. or mixtures thereof.
  • Fillers may includean organic or inorganic solid inert substance such as talc, clay, diatomaceous earth, magnesium aluminum silicate, white carbon black, pyrophyllite, light calcium carbonate, high clay, organic bentonite, etc. or mixtures thereof.
  • an organic or inorganic solid inert substance such as talc, clay, diatomaceous earth, magnesium aluminum silicate, white carbon black, pyrophyllite, light calcium carbonate, high clay, organic bentonite, etc. or mixtures thereof.
  • Surfactants may include sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, sodium alkyl sulfate, fatty alcohol sulfate, alkyl ethylsulfonate, Sodium methylnaphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether or a variety, etc. or mixtures thereof.
  • the surfactant is selected from sodium alkyl sulfate, formaldehyde condensates, sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, fatty alcohol sulfate, alkyl ethylsulfonat, Sodium methylnaphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, etc. or mixtures thereof.
  • composition is formulated as a solid composition.
  • composition is formulated as powder (WP).
  • WP powder
  • a process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and a stabilising system comprising silica and china clay, said process comprising:
  • Step-1 Pre-blending of pyrazosulfuron ethyl and stabilising system comprising silica and china clayoptionally with agrochemically acceptable excipients;
  • Step-2 Milling
  • Step-3 Post-blending and/or drying to get a composition with predefined % moisture.
  • a process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and a stabilising system comprising silica and china clay, said process comprising:
  • Step-1 Pre-blending of pyrazosulfuron ethyl and stabilising system comprising silica and china clay optionally with agrochemically acceptable excipients;
  • Step-3 Post-blending and/or drying to get a composition with predefined % moisture
  • Step-4 Formulating to a suitable form using a suitable equipment
  • step-1 the term‘stabilising system’ refers to stabilising system comprising silica and china clay, in stabilizing effective ratio.
  • the term‘agrochemically accepted excipients’ refers to additives of the composition that may be selected from dispersing agents, wetting agents, fillers, surfactants, etc.
  • agrochemically accepted excipients may be selected from, but not limited to, following stated agrochemically accepted excipients:
  • Dispersing agents may include ligno sulfonate, calcium lignin iodate, sodium lauryl polyoxyethylene ether sulfate, alkyl naphthalene condensate sulfonate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate, Alkyl polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene ether nonylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer , pull-open powder, high molecular carboxylate, sodium methylene biguanide sulfonate, polyvinyl alcohol, modified naphthalene sulfonate, polycarboxylate, alkylnaphthalene sulfonate, alkylphenol polyoxyl Vinyl ether, EO/PO block polyether, JFC, unrolled powder,
  • Wetting agents may include alkyl sulfates, alkyl sulfonates, naphthalene sulfonates, sodium lignosulfonate, fatty alcohol polyoxyethylene ethers, alkylphenol ethoxylates, short chain EO/PO block polyethers , nonylphenol ethoxylate, nonionic ethoxylate, sodium alkyl sulfate, sodium dodecyl sulfate, TERSPERSE 2700, TERSPERSE 1004, sodium lignosulfonate, NNO, polyoxyethylene polyoxypropylene one or a combination of two or more of an ether block copolymer, an alkylphenol polyoxyethylene ether phosphate, or a water-soluble polymer compound CMC or PVA, etc.
  • Fillers may include an organic or inorganic solid inert substance such as talc, clay, diatomaceous earth, magnesium aluminum silicate, white carbon black, pyrophyllite, light calcium carbonate, high clay, organic bentonite, etc. or mixtures thereof.
  • organic or inorganic solid inert substance such as talc, clay, diatomaceous earth, magnesium aluminum silicate, white carbon black, pyrophyllite, light calcium carbonate, high clay, organic bentonite, etc. or mixtures thereof.
  • Surfactants may include sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, sodium alkyl sulfate, fatty alcohol sulfate, alkyl ethylsulfonate, Sodium methylnaphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether or a variety, etc. or mixtures thereof.
  • the surfactant is selected from sodium alkyl sulfate, formaldehyde condensates, sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, fatty alcohol sulfate, alkyl ethylsulfonat, Sodium methylnaphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, etc. or mixtures thereof.
  • step-1 pre-blending is carried out in a time period of about 15 minutes to 2 hours by charging pyrazosulfuron ethyl, stabilising system comprising precipitated silica and china clay and agrochemically accepted excipients if any simultaneously.
  • step-2 provides a process for milling of pre -blended mixture of Step-1.
  • Step-2 comprises grinding of the pre-blended mixture of Step-1 at pressure 6 to 8 Kg / cm to obtain ground material with specific particle size.
  • the term‘specific particle size’ refers to D90 - less than 15 micron and/or wet sieve - 99.8 % passing through 500 BSS test.
  • step-3 provides a process for post-blending of ground pyrazosulfuron ethyl, stabilising system and agrochemically accepted excipients if any, obtained as product of step-2.
  • step-3 comprises blending of ground pyrazosulfuron ethyl, stabilising system and agrochemically accepted excipients if any, obtained as product of step-2 for a time period of about 15 min to 2 hours in order to facilitate complete homogenisation of resulting powder composition.
  • step-3 comprises drying of the blended mixture to get a product with predefined % moisture.
  • step-3 comprises drying of the blended mixture to get a product with % moisture ⁇ 2%.
  • step-3 comprises drying of the blended mixture to get a product with % moisture ⁇ 1%.
  • step-4 the process of formulating is not particularly limiting.
  • tin step-4 the composition according to the present invention is formulated in the form of powder.
  • the present invention provides a method of controlling undesired weeds, said method comprising applying to the weeds or to their locus an herbicidally effective amount of a storage stable agrochemical composition comprising:
  • astabilising system comprising silica and china clay.
  • the present invention provides a method controlling annual and perennial broad-leaved weeds and sedges, pre- or post-emergence, in wet-sown and transplanted rice crops, said method comprising applying to the weeds or to their locus an herbicidally effective amount of a storage stable agrochemical composition comprising:
  • a stabilising system comprising silica and china clay.
  • composition was prepared as follows:
  • Step-1 Pyrazosulfuron ethyl, precipitated Silica, china Clay, sodium alkyl sulphate and formaldehyde condensate were charged in required quantities in pre -blender. Blending was carried out for 20 Minutes.
  • Step-2 The pre-blended material was ground to desired particle size under grinding pressure
  • Step-3 Post-Blending: The ground material was blended in post blender for 15 min to achieve complete homogenization and dried to get the product having a moisture content ⁇ 1%.
  • compositions according to the present invention are listed in the below table (Example 2 and 3)
  • Comparative example (Example 4) A comparative composition of pyrazosulfuron ethyl was prepared as follows:
  • Example 1-3 demonstrates inventions according to the present invention.
  • Example 4 is a comparative example in which stabilizing system according to the invention is absent. Zero timedata was generated for all the samples. Studied were conducted by keeping the samples at 54 ° C for 14 days and 28 days. The results indicate that the stabilization system according to the present invention provides significant chemical stability to pyrazosulfuron ethyl in the composition.

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Abstract

The present invention provides a stabilizing system for preparing stable herbicide formulation comprising pyrazosulfuron ethyl.

Description

STABLE HERBICIDE FORMULATION OF PYRAZOSULFURON ETHYL
FIELD OF INVENTION
The present invention relates to a stable herbicide formulation comprising pyrazosulfuron ethyl. The present invention also relates to a stabilising system for formulation comprising pyrazosulfuron ethyl and method of preparation the formulation.
BACKGROUND OF THE INVENTION
Pyrazosulfuron ethyl is a pyrimidinylsulfonylurea herbicide having IUPAC name 5-[(4,6 dimethoxypyrimidin-2-ylcarbamoyl) sulfamoyl]-l -methyl pyrazole-4-carboxylic acid and chemical structure as follows:
Figure imgf000002_0001
Pyrazosulfuron ethylis a systemic herbicide used to control annual and perennial broad-leaved weeds and sedges, pre- or post-emergence, wet sown and transplanted rice crops.
Various agrochemical compositions comprising pyrazosulfuron ethyl as active ingredient are available in the market, but they are known to be degrading during the shelf life of the product. The degradation of the active ingredient is not suitable for formulation and will result in ineffective dose application when applied in the field thus resulting in poor control of weeds.
Hence, there is an urgent and unmet need of the stable formulation comprising pyrazosulfuron ethyl which is stable prevent degradation during its shelf life.
OBJECT OF THE INVENTION
It is an object of the present invention to provide a storage stable composition comprising pyrazosulfuron ethyl. It is another object of the present invention to provide a process for preparing a storage stable composition comprising pyrazosulfuron ethyl.
It is an object of the present invention to to provide a stable composition comprising pyrazosulfuron ethyl that does not undergo degradation.
SUMMARY OF INVENTION
In an aspect the present invention provides a storage stable agrochemical composition comprising:
a) pyrazosulfuron ethyl; and
b) astabilising system comprising silicaand china clay
In another aspect the present invention provides a process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and a stabilising system comprising silica and china clay, said process comprising:
Step-1: Pre-blending of pyrazosulfuron ethyl and stabilising system comprising silica and china clay optionally with agrochemically acceptable excipients;
Step-2: Milling; and
Step-3: Post-blending and/or drying to get a compositionwith predefined % moisture.
In another aspect the present invention provides a method of controlling undesired weeds, said method comprising applying to the weeds or to their locus an herbicidally effective amount of astorage stable agrochemical composition according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides an agrochemical composition and in particular a storage stable agrochemical composition.
It is surprising to found that a stabilising system comprising silica and china clay, helps to increase shelf life of the product comprising pyrazosulfuron ethyl of formula- 1. Formua-1:
Figure imgf000004_0001
Surprisingly the present inventors found a stabilizing system which is effective in increasing stability and shelf life of agrochemical compositions comprising pyrazosulfuron ethyl.
In an embodiment there is provided a storage stable composition comprising:
a) pyrazosulfuron ethyl; and
b) astabilising system comprising silicaand china clay.
In another embodiment the storage stable compositions according to the present invention further comprises other agrochemically acceptable surfactants.
Thus, in an embodiment there is provided a storage stable composition comprising:
a) pyrazosulfuron ethyl;
b) astabilising system comprising silicaand china clay; and
c) optionally an agrochemically acceptable surfactant.
In an embodiment storage stable composition comprises pyrazosulfuron ethyl as anactive ingredient.
In another embodiment storage stable composition comprises herbicidally effective amount of pyrazosulfuron ethyl as active ingredient.
In another embodiment storage stable composition according to the present invention comprisespyrazosulfuron ethyl in the concertation of from about 0.1% to about 25%.
In another embodiment storage stable composition comprises herbicidally effective amount of pyrazosulfuron ethyl in combination with other agrochemically active ingredient.
In another embodiment, according to the present invention, degradation of pyrazosulfuron ethyl is controlled. In another embodiment, according to the present invention, degradation of pyrazosulfuron ethyl is controlled to <5% of pyrazosulfuron ethyl present in the composition.
In an embodiment storage stable composition of pyrazosulfuron ethyl according to the present invention comprises a stabilising system.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl according to the present invention comprises silica and china clay.
In another embodiment, stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica selected from precipitated silica and fumed silica.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 0.1% to about 10%.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 0.1% to about 7%.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay.
In an embodiment china clay of stabilising system has water holding capacity of up to 75% by weight.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of 10% to 90%.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises precipitated silica and china clay, in a ratio from aboutl:5 to about 1:30.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises precipitated silica and china clay, in a ratio from about 1:7 to about 1:20. In an embodiment, the storage stable composition of pyrazosulfuron ethyl according to the present invention comprises an agrochemically acceptable surfactant.
Thus, in an embodiment, there is provided a storage stable composition comprising:
a) pyrazosulfuron ethyl;
b) astabilising system comprising silica and china clay; and
c) an agrochemically acceptable surfactant.
In an embodiment, the stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica selected from precipitated silica and fumed silica.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 0.1% to about 10%.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises silica in the concertation of from about 1% to about 7%.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of from about 10% to about 90%.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of from about 50% to about 90%.
In another embodiment stabilising system of storage stable composition of pyrazosulfuron ethyl comprises china clay in the concertation of from about 60% to about 80%.
In an embodiment of the present invention, agrochemically acceptable surfactant may be selected from dispersing agents, wetting agents, fillers and the like.
In stated embodiment, agrochemically accepted excipients may be selected from, but not limited to, following stated agrochemically accepted excipients: Dispersing agents may include lignosulfonate, calcium lignin iodate, sodium lauryl polyoxyethylene ether sulfate, alkyl naphthalene condensate sulfonate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate, Alkyl polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene ether nonylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer , pull-open powder, high molecular carboxylate, sodium methylene biguanide sulfonate, polyvinyl alcohol, modified naphthalene sulfonate, polycarboxylate, alkylnaphthalene sulfonate, alkylphenol polyoxyl Vinyl ether, EO/PO block polyether, JFC, unrolled powder, nonylphenol ethoxylate, octylphenol polyoxyethylene sulfate, fatty alcohol sulfate, alkylnaphthalene sulfonate, fatty amide N- Methanesulfonate, fatty alcohol sodium polyoxyethylene sulfate, fatty acid sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylbenzyldimethylammonium chloride, alkylamine oxide, etc. or mixture thereof.
Wetting agents may include alkyl sulfates, alkyl sulfonates, naphthalene sulfonates, sodium lignosulfonate, fatty alcohol polyoxyethylene ethers, alkylphenol ethoxylates, short chain EO/PO block polyethers , nonylphenol ethoxylate, nonionic ethoxylate, sodium alkyl sulfate, sodium dodecyl sulfate, TERSPERSE 2700, TERSPERSE 1004, sodium lignosulfonate, NNO, polyoxyethylene polyoxypropylene one or a combination of two or more of an ether block copolymer, an alkylphenol polyoxyethylene ether phosphate, or a water-soluble polymer compound CMC or PVA, etc. or mixtures thereof.
Fillers may includean organic or inorganic solid inert substance such as talc, clay, diatomaceous earth, magnesium aluminum silicate, white carbon black, pyrophyllite, light calcium carbonate, high clay, organic bentonite, etc. or mixtures thereof.
Surfactants may include sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, sodium alkyl sulfate, fatty alcohol sulfate, alkyl ethylsulfonate, Sodium methylnaphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether or a variety, etc. or mixtures thereof.
In another embodiment the surfactant is selected from sodium alkyl sulfate, formaldehyde condensates, sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, fatty alcohol sulfate, alkyl ethylsulfonat, Sodium methylnaphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, etc. or mixtures thereof.
In another embodiment there is provided a process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and astabilising system comprising silica and china clay.
In an embodiment the composition is formulated as a solid composition.
In a preferred embodiment the composition is formulated as powder (WP). llnan embodiment there is provided a process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and a stabilising system comprising silica and china clay, said process comprising:
Step-1: Pre-blending of pyrazosulfuron ethyl and stabilising system comprising silica and china clayoptionally with agrochemically acceptable excipients;
Step-2: Milling; and
Step-3: Post-blending and/or drying to get a composition with predefined % moisture.
In another embodiment there is provided a process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and a stabilising system comprising silica and china clay, said process comprising:
Step-1: Pre-blending of pyrazosulfuron ethyl and stabilising system comprising silica and china clay optionally with agrochemically acceptable excipients;
Step-2: Milling;
Step-3: Post-blending and/or drying to get a composition with predefined % moisture; and Step-4: Formulating to a suitable form using a suitable equipment
In above stated embodiment, in step-1, the term‘stabilising system’ refers to stabilising system comprising silica and china clay, in stabilizing effective ratio.
In above stated embodiment, in step-1, the term‘agrochemically accepted excipients’ refers to additives of the composition that may be selected from dispersing agents, wetting agents, fillers, surfactants, etc.
In above stated embodiment, in step-1, agrochemically accepted excipients may be selected from, but not limited to, following stated agrochemically accepted excipients:
Dispersing agents may include ligno sulfonate, calcium lignin iodate, sodium lauryl polyoxyethylene ether sulfate, alkyl naphthalene condensate sulfonate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate, Alkyl polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene ether nonylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer , pull-open powder, high molecular carboxylate, sodium methylene biguanide sulfonate, polyvinyl alcohol, modified naphthalene sulfonate, polycarboxylate, alkylnaphthalene sulfonate, alkylphenol polyoxyl Vinyl ether, EO/PO block polyether, JFC, unrolled powder, nonylphenol ethoxylate, octylphenol polyoxyethylene sulfate, fatty alcohol sulfate, alkylnaphthalene sulfonate, fatty amide N- Methanesulfonate, fatty alcohol sodium polyoxyethylene sulfate, fatty acid sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylbenzyldimethylammonium chloride, alkylamine oxide, etc. or mixture thereof.
Wetting agents may include alkyl sulfates, alkyl sulfonates, naphthalene sulfonates, sodium lignosulfonate, fatty alcohol polyoxyethylene ethers, alkylphenol ethoxylates, short chain EO/PO block polyethers , nonylphenol ethoxylate, nonionic ethoxylate, sodium alkyl sulfate, sodium dodecyl sulfate, TERSPERSE 2700, TERSPERSE 1004, sodium lignosulfonate, NNO, polyoxyethylene polyoxypropylene one or a combination of two or more of an ether block copolymer, an alkylphenol polyoxyethylene ether phosphate, or a water-soluble polymer compound CMC or PVA, etc. or mixtures thereof. Fillers may include an organic or inorganic solid inert substance such as talc, clay, diatomaceous earth, magnesium aluminum silicate, white carbon black, pyrophyllite, light calcium carbonate, high clay, organic bentonite, etc. or mixtures thereof.
Surfactants may include sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, sodium alkyl sulfate, fatty alcohol sulfate, alkyl ethylsulfonate, Sodium methylnaphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether or a variety, etc. or mixtures thereof.
In another embodiment the surfactant is selected from sodium alkyl sulfate, formaldehyde condensates, sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, fatty alcohol sulfate, alkyl ethylsulfonat, Sodium methylnaphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylic acid, lignosulfonate, alkylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, etc. or mixtures thereof.
In yet another embodiment, in step-1, pre-blending is carried out in a time period of about 15 minutes to 2 hours by charging pyrazosulfuron ethyl, stabilising system comprising precipitated silica and china clay and agrochemically accepted excipients if any simultaneously.
In anembodiment, step-2 provides a process for milling of pre -blended mixture of Step-1.
In another embodiment, Step-2 comprises grinding of the pre-blended mixture of Step-1 at pressure 6 to 8 Kg / cm to obtain ground material with specific particle size.
In the present invention, the term‘specific particle size’ refers to D90 - less than 15 micron and/or wet sieve - 99.8 % passing through 500 BSS test.
In another embodiment, step-3 provides a process for post-blending of ground pyrazosulfuron ethyl, stabilising system and agrochemically accepted excipients if any, obtained as product of step-2. In another embodiment, step-3 comprises blending of ground pyrazosulfuron ethyl, stabilising system and agrochemically accepted excipients if any, obtained as product of step-2 for a time period of about 15 min to 2 hours in order to facilitate complete homogenisation of resulting powder composition.
In another embodiment, step-3 comprises drying of the blended mixture to get a product with predefined % moisture.
In another embodiment, step-3 comprises drying of the blended mixture to get a product with % moisture <2%.
In a preferred embodiment, step-3 comprises drying of the blended mixture to get a product with % moisture <1%.
In another embodiment, in step-4, the process of formulating is not particularly limiting.
In a preferred embodiment tin step-4 the composition according to the present invention is formulated in the form of powder.
The present invention provides a method of controlling undesired weeds, said method comprising applying to the weeds or to their locus an herbicidally effective amount of a storage stable agrochemical composition comprising:
a) Pyrazosulfuron ethyl; and
b) astabilising system comprising silica and china clay.
In an embodiment, the present invention provides a method controlling annual and perennial broad-leaved weeds and sedges, pre- or post-emergence, in wet-sown and transplanted rice crops, said method comprising applying to the weeds or to their locus an herbicidally effective amount of a storage stable agrochemical composition comprising:
a) Pyrazosulfuron ethyl; and
b) a stabilising system comprising silica and china clay.
The invention will now be described further by reference to the following examples, which are intended to illustrate, but not limit, the scope of the appended claims. Example 1
Exemplary composition was prepared as follows:
Figure imgf000012_0001
Process conditions:
Step-1 (Pre-Blending): Pyrazosulfuron ethyl, precipitated Silica, china Clay, sodium alkyl sulphate and formaldehyde condensate were charged in required quantities in pre -blender. Blending was carried out for 20 Minutes.
Step-2 (Milling): The pre-blended material was ground to desired particle size under grinding pressure
Step-3 (Post-Blending): The ground material was blended in post blender for 15 min to achieve complete homogenization and dried to get the product having a moisture content < 1%.
The stability results of the exemplary composition prepared according to above formula are:
Figure imgf000012_0002
Figure imgf000013_0001
*(material passing through 75-micron test Sieve) (% w/w) % Degradationofpyrazosulfuron ethyl:
Figure imgf000013_0002
Compositions according to the present invention are listed in the below table (Example 2 and 3)
Figure imgf000013_0003
% Degradation of pyrazosulfuron ethyl:
Figure imgf000013_0004
Comparative example (Example 4): A comparative composition of pyrazosulfuron ethyl was prepared as follows:
Figure imgf000013_0005
Figure imgf000014_0001
% Degradation of pyrazosulfuron ethyl:
Figure imgf000014_0002
Example 1-3 demonstrates inventions according to the present invention. Example 4 is a comparative example in which stabilizing system according to the invention is absent. Zero timedata was generated for all the samples. Studied were conducted by keeping the samples at 54°C for 14 days and 28 days. The results indicate that the stabilization system according to the present invention provides significant chemical stability to pyrazosulfuron ethyl in the composition.

Claims

We Claim:
1. A storage stable agrochemical composition comprising:
a) pyrazosulfuron ethyl; and
b) astabilising system comprising silicaand china clay
2. A composition according to claim 1 wherein said pyrazosulfuron ethylis present in an amount from about 0.1% to about 25%by weight of the composition
3. A composition according to claim 1 wherein said silica is selected from precipitated silica and fumed silica
4. A composition according to claim 1 wherein said silica ispresent in an amount from about 0.1% to about 10% by weight of the composition.
5. A composition according to claim 1 wherein said china clay is present in an amount from about 10% to about 90% by weight of the composition.
6. A composition according to claim 1 wherein ratio of said precipitated silica and china clay varies from about 1:5 to about 1:30.
7. A composition according to claim 1 wherein degradation of pyrazosulfuron ethyl is controlled to <5% of pyrazosulfuron ethyl present in the composition
8. A process for preparation of storage stable composition comprising herbicidally effective amount of pyrazosulfuron ethyl and a stabilising system comprising silica and china clay, said process comprising:
Step-1: Pre-blending of pyrazosulfuron ethyl and stabilising system comprising silica and china clay optionally with agrochemically acceptable excipients;
Step-2: Milling;
Step-3: Post-blending and/or drying to get a composition with predefined % moisture; and
Step-4: Formulating to a suitable form using a suitable equipment
9. A process of claim 8 wherein said process provides said composition having a % moisture <2%.
10. A process of claim 8 wherein said process provides said composition in the form of powder.
1. A method of controlling undesired weeds, said method comprising applying to the weeds or to their locus an herbicidally effective amount of a storage stable agrochemical composition comprising:
a) Pyrazosulfuron ethyl; and
b) a stabilising system comprising silica and china clay.
PCT/IB2020/052677 2019-03-27 2020-03-23 Stable herbicide formulation of pyrazosulfuron ethyl Ceased WO2020194164A1 (en)

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