Composition

Abstract

An agrochemical composition comprising: a copolymer consisting of two monomers represented by the formula wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomer wherein R1 is selected from hydrogen or methyl; r2 is a C1-6 alkyl group; r3 is selected from hydrogen or methyl; r4 is selected from:-CONHm (C1-C6 alkyl) n (wherein m = 0, 1 or 2, n = 0, 1 or 2),-C5 heterocyclic ketone,-C (O) O (CH2CH2O) pH (wherein p = 1 to 50),-C (O) O (CH2CH2O) pR5 (wherein p = 1 to 20 and wherein R5 is C1-6 alkyl).

Description

[0001] This invention relates to compositions comprising copolymers, methods for their preparation, and uses thereof.

[0002] Solvent-based agrochemical formulations, such as dispersible concentrates (DC) and emulsifiable concentrates (EC), are attractive for several reasons. These formulations are homogeneous and therefore do not require anti-settling agents. Furthermore, solvent-based formulations typically do not require antifreeze or antimicrobial agents.

[0003] DC and EC formulations are very similar; both contain the active ingredient and a suitable surfactant, both dissolved in a non-aqueous solvent. For EC formulations, the solvent must be immiscible with water, meaning that upon dilution in water, these concentrates form a spontaneous emulsion. For DC formulations, the solvent must be miscible with water, meaning that upon dilution in water, these concentrates form a spontaneous dispersion of the active ingredient (AI) particles in water.

[0004] One particular issue associated with both solvent-based DC and EC formulations is the potential for uncontrolled crystal growth upon dilution in water. This is undesirable, as such crystals can interfere with agricultural equipment by clogging nozzles.

[0005] Conventional copolymer dispersants used to address crystal growth are ineffective at solving this problem, and carboxylic acid-based dispersants can exhibit sensitivity to pH levels.

[0006] To address these problems, the present invention therefore provides an agricultural chemical composition comprising:

[0007] A copolymer composed of two monomers represented by the following formula, wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomer:

[0008]

[0009] in

[0010] R 1 Selected from hydrogen or methyl;

[0011] R 2 It is C 1-6 alkyl,

[0012] R 3 Selected from hydrogen or methyl;

[0013] R 4 Selected from:

[0014] -CONH m (C 1-6 alkyl) n Where m = 0, 1, or 2, and n = 0, 1, or 2.

[0015] -C5 heterocyclic ketone

[0016] -C(O)O(CH2CH2O) p H, where p = 1 to 50, and

[0017] -C(O)O(CH2CH2O) p R 5 , where p = 1 to 20 and where R 5 It is C 1-6 alkyl.

[0018] Surprisingly, copolymers defined in this way have been found to reduce crystal growth in agrochemical formulations.

[0019] The terms “copolymer” and “polymer” are used interchangeably in this document.

[0020] The copolymer is advantageously a random copolymer.

[0021] polymer

[0022] R 2 It can be selected from methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), isobutyl (i-Bu), sec-butyl, and tert-butyl (t-Bu). More preferably, R 2 Derived from methyl or ethyl.

[0023] R 4 It can be selected from acrylamide, pyrrolidone and thiolactone, preferably N-vinylpyrrolidone or N,N-dimethylacrylamide.

[0024] More preferably, R 4 Preferably selected from:

[0025] —-CON(CH3)2,

[0026] —-NCO(CH2)3(2-pyrrolidone),

[0027] —-C(O)O(CH2CH2O) p H, where p = 1-19, such as p = 2-18, p = 3-17, or p = 4-16, preferably p = 5-15.

[0028] —-C(O)O(CH2CH2O) p R 5Where p = 1 to 19, such as p = 2-18, p = 3-17, or p = 4-16, preferably p = 5-15; and where R 5 It is C 1-6 alkyl.

[0029] R 1 and R 2 R 3 and R 4 The preferred combinations are shown below:

[0030]

[0031]

[0032] Any preferred embodiments described herein can be combined in any form, but R 1 R 2 R 3 and R 4 The favorable combinations are as follows:

[0033]

[0034] Advantageously, the molecular weight of the polymer is 900 to 500,000 g / mol, preferably 1,000 to 250,000 g / mol, such as 1,000 to 100,000 g / mol.

[0035] Preferably, the polymer has a monomer (I) : monomer (II) ratio of 80 : 20 to 20 : 80% w / w, more preferably 70 : 30 to 30 : 70% w / w.

[0036] It has been unexpectedly discovered that the compositions of the present invention are particularly stable at high pH levels. Without being bound by theory, commercial polymers used for crystal growth inhibition typically contain a large number of carboxylic acid units, and it is believed that the deprotonation of these carboxylic acid units at high pH levels leads to decreased stability.

[0037] surfactants

[0038] Advantageously, the composition further comprises a surfactant, preferably a nonionic surfactant and / or anionic surfactant. Preferably, the surfactant is present in an amount of 0.01 to 20% w / w, more preferably 0.1 to 15% w / w or even more preferably 0.5 to 10% w / w.

[0039] In fact, dispersible concentrates (DCs) typically contain surfactants that enable the precipitated solid particles to be dispersed uniformly and stably.

[0040] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. These surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants.

[0041] Suitable anionic surfactants are alkali metal salts, alkaline earth metal salts, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecylbenzene and tridecylbenzene, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates, or sulfosuccinamides. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols, or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohols or alkylphenol ethoxylates.

[0042] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds alkoxylated in amounts of 1 to 50 equivalents, such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters. Ethylene oxide and / or propylene oxide can be used for alkoxylation, with ethylene oxide being preferred. Examples of N-substituted fatty acid amides are fatty acid glucosamides or fatty acid alkylolamides.

[0043] Examples of esters are fatty acid esters, glycerides, or monoglycerides. Examples of sugar-based surfactants are sorbitol, ethoxylated sorbitol, sucrose and glucose esters, or alkyl polyglucosides.

[0044] Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol, epoxides, or vinyl acetate.

[0045] Suitable cationic surfactants are quaternary ammonium salt surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines.

[0046] Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are AB or ABA type block polymers containing polyethylene oxide and polypropylene oxide blocks, or ABC type block polymers containing alkanols, polyethylene oxide and polypropylene oxide.

[0047] Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyethyleneamine or polyethyleneimine.

[0048] Active ingredients

[0049] The composition may contain an active ingredient. Typically, the active ingredient has a water solubility of less than 10,000 mg / L, preferably less than 5,000 mg / L. Preferred agrochemicals are adepidyn®, dimethomorph, cycloflufenoxam, and fluthiazopyrone.

[0050] Preferably, the ratio of copolymer to active ingredient is 10:1 to 1:10, more preferably 5:1 to 1:5, and more preferably 2:1 to 1:2.

[0051] Advantageously, the active ingredient is present in an amount of 0.01 to 50% w / w, preferably 1 to 40% w / w, more preferably 5 to 25% w / w.

[0052] Solvent and formulation types

[0053] The composition preferably contains a non-aqueous solvent.

[0054] The non-aqueous solvent can, in principle, be any solvent or solvent mixture capable of dissolving the active ingredient in a sufficiently high amount and being fully miscible with water. Preferably, dissolving the active ingredient in a non-aqueous solvent advantageously ensures complete dissolution of the active ingredient in the non-aqueous solvent.

[0055] Typically, the non-aqueous solvent has a solubility in water of 1 g / L, preferably at least 10 g / L, and even more preferably at least 100 g / L, at 20°C. In one embodiment, the non-aqueous solvent is miscible with water in all ratios.

[0056] Typically, non-aqueous solvents have a dynamic viscosity of less than 100 mPas, preferably less than 50 mPas, or 10 mPas, as determined by a rotational viscometer (apparent viscosity determined at a shear rate of 100 s⁻¹) according to CIPAC MT 192. Non-aqueous solvents may include small amounts of water, provided that the liquid mixture maintains sufficient solubility of the biocide therein. Non-aqueous solvents typically contain less than 10 wt% water, preferably less than 5 wt% water, more preferably less than 1 wt% water, in each case based on the non-aqueous solvent and water. In preferred embodiments, the non-aqueous solvent is water-free. In this context, "water-free" means that such a non-aqueous solvent contains only the amount of water typically present in commercially available non-aqueous solvents.

[0057] Examples of solvents suitable as non-aqueous solvents in many cases include: alcohols (such as methanol, ethanol, n-propanol, and isopropanol), glycols (such as ethylene glycol, diethylene glycol, or triethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,2-butanediol), glycerol, dimethyl sulfoxide, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, 1-butoxy-2-propanol, dipropylene glycol monomethyl ether, cyclohexanone, acetophenone, benzyl alcohol, N,N-dimethyl lactamide, γ-butyrolactone, γ-valerolactone, ethyl (S)-2-hydroxypropionate, N-acetylmorpholine, Rhodiasolv Polar Clean (i.e., methyl 5-(dimethylamino)-2-methyl-5-oxovalerate), and Armid. FMPC, N-octylpyrrolidone, N-butylpyrrolidone and esters (such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate or butyl acetate), propylene carbonate, butyl carbonate and tetrahydrofurfuryl alcohol or any mixture of these solvents.

[0058] Preferred non-aqueous solvents are dimethyl sulfoxide, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetophenone, benzyl alcohol, N,N-dimethyl lactamide, γ-butyrolactone, γ-valerolactone, ethyl (S)-2-hydroxypropionate, ethylene carbonate, N-acetylmorpholine, N-butylpyrrolidone, propylene carbonate, butylene carbonate, and tetrahydrofurfuryl alcohol, or mixtures thereof.

[0059] Typically, the compositions of the present invention comprise 20 wt% to 95 wt%, preferably 25 wt% to 92 wt%, more preferably 30 wt% to 80 wt% of a non-aqueous solvent, in each case based on the composition.

[0060] Preferably, the composition is an emulsion concentrate (EC) or a dispersible concentrate (DC).

[0061] Aggregation methods

[0062] A method for preparing polymers as defined herein is also provided, comprising free radical polymerization (FRP), reversible addition-fragmentation chain transfer (RAFT), atom transfer radical polymerization (ATRP), or nitroxide radical-controlled polymerization (NMP).

[0063] The polymerization reaction to obtain the polymer is preferably carried out at a temperature between 60°C and 100°C. Suitable non-aqueous organic solvents are, for example, alcohols such as methanol, ethanol, n-propanol, and isopropanol, and glycols such as ethylene glycol, diethylene glycol, or triethylene glycol, and glycerol. Other suitable solvents are esters, such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, or butyl acetate, or other non-aqueous solvents as described above.

[0064] Polymerization is initiated using a free radical initiator. The amount of initiator or initiator mixture used is between 0.001% and 10% by weight, preferably between 0.03% and 5% by weight, depending on the monomer used. Both organic and inorganic peroxides are suitable, such as sodium persulfate, or azo initiators such as azobisisobutyronitrile, azobis(2-amidopropane) dihydrochloride, or 2,2'-azobis(2-methylbutyronitrile). Examples of peroxide initiators are benzoyl peroxide, diacetyl peroxide, succinyl peroxide, tert-butyl perpentanoate, tert-butyl perethylhexanoate, tert-butyl peroxyneodecanate, tert-butyl permaleate, bis-(tert-butylper)cyclohexane, tert-butylperoxyisopropyl carbonate, tert-butyl peracetate, 2,2-bis(tert-butylperoxy)butane, dicumyl peroxide, ditert-pentyl peroxide, ditert-butyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide, and mixtures of said initiators. These initiators can also be used in combination with redox components such as ascorbic acid. Particularly suitable initiators are tert-butyl perpentanoate, tert-butyl perpentanoate, or tert-butyl perethylhexanoate.

[0065] If appropriate, free radical polymerization can be carried out in the presence of emulsifiers, additional protective colloids if appropriate, molecular weight regulators if appropriate, buffer systems if appropriate, and subsequently with pH adjustment using base or acid if appropriate.

[0066] Suitable molecular weight regulators are thiol compounds, such as alkyl thiols, e.g., n-dodecyl thiol, tert-dodecyl thiol, thioglycerol, thioglycolic acid and its esters (e.g., 2-ethylhexyl thioglycolic acid), and thiols such as mercaptoethanol. The necessary amount of the molecular weight regulator is in the range of 0% to 5% by weight based on the amount of (co)monomer to be polymerized. If a regulator is used, the amount employed is preferably in the range of 0.05% to 2% by weight, and particularly preferably 0.1% to 1.5% by weight. The monomer or monomer mixture is introduced into the stirred reactor at the polymerization temperature along with the initiator, which is normally present in solution (batch polymerization), or, if appropriate, continuously metered or introduced into the polymerization reactor in multiple continuous stages (feed polymerization). During the feeding process, usually before the actual polymerization begins, in addition to the solvent (so that the reaction mixture can be stirred), a portion (rarely intended for the total amount used in polymerization) of starting materials such as emulsifiers, protective colloids, monomers, regulators, etc., or a portion of the feed (usually monomer feed or emulsion feed and initiator feed) is added.

[0067] Polymerization can take place at atmospheric pressure or under high pressure in a closed reactor. In either case, polymerization can be carried out at a predetermined pressure during the reaction, or the pressure can be adjusted by injecting gas or by creating a vacuum. The pressure can also be controlled by depressurizing a portion of the reactor into a condenser.

[0068] After polymerization, commonly known methods for reducing residual monomers can be employed. Examples of such methods include the further addition of an initiator at the end of polymerization, acid hydrolysis of the vinyl lactam monomer, treatment of the polymer solution with a solid phase such as an ion exchanger, feeding well-copolymerized monomers, membrane filtration, polymer precipitation, and other conventional methods.

[0069] Additive components

[0070] Furthermore, the compositions of the present invention may contain other adjuvants that act in various ways either in the formulation itself, when diluted with water, or when the product is applied.

[0071] Suitable additives include liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, adhesives, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, defoamers, colorants, thickeners and binders.

[0072] Suitable adjuvants are compounds that have negligible or no harmful biological activity and improve the biological performance of the compound against the target.

[0073] Examples include surfactants, mineral or vegetable oils, and other additives.

[0074] Suitable bactericides are bromonitol and isothiazolinone derivatives, such as alkylisothiazolinone and benzisothiazolinone.

[0075] Suitable defoamers are salts of silicones, long-chain alcohols, and fatty acids.

[0076] Suitable colorants (e.g., red, blue, or green) are low-water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, ferric hexacyanate ferrite) and organic colorants (e.g., alizarin colorants, azo colorants, and phthalocyanine colorants).

[0077] Suitable tackifiers or adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylate, biowax or synthetic wax, and cellulose ether.

[0078] Use of the composition

[0079] DC and EC formulations are intended for dilution with water. Traditional carboxylic acid-based dispersants can exhibit sensitivity to high pH levels. Surprisingly, the polymers of the present invention have been found to be effective at pH 7 and above.

[0080] Therefore, the use of the formulation in high pH solutions (preferably 8 to 14) for reducing crystal growth is provided.

[0081] Therefore, methods for preparing compositions as defined herein and their use in treating weeds, pests and / or fungi are provided.

[0082] In a second aspect of the invention, a polymer composed of two monomers represented by the following formula is provided for use in inhibiting the crystal growth of an active ingredient, wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomer.

[0083]

[0084] in

[0085] R 1 Selected from hydrogen or methyl;

[0086] R 2 It is C 1-6 alkyl,

[0087] R 3 Selected from hydrogen or methyl;

[0088] R 4 Selected from:

[0089] -CONH m (C 1-6 alkyl) n Where m = 0, 1, or 2, and n = 0, 1, or 2

[0090] -C5 heterocyclic ketone

[0091] -C(O)O(CH2CH2O) p H, where p = 1 to 50

[0092] -C(O)O(CH2CH2O) p R 5 Where p = 1 to 20

[0093] R 5 It is C 1-6 alkyl.

[0094] Preferably, the described polymer is used after being diluted in water, and advantageously diluted in an alkaline solution, such as a solution with a pH of 8 to 14.

[0095] Unless otherwise stated, all percentages are given as percentages by total weight, and all embodiments and preferred features can be combined in any combination.

[0096] The present invention is described by way of the following non-limiting examples. Example

[0097] copolymer

[0098] The six copolymers according to the present invention are synthesized as follows.

[0099] Synthesis of Polymer 1 (P1):

[0100] Add MMA (5.00 g, 0.05 mol) and DMA (5.03 g, 0.05 mol) monomers and a suitable reaction solvent (dioxane, 25.01 g) to a 50 mL round-bottom flask. Add a suitable initiator, such as azobisisobutyronitrile (AIBN, 164 mg, 1 mmol), followed by the chain transfer agent 4,4′-thiobisphenylthiol (252 mg, 1 mmol). Then, cool the flask equipped with a rubber septum to 0°C (ice bath) and bubble with nitrogen for 20 min. Seal the flask and heat to 70°C for 16 h. The resulting copolymer was then purified by precipitation into diethyl ether (10-fold excess).

[0101] Polymers 2 and 4 (P2, P4) were also synthesized according to the same scheme used for polymer 1, except that the molar ratio was adjusted accordingly.

[0102] Synthesis of Polymer 3 (P3):

[0103] Add MMA (5.00 g, 0.05 mol) and DMA (5.03 g, 0.05 mol) monomers and a suitable reaction solvent (dioxane, 24.1 g) to a 50 mL round-bottom flask. Add a suitable initiator (AIBN, 33 mg, 0.2 mmol), followed by a RAFT reagent, such as 2-(butylthiocarbonylthio)propionic acid (239 mg, 1 mmol). Then, cool the flask equipped with a rubber septum to 0°C (ice bath) and bubble with nitrogen for 20 min. Seal the flask and heat to 70°C for 16 h. The resulting copolymer was then purified by precipitation into diethyl ether (10-fold excess).

[0104] Synthesis of Polymer 5 (P5):

[0105] Add MMA (5.00 g, 0.05 mol) and NVP (5.55 g, 0.05 mol) monomers and a suitable reaction solvent (dioxane, 25.01 g) to a 50 mL round-bottom flask. Add a suitable initiator such as AIBN (164 mg, 1 mmol), followed by a chain transfer agent, such as 4,4′-thiobisphenylthiol (252 mg, 1 mmol). Then cool the flask equipped with a rubber septum to 0°C (ice bath) and bubble with nitrogen for 20 min. Then seal the flask and heat to 70°C for 16 h. The resulting copolymer was then purified by precipitation into diethyl ether (10-fold excess).

[0106] Synthesis of Polymer 6 (P6):

[0107] Polymer 6 was synthesized according to the two-step scheme outlined below.

[0108] Step 1 – Preparation of PMMA precursor.

[0109] Add MMA (15.00 g, 0.15 mol) monomer and a suitable reaction solvent (24 g, toluene / isopropanol, 1:1 v / v) to a 50 mL round-bottom flask. Add AIBN (49 mg, 0.3 mmol), followed by RAFT reagent and 4-((((2-carboxyethyl)thio)thiocarbonyl)thio)-4-cyanopentanoic acid (0.92 g, 3 mmol). Then cool the flask equipped with a rubber septum to 0°C (ice bath) and bubble with nitrogen for 20 min. Seal the flask and heat to 70°C for 6 h. The resulting copolymer was then purified by precipitation into methanol (10-fold excess). 1 1H NMR analysis showed that the average PMMA DP was 50.

[0110] Step 2 – Use DMA on PMMA 50 Precursor chain extension

[0111] Add PMMA to a 50 ml round-bottom flask 50 Macro-CTA (4.45 g, 0.92 mmol) and a suitable reaction solvent (20.5 g, toluene) were prepared. Azobisisobutyronitrile (AIBN, 30 mg, 0.19 mmol) was added, followed by DMA (4.56 g, 46 mmol). The flask equipped with a rubber septum was then cooled to 0°C (ice bath) and bubbled with nitrogen for 20 min. The flask was then sealed and heated to 70°C for 16 h. The resulting copolymer was then purified by precipitation into diethyl ether (10-fold excess).

[0112] The polymers are summarized in Table 1.

[0113] Table 1

[0114]

[0115] PDMA = poly(N'N' dimethacrylamide), PMMA = poly(methyl methacrylate), and PVP = poly(N-vinylpyrrolidone).

[0116] For comparative purposes, commercially available Atlox 4913 was used. This is a copolymer of methyl methacrylate, methacrylic acid, and polyethylene glycol methacrylate, having the following structure:

[0117]

[0118] Preparations

[0119] Prepare the following formulations.

[0120] Dispersible concentrate (DC) formulations

[0121] Three different active ingredients in dispersible concentrate (DC) formulations containing polymers P1 through P5 were analyzed: fluopyram [AI1], cyclofluopyram [AI2], and dicytosyl acetamiprid [AI3]. A comparative formulation containing the commercially available dispersant Atlox 4913 was also prepared.

[0122] The preparations are listed as DC 1 to DC 9, as shown in Table 2, where the values ​​are given as a weight percentage.

[0123] Dilutes of each formulation were prepared in deionized water (1% v / v). The duration for which the dilutes were allowed to stand without stirring was specified. Observations were made over 24 hours to monitor changes in appearance and homogeneity, and analysis was performed via optical microscopy to determine the presence of crystals. The results are listed in Tables 3.1 and 3.2.

[0124] Table 2

[0125]

[0126] DML = dimethyl lactamide

[0127] Emuls. = Tristyrylphenol ethoxylate phosphate

[0128] Table 3.1

[0129]

[0130] Table 3.2

[0131]

[0132] Fluopyram DC formulation [AI1]

[0133] In formulations containing Atlox 4913 as a CGI, crystallization was evident after 24 hours. After approximately 5 hours, these formulations became heterogeneous and precipitated. Optical microscopy revealed the presence of elliptical crystals.

[0134] However, when polymers 1, 4, or 5 were used, the appearance of the formulation did not change within 24 hours. Furthermore, optical microscopy confirmed the absence of crystals in the samples. Polymers 1, 4, and 5 successfully inhibited the crystallization of fluopyram during the duration of the experiment.

[0135] Cycloflufenicol DC formulation [AI2]

[0136] In formulations containing Atlox 4913 as a CGI, crystallization was evident after 24 hours. After approximately 5 hours, these formulations became heterogeneous and precipitated. Optical microscopy revealed the presence of needle-like crystals.

[0137] However, when Polymer 2 was used instead of Atlox 4913, the appearance of the formulation remained unchanged within 24 hours. Furthermore, optical microscopy confirmed the absence of crystals in the sample. Polymer 2 successfully inhibited the crystallization of cycloflufenicol throughout the experimental duration.

[0138] Diyrylamide DC formulation [AI3]

[0139] In formulations containing Atlox 4913 as a CGI, crystallization was evident after 24 hours. After approximately 5 hours, the formulation became heterogeneous and sedimentation occurred. Optical microscopy revealed the presence of needle-like crystals.

[0140] However, when Polymer 3 was used instead of Atlox 4913, the appearance of the formulation remained unchanged within 24 hours. Furthermore, optical microscopy confirmed the absence of crystals in the sample. Polymer 3 successfully inhibited the crystallization of dimethomorph throughout the experimental duration.

[0141] Emulsifiable concentrate (EC) formulations

[0142] Polymers 1 and 5 were further investigated in the model fluopyram [AI1] EC formulation. Their compositions are shown in Table 6. Formulations were prepared with and without polymers. The polymer concentration was 7% w / w.

[0143] The formulation was prepared using anisaldehyde in a water-immiscible solvent, and the results are listed in Table 4.

[0144] Table 4

[0145]

[0146] In the formulations without polymers, crystallization was evident after 24 hours. Large white crystals were present in the samples. However, when polymers 1 and 5 were used, the appearance of the formulations did not change within 24 hours, and polymers 1 and 5 provided CGI activity to these EC formulations.

[0147] Testing was conducted at high pH levels.

[0148] Atlox 4913 contains a significant number of carboxylic acid units and can exhibit sensitivity when used under high pH conditions.

[0149] Two fluthiazopyrone [AI4] DC formulations, DC 10 and 11, were prepared to test the effectiveness of the dispersant at high pH (300 ppm bicarbonate solution, pH = 8). Their compositions are shown in Table 5, with the levels of polymer 1 and Atlox 4913 maintained at 5.9% w / w.

[0150] Table 5

[0151]

[0152] In formulations containing Atlox 4913 (DC 10), crystallization was evident after 48 hours, the dilution was heterogeneous, and large elliptical crystals were observed under an optical microscope. However, when using polymer 1, the appearance of the formulation did not change within 48 hours, and crystal growth was inhibited.

[0153] As can be seen, the composition according to the present invention exhibits improved crystal growth inhibition compared to compositions in the art.

[0154] This invention is defined by the claims.

Claims

1. An agricultural chemical composition comprising: A copolymer composed of two monomers represented by the following formula, wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomer. in R 1 Selected from hydrogen or methyl; R 2 It is C 1-6 alkyl; R 3 Selected from hydrogen or methyl; R 4 Selected from: -CONH m (C 1-6 alkyl) n Where m = 0, 1, or 2, and n = 0, 1, or 2. -C5 heterocyclic ketone -C(O)O(CH2CH2O) p H, where p = 1 to 50, -C(O)O(CH2CH2O) p R 5 , where p = 1 to 20 and where R 5 It is C 1-6 alkyl.

2. The composition according to claim 1, wherein, The molecular weight of the polymer is from 900 g / mol to 500,000 g / mol.

3. The composition according to any one of claims 1 or 2, wherein, The polymer has a monomer (I) : monomer (II) ratio of 80 : 20 to 20 : 80% w / w.

4. The composition according to any one of the preceding claims, wherein, The polymer is a random copolymer.

5. The composition according to any one of the preceding claims further comprises a surfactant, preferably wherein the surfactant is a nonionic surfactant and / or anionic surfactant.

6. The composition according to claim 5, wherein, The surfactant is present in an amount of 0.01 to 20% w / w.

7. The composition according to any one of the preceding claims, wherein, The composition contains an active ingredient.

8. The composition according to claim 7, wherein, The ratio of the polymer to the active ingredient is from 10:1 to 1:

10.

9. The composition according to any one of the preceding claims, wherein, The active ingredient is present in an amount of 0.01 to 50% w / w.

10. The composition according to any one of the preceding claims, wherein the composition comprises a non-aqueous solvent.

11. A method for preparing a polymer as defined in any one of claims 1 to 10, the method comprising free radical polymerization (FRP) or reversible addition-fragmentation chain transfer polymerization (RAFT).

12. A method for preparing the composition according to any one of claims 1 to 10.

13. The use of a polymer composed of two monomers represented by the following formula for inhibiting the crystal growth of an active ingredient, wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomer. in R 1 Selected from hydrogen or methyl; R 2 It is C 1-6 alkyl, R 3 Selected from hydrogen or methyl; R 4 Selected from: -CONH m (C 1-6 alkyl) n Where m = 0, 1, or 2, and n = 0, 1, or 2. -C5 heterocyclic ketone -C(O)O(CH2CH2O) p H, where p = 1 to 50, -C(O)O(CH2CH2O) p R 5 , where p = 1 to 20 and where R 5 It is C 1-6 alkyl.

14. The use according to claim 13, wherein, The polymer is diluted in water, preferably in a solution with a pH of 8 to 14.

15. Use of the composition according to claims 1 to 10 for treating weeds, pests and / or fungi.

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