EA044193B1 - COMPOSITIONS BASED ON FUNGICIDES WITH A REDUCED CRYSTAL GROWTH RATE - Google Patents

Description

The invention relates to a composition containing a compound of formula (I) and an agrochemical active ingredient selected from ADEPIDYN™ (pidiflumetofen), oxathiapiproline, sedaxane and azoxystrobin;

RiO[C(R ₂ )(H)C(R ₃ )(H)O] _n X (I), where R1 is C ₆ . ₁₂ alkyl or C ₆ . ₁₂ alkenyl; n equals 5-50;

independently, each [C(R ₂ )(H)C(R ₃ )(H)O] unit contains R2 and R ₃ that are both hydrogen, or in which one of R2 and R ₃ is hydrogen and the other is is phenyl, provided that at least one [C(R ₂ )(H)C(R ₃ )(H)O] unit contains one of R2 and R ₃ which is hydrogen and another which is phenyl, and X is hydrogen or selected from C ₁ . ₄ alkyl;

and to the use of a compound of formula (I) to reduce the particle growth rate (such as nucleation, crystal growth or Ostwald ripening) of an agrochemical active ingredient.

Agrochemical compositions may exhibit undesirable particle growth, such as crystal growth, nucleation, or Ostwald ripening, when stored for certain periods of time (for example, in a distributor's warehouse or farm store), particularly under conditions of varying temperature (for example, during a freeze-thaw cycle). . Such properties can lead to undesirable characteristics of agrochemical compositions (including separation, sedimentation, compaction of the agrochemical concentrate; blocking of spray nozzles when attempting to apply the agrochemical in either concentrated or diluted form, as well as insufficient biological effectiveness of the agrochemical, possibly due to limited availability of the agrochemical to the intended site of biological action due to large particle sizes, which have a lower surface area to volume ratio compared to corresponding smaller particles and therefore lower bioavailability).

It has now been discovered that certain ethylene oxide styrene oxide copolymer monoalkyl ether polymers are capable of reducing or overcoming crystal growth properties and therefore associated physical and biological problems.

Certain compositions containing an ethylene oxide styrene oxide copolymer monoalkyl ether polymer and specific agrochemical active ingredients are new.

The compounds of formula (I) are known only as wetting agents and not as crystal growth inhibitors.

Therefore, the present invention provides a composition containing a liquid continuous phase, a compound of formula (I) and an agrochemical active ingredient selected from pidiflumetofen, oxathiapiproline, sedaxane and azoxystrobin;

RiO[C(R ₂ )(H)C(R ₃ )(H)O] _n X (I), where R1 represents C _6-12 alkyl or C _6-12 alkenyl; n equals 5-50;

independently, each [C(R2)(H)C(R3)(H)O] unit contains R2 and R3, which are both hydrogen, or in which one of _R2 and _R3 is hydrogen and the other is phenyl provided that at least one [C(R ₂ )(H)C(R ₃ )(H)O] unit contains one of R2 and R ₃ which is hydrogen and the other which is phenyl, and X is hydrogen or selected from C _1-4 alkyl.

This means that each link in the fragment [C(R ₂ )(H)C(R ₃ )(H)O] _n is characterized by the formula [C(R ₂ )(H)C(R ₃ )(H)O], however, each unit is independently selected from the following: R2 is hydrogen and R3 is hydrogen, or R2 is hydrogen and R3 is phenyl, or _R2 is phenyl and _R3 is hydrogen, provided that in at least one [C(R ₂ )(H)C(R ₃ )(H)O] unit, R ₂ is hydrogen and R ₃ is phenyl, or R ₂ is hydrogen and R ₃ is phenyl.

The [C(R2)(H)C(R ₃ )(H)O] _n fragment is a random copolymer or block copolymer.

Preferably n is 5-40 (more preferably 5-20).

Preferably X is hydrogen.

Alkyl and alkenyl chains can be linear or branched.

Preferably R1 is C _6-12 alkyl, more preferably R1 is C _8-10 alkyl, even more preferably R1 is C ₈ alkyl.

Preferably, the compound of formula (I) is a compound of formula (Ia), R ₁ O[C(R ₄ )(H)C(R ₅ )(H)O] _r [CH ₂ CH ₂ O] _s X (la), where independently in each unit C(R ₄ )(H)C(R ₅ )(H)O R4 is hydrogen and R5 is phenyl, or R4 is phenyl and R5 is hydrogen, r is 1-25 , and s is 1-25, and R1 is as above or below.

Preferably, r is 1-10 (more preferably 3-7).

Preferably s is 1-10 (more preferably 3-7).

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Preferably n is an average (mean, median or modal) value.

In another aspect, the present invention provides a novel use of a compound of formula (I), as defined above or below, to reduce the rate of particle growth (such as nucleation, crystal growth or Ostwald ripening) in a composition containing a liquid continuous phase and an agrochemical active ingredient.

The composition may be a solution of an agrochemical (such as a soluble concentrate (SL) or an emulsifiable concentrate (EC)), a suspension of a solid (at room temperature) agrochemical in a liquid continuous phase (water (SC) or oil (OD)), an emulsion where droplets containing an agrochemical are dispersed in a liquid continuous phase (water (EW) or oil (EO)), or may be a suspoemulsion (SE).

The composition may further contain a surfactant. It is possible that the presence of a surfactant may increase the likelihood of nucleation, crystal growth or Ostwald ripening properties, which the compound of formula (I) is used to reduce. Surfactants are compounds that reduce the surface tension of water. Examples of surfactants are ionic (anionic, cationic or amphoteric) and non-ionic surfactants.

The noun agrochemical and the term agrochemical active ingredient are used interchangeably herein and include herbicides, insecticides, nematicides, molluscicides, fungicides, plant growth regulators and antidotes, preferably herbicides, insecticides and fungicides.

An agrochemical or a salt of an agrochemical selected from the following may be suitable for the present invention.

Suitable herbicides include pinoxaden, bicyclopyrone, mesotrione, fomesafen, tralkoxydim, napropamide, amitraz, propanil, pyrimethanil, dicloran, tecnazen, toclofos-methyl, flamprop M, 2,4-D, MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, haloxyfop, quizalofop-R, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben, tebutam, chlorthaldimethyl, benomyl, benfuresate, dicambu, dichlobenil, benazoline, triazoxide, fluazuron, teflubenzuron, phenmedipham, acetochlor, alachlor, metolachlor, pretilachlor, tenylchlor, alloxydim, butroxydim, clethodim, cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb, bifenox, oxyfluorfen, acifluorfen, fluazifop, S-metolachlor, glyphosate, glufosinate, paraquat, diquat, fluoroglycophene-ethyl, bromoxynil, ioc blue, imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumioxazin, flumiclorac-pentyl, pichloram, amodosulfuron, chlorsulfuron, nicosulfuron, rimsulfuron, triasulfuron, triallate, pebulate, prosulfocarb, molinate, atrazine, simazine, cyanazine, ameter in, prometrin, terbutylazine, terbutryn, sulcotrione, isoproturon, linuron, fenuron, chlortoluron, methoxuron, iodosulfuron, mesosulfuron, diflufenican, flufenacet, fluroxypyr, aminopyralide, piroxulam, Rinskor XDE-848 and halauxifen-methyl.

Suitable fungicides include isopyrazam, mandipropamide, azoxystrobin, trifloxystrobin, kresoxim-methyl, mefenoxam, famoxadone, metominostrobin and picoxystrobin, cyprodanil, carbendazim, thiabendazole, dimethomorph, vinclozolin, iprodione, dithiocarbamate, imazalil, prochloraz, fluquinconazole, ep oxiconazole, flutriafol, aconazole, bitertanol , bromuconazole, cyproconazole, difenoconazole, hexaconazole, paclobutrazol, propiconazole, tebuconazole, triadimefon, triticonazole, fenpropimorph, tridemorph, fenpropidine, mancozeb, metiram, chlorothalonil, thiram, ciram, captafol, captan, folpet, fluazinam, flutolanil, carboxin, metalaxyl, bupirimate , ethirimol, dimoxystrobin, fluoxastrobin, orysastrobin, methominostrobin, prothioconazole, adepidine, bixafen, fludioxonil, fluxapyroxad, prothioconazole, pyraclostrobin, Revisol, solatenol and Xemium.

Suitable insecticides include thiamethoxam, imidacloprid, acetamiprid, clothianidin, dinotefuran, nitenpyram, fipronil, abamectin, emamectin, tefluthrin, emamectin benzoate, bendiocarb, carbaryl, fenoxycarb, isoprocarb, pirimicarb, propoxur, xylylcarb, asulam, chlorpropham, endosulfan , heptachlor, tebufenozide, bensultap, diethofencarb, pirimiphos-methyl, aldicarb, methomyl, cypermethrin, bioallethrin, deltamethrin, lambda-cyhalothrin, cyhalothrin, cyfluthrin, fenvalerate, imiprothrin, permethrin, galfenprox, chlorantraniliprole, oxamyl, flupyradifuron, sedaxane, inscalis, rinaxipir , sulfoxaflor and spinetoram.

Suitable plant growth regulators include paclobutrazol, trinexapac-ethyl and 1methylcyclopropene.

Suitable antidotes include benoxacor, cloquintocet-mexyl, ciometrinil, dichlormide, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, mefenpyr-diethyl, MG-191, naphthalene anhydride and oxabetrinil.

The various editions of The Pesticide Manual [especially the 14th and 15th editions] also disclose detailed information on agrochemicals, any of which may be suitably used in the present invention.

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Preferably, the agrochemical is present in the composition at a concentration of from 0.5 to

50.0% (more preferably 1.0 to 30; even more preferably 3.0 to 20.0; most preferably 5.0 to 15.0%) by weight.

Preferably the agrochemical is in suspended form in a continuous phase.

Preferably, the agrochemical is ADEPIDYN™ (pydiflumetofen), oxathiapiproline, sedaxane or azoxystrobin.

Preferably the continuous phase is aqueous.

An additional agrochemical may be present in the composition of the present invention.

Preferably, the additional agrochemical is present in the composition at a concentration of from 0.5 to 50.0% (more preferably from 1.0 to 30; even more preferably from 3.0 to 20.0; most preferably from 5.0 to 15. 0%) by weight.

Preferably, the first agrochemical is present in suspended form in a continuous phase, while the additional agrochemical is present in emulsified form.

If more than one agrochemical is present, preferably ADEPIDYN™ (pydiflumetofen) is in suspended form while propiconazole is present as an emulsion, or oxathiapiproline is in suspended form while mefenoxam is present as an emulsion. In such a situation, preferably the continuous phase is aqueous and the composition is a suspoemulsion.

Preferably, the compound of formula (I) is present in the composition at a concentration of from 0.1 to 10.0% (more preferably from 0.3 to 5.0; even more preferably from 0.5 to 2.0; most preferably from 0 .5 to 1.0%) by weight.

The following examples demonstrate crystal growth associated with the compositions of the present invention. Unless otherwise noted, all concentrations and ratios are by weight.

Particle size distribution is reported as the number of particles that fall within each of the different size ranges, presented as a percentage of the total number of all sizes in the sample of interest.

Thus, DV95 (for example) represents summary data; 95 means that no more than 95% percent of all particles are smaller than this number. For example, if the DV 95 is 7 µm, this means that 95% of the particles are smaller than 7 µm and 5% are larger than 7 µm.

Break-Thru™ DA647 and Break-Thru™ DA675 are examples of compounds of formula (I).

Break-Thru™ DA647 is an oxirane, phenyl, oxirane polymer, monooctyl ether (CAS No.: 83653-00-3); it is also known as TEGO™ XP 11010 (from Degussa).

Break-Thru™ DA675 is an oxirane, 2-phenyl-, oxirane polymer, mono(3,5,5trimethylhexyl)ether (CAS number: 303150-42-7); it is also known as TEGO™ VISCOPLUS 3030 and TEGO™ VISCOPLUS 3060 (from Degussa).

Example 1.

This example presents data regarding suspoemulsions (SE) containing ADEPIDYN™ (pydiflumetofen) suspended in water and propiconazole present as an oil-in-water emulsion. All SE-based formulations were prepared and analyzed for particle size using conventional methods known to those skilled in the art.

In table 1 shows for each SE a list of ingredients and particle size data obtained during freeze-thaw (F/T) storage of SE samples; used a freeze-thaw cycling stress test to physically store the samples, with the storage freezer/oven temperature changed from -10 to 45°C every 24 h (and then back again after 24 h). Under conditions of such extreme temperature change, the material under stress can induce significant particle growth of the active ingredients, however, as shown in Table. 1, this can be mitigated by the presence of a compound of formula (I).

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Table 1

Ingredients ADE-1 ADE-2 Propiconazole 12.5 12.5 Adepidyn™ 15 15 1,2,3 -Propanetriol 3.7 3.7 Butyl polyalkylene oxide block copolymer 6.0 5.5 Castor oil, ethoxylated 8.0 8.2 Lignosulfonic acid, sodium salt 1.5 0.5 Methyl methacrylate polymer with methacrylic acid and methoxypolyoxyethylene methacrylate 1.0 0.8 Break-Thru™ DA647 0 2.2 Magnesium aluminum silicate dispersion 4.0 4.6 Biocides 0.2 0.2 Thickener 3.9 3.9 pH regulator 0.2 0.2 Defoamer 0.05 0.05 Water up to 100% up to 100% Initial particle size DV(95) cm 7.2 7.1 After 2 weeks of F/T cycle: particle size DV(95) cm 71.3 14.3 Particle size increase factor More than 10 times 2x

Conclusion: ADE-1 and ADE-2 are extremely similar formulations, with the key difference being that ADE-2 contains Break-Thru™ DA647, which is not present in ADE-1; as shown in table. 1, the presence of Break-Thru™ DA647 significantly reduces the rate of particle growth (crystal growth).

Example 2.

This example presents data regarding fungicide suspoemulsions (SE) containing OXTP (oxathiapiproline) suspended in water and MFX (mefenoxam) present as an oil-in-water emulsion. All SE-based formulations were prepared and analyzed for particle size using conventional methods known to those skilled in the art.

In table Table 2 provides a list of ingredients and particle size data obtained during storage of SE samples for each SE.

table 2

Composition and particle size growth of OXTP/MFX after storage at 54°C

Ingredient OXTP-1 OHTR-2 OHTR-3 OHTR-4 OHTR-5 OHTR 5 5 5 5 5 MFX 15 15 15 15 15 Pluronic ^1M PE10400 0.5 0.5 0.5 0.5 0.5 Toximul™ 8320 1 1 1 1 1 Break-Thru ^1M DA675 0 0.5 1 Break-Thru ^1M DA647 0 0.5 1 Xanthan pregel 20 20 20 20 20 Defoamer Xiam enter 1510 ο,ι OD OD 0.1 0.1 Water 58.4 57.9 57.4 57.9 57.4 Total 100 100 100 100 100

Initial particle size Dv50 (µm) 1.69 1.75 1.51 1.77 1.87 Original size 6.44 5.12 5.01 6.74 6.84

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Ingredient particles Dv95 (µm) Particle size after storage at 54°C for 4 weeks. Dv50 (µm) 5.32 1.94 1.54 2.80 2.87 Particle size after storage at 54°C for 4 weeks. Dv95 (µm) 12.07 5.27 5.39 5.62 6.14 Growth of Dv50 after 54°C for 4 weeks. (%) 215.5 10.6 2.0 58.2 53.5

Conclusion: OXTR-1 - OXTR-5 formulations are extremely similar compositions, with the key difference being that OXTR-2 - OXTR-5 formulations contain Break-Thru™ DA647 or DA675, which are not present in OXTR-1; as shown in table. 2, the presence of Break-Thru™ DA647 or DA675 significantly reduces the rate of particle growth (crystal growth).

Example 3.

This example presents data regarding fungicide suspension concentrates (SC) containing sedaxane suspended in water. All SC-based formulations were prepared and analyzed for particle size using conventional methods known to those skilled in the art. In table Figure 3 provides a list of ingredients and particle size data obtained during storage of SC samples for each SC.

Table 3

Compositions based on a composition based on sedaxane and the growth of their particle size

Ingredient SDX-1 SDX-2 SDX-3 Sedaksan 5 5 5 Wetting agent Rhodacal™ DS10 0.2 0.2 0.2 Dispersant Toximul™ 8320 1 Dispersant REAX™ 100M 1 BreakThru™ Dispersant DA-675 1 Rhodiasolve™ Polarclean (water miscible solvent) 10 10 10 Xanthan pregel 25 25 25 Defoamer Xiamenter™ 1510 0.1 0.1 0.1 Water 58.7 58.7 58.7 Total 100 100 100 Initial particle size Dv50 (µm) z, z z, z z, z Particle size after storage at 50°C for 4 weeks. Dv50 (µm) 5.4 7.48 3.33 Growth of Dv50 after 50°C for 4 weeks. (%) 62 127 1

Conclusion: Formulations SDX-1 - SDX-3 are extremely similar compositions, with the key difference being that they contain different dispersants; SDX-3 contains BreakThru™ DA675, which is absent from SDX-1 and SDX-2 and is replaced by dispersants of a different chemical nature; as shown in table. 3, the presence of Break-Thru™ DA675 significantly reduces the rate of particle growth (crystal growth).

Example 4.

This example presents data regarding fungicide suspension concentrates (SC) containing azoxystrobin suspended in water. All SC-based formulations were prepared and analyzed for particle size using conventional methods known to those skilled in the art.

Claims (10)

new field of technology. In table Figure 4 shows for each SC a list of ingredients and particle size data obtained during storage of SC samples. Table 4 Azoxystrobin-based compositions and their particle size growth after storage at 50°C for 4 weeks Ingredient AZ-1 AZ-2 AZ-3 Azoxystrobin 5 5 5 Wetting agent Morwet™ D425 o, s o, s o, s Dispersant Toximul™ 8320 1 Dispersant REAX™ 100M 1 Break-Thru™ Dispersant DA-675 1 Rhodiasolve ^1M Polarclean (water miscible solvent) 10 10 10 Xanthan pregel 25 25 25 Xiameter™ 1510 Defoamer 0.1 0.1 0.1 Water 58.6 58.6 58.6 Total 100 100 100 Initial particle size, Dv50 (µm) 1.16 1.16 1.16 Particle size after storage at 50°C for 4 weeks, Dv50 (µm) 1.48 1.58 1.23 Growth of Dv50 after 50°C for 4 weeks. (%) 27.5 36.6 6.1 Conclusion: Formulations AZ-1 - AZ-3 are extremely similar compositions, with the key difference being that they contain different dispersants; composition AZ-3 contains Break-Thru™ DA675, which is absent in compositions AZ-1 and AZ-2 and is replaced by dispersants of a different chemical nature; as shown in table. 4, the presence of Break-Thru™ DA675 significantly reduces the rate of particle growth (crystal growth). CLAIM 1. A composition containing a liquid continuous phase, a compound of formula (I) and an agrochemical active ingredient selected from pidiflumetofen, oxathiapiproline, sedaxane and azoxystrobin, R1O[C(R2)(H)C(R3)(H)O] _n X ( I), where R1 represents Cg _-10 alkyl; n equals 10-50; independently, each [C(R ₂ )(H)C(R ₃ )(H)O] unit contains R2 and R ₃ that are both hydrogen, or in which one of R2 and R ₃ is hydrogen and the other is is phenyl, provided that at least one [C(R ₂ )(H)C(R ₃ )(H)O] unit contains one of R2 and R3 that is hydrogen and another that is phenyl , and X represents hydrogen or selected from C _1-4 alkyl. 2. The composition according to claim 1, where X represents hydrogen. 3. Composition according to claim 1 or 2, where n is 5-40. 4. A composition according to claim 1, wherein the compound of formula (I) is a compound of formula (Ia), R1O[C(R4)(H)C(R5)(H)O]r[CH2CH2O]sX (Ia), where independently in each C(R4)(H)C(R ₅ )(H)O unit, R4 is hydrogen and R5 is phenyl, or R4 is phenyl and R5 is hydrogen, r is 1-25, and s equals 1-25. 5. The composition according to any one of claims 1 to 4, wherein the additional agrochemical is present, and wherein the first agrochemical is present in suspended form in a continuous phase, while the additional agrochemical is present in emulsified form. 6. The composition according to claim 5, wherein the first agrochemical is pidiflumetofen, which is in suspended form, and the additional agrochemical is propiconazole, which is present in emulsified form. 7. Use of a compound of formula (I) to reduce the rate of particle growth in a composition containing a liquid continuous phase and an agrochemical active ingredient R1O[C(R2)(H)C(R3)(H)O]nX (I), where R1 is Cg _-10 alkyl; n equals 5-50; independently, each unit [C(R ₂ )(H)C(R ₃ )(H)O] contains R ₂ and R ₃ , which simultaneously represent hydrogen, or in which one of R ₂ and R ₃ represents is hydrogen and the other is phenyl, provided that at least one [C(R ₂ )(H)C(R ₃ )(H)O] unit contains one of R ₂ and R ₃ which represents hydrogen, and another which represents phenyl, and X represents hydrogen or selected from C1. ₄ alkyl. 8. Use according to claim 7, wherein X represents hydrogen. 9. Application according to claim 7 or 8, where η is equal to 5-40. 10. Use according to claim 7, wherein the compound of formula (I) is a compound of formula (1a), R ₁ O[C(R ₄ )(H)C(R ₅ )(H)O] _r [CH ₂ CH ₂ O] _s X (la), where independently in each unit C(R4)(H)C(R5)(H)O R4 is hydrogen and R ₅ is phenyl, or R ₃ is phenyl and R ₅ represents hydrogen, g equals 1-25, and s equals 1-25. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky lane, 2