WO2011003240A1 - Préparation comprenant un terpolymère et une substance active et procédé de préparation associé - Google Patents

Préparation comprenant un terpolymère et une substance active et procédé de préparation associé Download PDF

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Publication number
WO2011003240A1
WO2011003240A1 PCT/CN2009/072723 CN2009072723W WO2011003240A1 WO 2011003240 A1 WO2011003240 A1 WO 2011003240A1 CN 2009072723 W CN2009072723 W CN 2009072723W WO 2011003240 A1 WO2011003240 A1 WO 2011003240A1
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WIPO (PCT)
Prior art keywords
active substance
formulation
terpolymer
formulation according
monomer
Prior art date
Application number
PCT/CN2009/072723
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English (en)
Inventor
Qi Wu
Weidong He
Jing Dreher
Uwe Kardorff
Guangzhao Zhang
Original Assignee
Basf (China) Company Limited
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf (China) Company Limited, Basf Se filed Critical Basf (China) Company Limited
Priority to PCT/CN2009/072723 priority Critical patent/WO2011003240A1/fr
Priority to PCT/EP2010/059767 priority patent/WO2011003961A2/fr
Publication of WO2011003240A1 publication Critical patent/WO2011003240A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • 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
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N25/26—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 in coated particulate form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen

Definitions

  • the present invention relates to a type of formulations comprising a terpolymer and an active substance, preparation thereof, and the use thereof in the preparation of ready-for-use formulations.
  • active substances are ideally used as aqueous formulations (mainly as aqueous solutions or aqueous dispersions) in various fields.
  • active substances such as insecticides, acaricides, nematicides, fungicides and herbicides as well as growth regulators are frequently formulated and sold as concentrates, such as aqueous concentrates or as concentrates in organic solvent, for example suspensions or emulsions, and also as solid concentrates, such as powders, dusts or granules.
  • concentrates such as aqueous concentrates or as concentrates in organic solvent, for example suspensions or emulsions, and also as solid concentrates, such as powders, dusts or granules.
  • pharmaceutically and cosmetically active substances and food additives as well as active substances used in biological field, such as vitamins, provitamins, proteins, RNA and DNA and the like, are also generally formulated into formulations in aqueous medium for transportation and/or usage.
  • active substances used in biological field such as vitamins, provitamins, proteins, RNA and DNA and the like.
  • the main problems are that, many active substances have low solubility, i.e., generally less than 10 g/1 at 23°C/1 atm. (1013 mbar).
  • these active substances When these active substances are formulated into aqueous formulations or aqueous ready-for-use formulations, they form unstable heterogeneous systems in which the active substance is present as emulsified or dispersed phase in a continuous aqueous phase.
  • the active substances tend to separate out of the system, for example by crystallization or creaming or sedimentation. This reduces the availability of the active substance, resulting in low utilization of the active substance.
  • WO2008/040786 disclosed a comb-copolymer, and the use of the comb-copolymer in stabilizing the aqueous phase that contains an insoluble or slightly soluble active substance, to obtain a stable aqueous formulation.
  • the comb-copolymer is used as dispersant for dispersing and stabilizing the active substances that have been divided into small size, in water.
  • the present invention solved the problems in the prior art by synthesizing a terpolymer and preparing a formulation based on the visco-elastic behavior of the macromolecule.
  • the inventive terpolymer there is a strong interaction between the inventive terpolymer and the active substance, thus for a given amount of formulation of the present invention, the loading level of the active substance can be substantively increased.
  • the introduction of hydrophilic component in the terpolymer can shorten the interaction time among dispersed microparticles. More importantly, the introduction of hydrophobic component and a proper chain extension, not only the formation of the dispersed microparticles is induced and promoted, but also the relaxation time of the chains inside each microparticle is prolonged.
  • the dispersion state of the formulations can be adjusted when the formulation is diluted with substantive amount of water.
  • the relaxation time of the chains inside the dispersed phase can be made much longer than the interaction time between the dispersed phases. In other words, within the relatively shorter interaction time, the dispersed phase is in glassy state which prevents aggregation, and thus enables the formation of a stable formulation system.
  • the formulations can be prepared with simple procedures and easy to apply.
  • the invention relates to a formulation comprising terpolymer and active substance (D), said terpolymer comprises main chain segment (A), hydrophobic pendent chains (B), and hydrophilic pendent chains (C).
  • the formulation according to the invention is described as comprises core-shell particles formed by the terpolymer and the active substances (D), wherein the hydrophilic pendent chains (C) forms said shell, the hydrophobic pendent chains (B) forms said core, and said main chain segment (A) of the terpolymer combines with said active substance (D), and said active substance (D) is encapsulated between said core and said shell.
  • the invention is not to be limited by this description.
  • the said core-shell structure is only provided for the convenience of describing and understanding the invention, not for limiting the invention in any way.
  • Structure of the inventive terpolymer comprises main chain segment (A), hydrophobic pendent chains (B) and hydrophilic pendent chains (C).
  • the main chain segment (A) can be either hydrophobic or hydrophilic, depending on the condition.
  • the molecular weight of the inventive terpolymer is at least 100,000 g/mol, preferably at least 150,000 g/mol, more preferably at least 200,000 g/mol, and at most 4,000,000 g/mol, preferably at most 3,000,000 g/mol, more preferably at most 2,000,000 g/mol, most preferably at most 1,000,000 g/mol. In a preferred embodiment of the invention, the molecular weight of the inventive terpolymer is l,300,000g/mol.
  • the main chain segment (A) interacts with the active substance (D) to weaken the aggregation tendency of the active substance (D), in particular the tendency of separating, crystallizing, flocculating or precipitating out of the system, so as to enables the formation of stable formulations.
  • an environment sensitive component is used as the main chain segment (A), i.e., the main chain segment (A) will change its property (such as being hydrophilic or hydrophobic) under different conditions (such as changing in temperature and pH value).
  • the main chain segment (A) of the terpolymer which is formed with monomer (a) is hydrophobic under low pH conditions and may combine with the active substance (D), while being hydrophilic at high pH conditions and may release the active substance (D).
  • This property of main chain segment (A) will help encapsulating said active substance (D) in the stable formulations under certain conditions, while releasing the active substance from the stable formulation under other conditions.
  • said main chain segment (A) is derived from monomer (a)
  • said hydrophobic pendent chain (B) is derived from monomer (b)
  • said hydrophilic pendent chain (C) is derived from monomer (c).
  • monomers (a), (b) and (c) are copolymerized to form the inventive terpolymer.
  • the functional groups contained in monomer (a) will constitute the main chain segment (A) which in turn will complex with the active substance (D), while monomers (b) and (c) copolymerized into the main chain segment (A), and the groups contained in monomers (b) and (c) form the pendent chain (B) and (C) respectively.
  • pendent chains (B) and (C) are attached to the main chain segment (A) during the formation of the main chain segment (A).
  • Monomer (a) that contributes to the formation of the main chain segment (A) can be a member selected from the group consisting of (meth)acrylic acids, vinyl benzene sulfonic acid, vinyl pyridine, and N-isopropyl acrylamide, and the like.
  • Monomer (b) that contributes to the formation of the hydrophobic pendent chain (B) can be for example a hydrophobic vinyl monomer, such as alkyl (meth)acrylate, styrene and/or vinyl acetate.
  • alkyl (meth)acrylate When alkyl (meth)acrylate is used as monomer (b), the number of the carbon atom in the alkyl group is at least 8, preferably at least 10, more preferably at least 12, and at most 30, preferably at most 24, more preferably at most 20, and most preferably 18.
  • Monomer (c) that contributes to the formation of the hydrophobic pendent chain (C) can be a member selected from the group consisting of for example (polyethylene glycol monomethylether) acrylate (i.e., PEG acrylate), acrylamide, vinylpyrrolidone, and N,N-dimethylacrylamide.
  • the molecular weight of the PEG is at least 500g/mol, preferably at least lOOOg/mol, and up to 8000g/mol, preferably up to lOOOOg/mol.
  • the term "terpolymer” according to the invention does not exclude the presence of a small amount of other structures such as other hydrophobic pendent chains other than the hydrophobic pendent chain (B).
  • said other hydrophobic pendent chains is the ones that are derived from di(meth)acrylates.
  • the terpolymer of the present invention can be illustrated as following.
  • hydrophobic pendent chain (B) and the hydrophobic pendent chain (C) constitute the chain of the terpolymer together with the main chain segment (A).
  • the ratios between main chain segment (A), the hydrophobic pendent chain (B) and the hydrophilic pendent chain (C) influence the formation of hydrophobic core structure and hydrophilic shell structure as well as the loading of active substance (D) in said core-shell structure.
  • the amount of the main chain segment (A) is 17-60% by weight
  • the amount of the hydrophobic pendent chain (B) is 20-56% by weight
  • the amount of the hydrophilic pendent chain (C) is 20-40% by weight, all based on the total weight of the terpolymer.
  • a di(meth)acrylate can be further added as a comonomer, such as ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or polyethylene glycol di(meth)acrylate.
  • the structural unit of monomer (b) is randomly distributed along the main chain of the terpolymer.
  • each of the structural unit has a hydrocarbon type pendent chain of preferably more than 12 carbon atoms, more preferably each of the structural unit has a hydrocarbon type pendent chain of 12 -24 carbon atoms, more preferably 18 carbon atoms.
  • Active substances in the sense of the present invention are defined as substances that can manifest a particular activity or function or reactive under particular circumstance.
  • the terms "active substance” and “effect substance” are used interchangeably and are synonymous in the context of this patent application.
  • suitable active substance include small molecule active substance such as insecticides, acaricides, nematicides, fungicides and herbicides and growth regulators, and high molecular weight active substance such as proteins, RNA and DNA.
  • the inventive terpolymer can also be used to disperse and stabilize functional inorganic compounds, such as quantum-dots, as well as magnetic, light-emitting and catalytic substances, into polymeric core-shell particles.
  • slightly soluble means a solubility of the active substance in water of less than 10 g/1, usually of less than 5 g/1 and in particular of less than 1 g/1 and especially of less than 0.1 g/1, at 25 0 C and 1 atm (1013 mbar).
  • the interaction between the main chain segment (A) and the active substance (D) is strong that hinders the aggregation tendency of the active substance (D).
  • Examples of such interaction include hydrogen bond, charge interaction, hydrophobicity interaction, etc.
  • the particle with core-shell structure formed according to the invention has the particle size and particle size distribution of from hundreds nanometers to tens of microns, more frequently from hundreds nanometers to several microns.
  • Loading of active substance (D) in the formulation according to the invention can be up to about 350% by weight based on the polymer used, and up to about 200mg/ml based on the solvent used.
  • Another aspect of the present invention relates to a process for the preparation of the inventive formulation.
  • said process include the steps of:
  • the appearance of the obtained formulation can be clear and transparent, or can be a milky colloid.
  • reaction type involved in above process is not critical to the implementation of the present invention. They can be any of commonly known reaction type, such as radical polymerization.
  • reaction temperature can be determined by those skilled in the art.
  • the lower limit of the reaction temperature used in polymerization is O 0 C, preferably 2O 0 C, more preferable 3O 0 C, while the upper limit is 100 0 C, preferably 8O 0 C, more preferably 7O 0 C, particular preferably 6O 0 C.
  • Solvent used in the process of the present invention is important for the implementation of the present invention.
  • Said solvent must be able to dissolve all the reactant involved in the reactions and active substance (D), and essentially inert to the reactions.
  • Said solvent preferably comprises ester of lower aliphatic carboxylic acid with lower aliphatic alcohol, such as ethyl acetate and butyl acetate.
  • pH vale of inventive formulation is preferably from about 1 to about 5.
  • Molar ratio of monomer (a) : monomer (b) : monomer (c) : active substance (D) in step a2) can be determined by a skilled person through experiments.
  • stably dispersed inventive formulation could be obtained directly.
  • the formulation can be readily used after dilution 50-100 times with water.
  • the present invention also relates to a process for the preparation of a ready-for-use formulation comprising the inventive formulation, said process including the step of mixing the inventive formulation with water, preferably 50-100 times of water.
  • Epoxiconazole (EP), PEG acrylate, methacrylic acid (MAA), octodecyl acrylate (ODA) and azo-bis-isobutyronitrile (AIBN) were added into ethyl acetate (30 mL) according to the concentration as shown in Table 1 respectively, and homogenized with agitation. After that, a small amount of ethylene dimethacrylate (EDMA) was added to the polymerization mixture and the copolymerization was performed at 60 0 C under nitrogen atmosphere for 24 h. The procedure was repeated five times with the changing of the amount of epoxiconazole (EP) to obtain five test samples 1-5 of the formulation. Table 1 shows the visual appearance of the formulation after polymerization.
  • EDMA ethylene dimethacrylate
  • a formulation with 66.7 g/1 epoxiconazole is obtainable from the polymerization of methacrylic acid (8.3 g/1), octodecyl acrylate (16.7 g/1), PEG acrylate (8.3 g/1) and a small amount of ethylene dimethacrylate (0.5 g/ml) in ethyl acetate.
  • the formulation is a emulation and has no precipitate over 2 hours. After latex particles separated out, the system was in a homogeneous state with slight stirring.
  • **A formulation with 166.7 g/1 epoxiconazole is obtainable from the polymerization of methacrylic acid (26.7 g/1), octodecyl acrylate (16.7 g/1), PEG acrylate (8.3 g/1) and a small amount of ethylene dimethacrylate (0.6 g/ml) in ethyl acetate.
  • the formulation has no aggregrative particle.
  • Epoxiconazole (EP), PEG acrylate, methacrylic acid (MAA), octodecyl acrylate (ODA) and azo-bis-isobutyronitrile (AIBN) were added into ethyl acetate (20 ml) according to the concentration as shown in Table 2, and homogenized with agitation. The reaction was performed at 60 0 C under nitrogen atmosphere for 24 h. The procedure was repeated five times with the changing of the amount of MAA to obtain five test samples 1-5 of the formulation. Table 2 shows the visual appearance of the formulation after polymerization.
  • Sample A, sample B and sample C are obtained from Test 6, Test 9 and Test 8 in Table 2, respectively.
  • Sample A-I, sample B-I and sample C-I are the mixture prepared by the re-dispersion of sample A, sample B and sample C in water, respectively.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Cosmetics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne une préparation comprenant un terpolymère et une substance active et le procédé de production associé. Ledit terpolymère comprend 17 à 60 % en poids de segment de chaîne principale, 20 à 56 % en poids de chaînes pendantes hydrophobes, et 20 à 40 % en poids de chaînes pendantes hydrophiles, sur la base du poids total du terpolymère. Le segment de chaîne principale est formé à partir du monomère qui est choisi parmi l’acide (méth)acrylique, l’acide vinyl benzène sulfonique ou le N-isopropyl acrylamide. La chaîne pendante hydrophobe est dérivée du vinyle hydrophobe, comme le (méth)acrylate d’alkyle, le styrène et/ou l’acétate de vinyle. La chaîne pendante hydrophile est dérivée du monomère qui est choisi parmi le (polyéthylène glycol monométhyléther) acrylate, l’acrylamide, le vinylpyrrolidone, ou le N,N-diméthylacrylamide.
PCT/CN2009/072723 2009-07-10 2009-07-10 Préparation comprenant un terpolymère et une substance active et procédé de préparation associé WO2011003240A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2009/072723 WO2011003240A1 (fr) 2009-07-10 2009-07-10 Préparation comprenant un terpolymère et une substance active et procédé de préparation associé
PCT/EP2010/059767 WO2011003961A2 (fr) 2009-07-10 2010-07-08 Formulations comprenant un terpolymère et une substance active, leur préparation et leur utilisation

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Application Number Priority Date Filing Date Title
PCT/CN2009/072723 WO2011003240A1 (fr) 2009-07-10 2009-07-10 Préparation comprenant un terpolymère et une substance active et procédé de préparation associé

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WO2011003240A1 true WO2011003240A1 (fr) 2011-01-13

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PCT/EP2010/059767 WO2011003961A2 (fr) 2009-07-10 2010-07-08 Formulations comprenant un terpolymère et une substance active, leur préparation et leur utilisation

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Cited By (2)

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WO2013149856A1 (fr) * 2012-04-04 2013-10-10 Basf Se Formulation agricole comprenant un copolymère d'un amide, de polyalkylène glycol (meth)acrylate et d'alkyl (meth)acrylate
WO2013149925A1 (fr) * 2012-04-04 2013-10-10 Basf Se Formulation agronomique comprenant un copolymère de vinyllactame, n-alkylacrylamide et (méth)acrylate d'alkyle

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US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013149856A1 (fr) * 2012-04-04 2013-10-10 Basf Se Formulation agricole comprenant un copolymère d'un amide, de polyalkylène glycol (meth)acrylate et d'alkyl (meth)acrylate
WO2013149925A1 (fr) * 2012-04-04 2013-10-10 Basf Se Formulation agronomique comprenant un copolymère de vinyllactame, n-alkylacrylamide et (méth)acrylate d'alkyle
CN104202975A (zh) * 2012-04-04 2014-12-10 巴斯夫欧洲公司 包含酰胺、聚亚烷基二醇(甲基)丙烯酸酯和(甲基)丙烯酸烷基酯的共聚物的农业配制剂
CN104202978A (zh) * 2012-04-04 2014-12-10 巴斯夫欧洲公司 包含乙烯基内酰胺、n-烷基丙烯酰胺和(甲基)丙烯酸烷基酯的共聚物的农业配制剂
CN104202978B (zh) * 2012-04-04 2016-06-22 巴斯夫欧洲公司 包含乙烯基内酰胺、n-烷基丙烯酰胺和(甲基)丙烯酸烷基酯的共聚物的农业配制剂
CN104202975B (zh) * 2012-04-04 2016-08-24 巴斯夫欧洲公司 包含酰胺、聚亚烷基二醇(甲基)丙烯酸酯和(甲基)丙烯酸烷基酯的共聚物的农业配制剂
US9700048B2 (en) 2012-04-04 2017-07-11 Basf Se Agroformulation comprising copolymer of vinyllactam, N-alkyl acrylamide, and alkyl (meth)acrylate
EA032035B1 (ru) * 2012-04-04 2019-03-29 Басф Се Пестицидная композиция, содержащая сополимер амида, (мет)акрилата полиалкиленгликоля и алкил(мет)акрилата, способ ее получения, способы борьбы с фитопатогенными грибами, нежелательным ростом растений и нашествием насекомых или клещей, способ регулирования роста растений и семена, обработанные композицией

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