Agricultural chemical component and methods for preparing this component.

Abstract

The agrochemical component contains: a copolymer consisting of two monomers represented by the following formulas where (I) is a hydrophobic monomer and (II) is a hydrophilic monomer where R1 is chosen from hydrogen or methyl; R2 is a C1-6 alkyl group; R3 is chosen from hydrogen or methyl; R4 is chosen from: -CONHm(C1-6 alkyl)n where m = 0, 1 or 2, n = 0, 1 or 2, -C5 heterocyclic ketone, -C(O)O(CH2CH2O)pH where p = 1 to 50, -C(O)O(CH2CH2O)pR5 where p = 1 to 20 and where R5 is a C1-6 alkyl. In addition, the invention relates to a method for preparing this polymer or component.

Description

[0001] Composition

[0002] The present invention relates to compositions comprising a copolymer, methods of preparing and uses of the same.

[0003] Solvent-based agrochemical formulations, such as dispersible concentrates (DC) and emulsifiable concentrates (EC), are attractive for several reasons. Such formulations are homogeneous and therefore do not require anti settling agents. Moreover, solvent based formulations generally do not require antifreeze or antimicrobial agents.

[0004] DC and EC formulations are very similar in that both comprise an active ingredient and suitable surfactants all dissolved in a non-aqueous solvent. For EC formulations, the solvent must be water-immiscible, meaning that upon dilution in water these concentrates form spontaneous emulsions. For DC formulations, the solvent must be water-miscible, meaning that upon dilution in water these concentrates form spontaneous dispersions of active ingredient (Al) particles in water.

[0005] One particular problem associated with both solvent-based DC and EC formulations is that uncontrolled crystal growth may occur upon dilution in water. This is undesirable as such crystals can interfere with agricultural equipment by blocking spray nozzles.

[0006] Conventional copolymer dispersants used to address crystal growth struggle to address this and those based on carboxylic acids can exhibit sensitivity towards pH levels.

[0007] In order to address these problems, the present invention therefore provides an agrochemical composition comprising: a copolymer consisting of two monomers represented by the following formulae wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomer: wherein

[0008] R1is selected from hydrogen or methyl; R2is a C1-6 alkyl group,

[0009] R3is selected from hydrogen or methyl;

[0010] R4is selected from

[0011] -CONHm(Ci-6 alkyl)nwhere m = 0,1 or 2 n = 0, 1 or 2,

[0012] -Cs heterocyclic ketones,

[0013] -C(O)O(CH2CH2O)PH wherein p = 1 to 50, and

[0014] -C(O)O(CH2CH2O)PR5wherein p = 1 to 20 and wherein R5is C1-6 alkyl.

[0015] It has surprisingly been found that the copolymer as so defined acts to reduce the crystal growth in agrochemical formulations.

[0016] The term ‘copolymer’ and ‘polymer’ are used interchangeably herein.

[0017] The copolymer is advantageously a random copolymer.

[0018] Polymer

[0019] R2may be selected from methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl ( / -Pr), n-butyl (n-Bu), isobutyl ( / -Bu), sec-butyl and tert-butyl (f-Bu). More preferably R2is from methyl or ethyl.

[0020] R4may be selected from acrylamides, pyrrolidone and thiolactones, preferably N-vinyl pyrrolidone or N,N-Dimethylacrylamide.

[0021] More preferably R4is preferably selected from:

[0022] - CON(CH3)2,

[0023] - NCO(CH2)3(2-pyrrolidone),

[0024] - C(O)O(CH2CH2O)PH wherein p = 1-19, such as p=2-18, p=3-17, or p=4-16, preferably p=5-15,

[0025] - C(O)O(CH2CH2O)PR5wherein p = 1 to 19, such as p=2-18, p=3-17, or p=4-16, preferably p=5-15; and wherein R5is C1-6 alkyl. Preferred combinations of R1and R2, R3and R4are shown below:

[0026] Any preferred embodiments described herein may be combined in any form but advantageous combinations of R1, R2, R3and R4are shown below:

[0027] Advantageously, the molecular weight of the polymer is from 900 to 500000 g / mol, preferably from 1000 to 250 000 g / mol, such as from 1000 to 100,000 g / mol. Preferably the polymer has a ratio of monomer (I): monomer (II) from 80:20 to 20:80 %w / w, more preferably from 70:30 to 30:70 %w / w.

[0028] It has surprisingly been found that the compositions of the present invention are particularly stable at high pH levels. Without wishing to be bound by theory, commercial polymers used for crystal growth inhibition typically contain a high number of carboxylic acid units and it is believed that deprotonation of these carboxylic acid units at high pH levels results in a reduction of stability.

[0029] Surfactant

[0030] Advantageously, the composition further comprises a surfactant, preferably wherein the surfactant is a non-ionic surfactant and / or an anionic surfactant. Preferably the surfactant is present in an amount from 0.01 to 20 %w / w, preferably 0.1 to 15%w / w or more preferably 0.5 to 10%w / w.

[0031] Indeed, Dispersible Concentrates (DCs) often contain surfactants that make a uniform and stable dispersion of the precipitated solid particles.

[0032] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant.

[0033] Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

[0034] 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 such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanol amides.

[0035] Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl polyglucosides.

[0036] Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl alcohols, alkylene oxides or vinyl acetate.

[0037] Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.

[0038] Suitable amphoteric surfactants are alkyl betains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.

[0039] Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.

[0040] Active Ingredient

[0041] The composition may comprise an active ingredient. Typically, the active ingredient has a water solubility of less than 10 000 mg / L, preferably less than 5000 mg / L. Preferred agrochemicals are pydiflumetofen (Adepidyn®), Mandipropamid, Cyflufenamid, and Oxathiapiprolin.

[0042] Preferably, the ratio of the copolymer : active ingredient is from 10:1 to 1 :10, preferably 5:1 to 1 :5 more preferably 2:1 to 1 :2. Advantageously, the active ingredient is present in an amount from 0.01 to 50 %w / w, preferably 1 to 40 % w / w, more preferably 5 to 25 % w / w.

[0043] Solvent and Formulation Type

[0044] The composition preferably comprises a non-aqueous solvent.

[0045] The nonaqueous solvent can in principle be any solvent or solvent mixture that is capable of dissolving an active ingredient in sufficiently high amounts and that is sufficiently miscible with water. Preferably, the active ingredient is dissolved in the non-aqueous solvent, advantageously the active ingredient fully dissolved in the non-aqueous solvent.

[0046] Typically, the nonaqueous solvent has a solubility in water of 1 g / l at 20 C, preferably at least 10 g / l, even more preferably at least 100 g / l. In one embodiment, the nonaqueous solvent is miscible with water in all ratios.

[0047] Typically, the nonaqueous solvent has a dynamic viscosity of less than 100 mPas, preferably of less than 50 mPas or 10 mPas, as determined by as determined according to CIPAC MT 192 by using a rotational viscometer (apparent viscosity determined at shear rate of 100 s-1). The nonaqueous solvent may include small amounts of water as long as the liquid mixture maintains sufficient solubility of the pesticides in it. The nonaqueous solvent typically contains less than 10 wt% water, preferably less than 5 wt% water, more preferably less than 1 wt% water, in each case based on the nonaqueous solvent and water. In one preferred embodiment, the nonaqueous solvent contains no water. 'No water' this context means that such a nonaqueous solvent contains water only in an amount as it is typically present in commercial grades of such nonaqueous solvent.

[0048] Examples of solvents that are in many cases suitable as nonaqueous solvents are: alcohols (such as methanol, ethanol, n-propanol and isopropanol), glycols (such as ethylene glycol, diethylene glycol or triethylene glycol, 1 ,2-propylene glycol, 1 ,3 propylene glycol, 1 ,2-butylene glycol), 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, gamma-butyrolactone, gamma-valerolactone, ethyl (S)-2-hydroxypropionate, N-acetyl morpholine, Rhodiasolv Polar Clean (i.e. methyl-5-(dimethylamino)-2-methyl-5- oxopentanoate), Armid FMPC, N-octyl pyrrolidone, N-butyl pyrrolidone and esters (such as, for example, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate or butyl acetate), propylene carbonate, butylene carbonate and Tetrahydrofurfuryl alcohol or mixtures any of these solvents.

[0049] Preferred nonaqueous solvents are dimethyl sulfoxide, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetophenone, benzyl alcohol, N,N-dimethyl lactamide, gamma-butyrolactone, gamma-valerolactone, ethyl (S)-2-hydroxypropionate, ethylene carbonate, N-acetyl morpholine, N-butyl pyrrolidone, propylene carbonate, butylene carbonate and Tetrahydrofurfuryl alcohol, or mixtures thereof.

[0050] Typically, compositions of the invention comprise 20 to 95 wt% of nonaqueous solvent, preferably 25 to 92 wt%, more preferably 30 to 80 wt%, in each case based on the composition.

[0051] Preferably the composition is an Emulsion Concentrate (EC) or a Dispersible Concentrate (DC).

[0052] Polymerisation Method

[0053] There is also provided a method of preparing a polymer as defined herein, comprising free- radical polymerisation (FRP), reversible addition-fragmentation chain-transfer (RAFT), atomtransfer radical polymerisation (ATRP) or nitroxide mediated polymerisation (NMP).

[0054] The polymerisation reaction for obtaining the polymer is preferably carried out at temperatures from 60 to 100 °C. Suitable nonaqueous 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. Further suitable solvents are esters such as, for example, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate or butyl acetate or other nonaqueous solvents as described above.

[0055] Free-radical initiators are employed to initiate the polymerisation. The amounts of initiator or initiator mixtures used, based on monomer employed, are between 0.001 and 10% by weight, preferably between 0.03 and 5% by weight. Depending on the nature of the solvent used, both organic and inorganic peroxides are suitable, such as sodium persulfate or azo initiators such as azobisisobutyronitrile, azo-bis(2-amidopropane) dihydrochloride or 2,2'-azobis(2- methylbutyronitrile). Examples of peroxide initiators are dibenzoyl peroxide, diacetyl peroxide, succinyl peroxide, tert-butyl peroxypivalate, tert-butyl perethylhexanoate, tert-butyl peroxyneodecanoate, tert-butyl permaleate, bis-(tert-butylper)cyclohexane, tert- butylperoxyisopropyl carbonate, tertbutyl peracetate, 2,2-bis(tert-butylperoxy)butane, dicumyl peroxide, di-tert-amyl peroxide, di-tertbutyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide, tertbutyl hydroperoxide, hydrogen peroxide and mixtures of said initiators. Said initiators can also be used in combination with redox components such as ascorbic acid. Particularly suitable initiators are tert-butyl perneodecanoate, tert-butyl perpivalate or tert-butyl per-ethylhexanoate.

[0056] The free-radical polymerisation can take place if appropriate in the presence of emulsifiers, if appropriate further protective colloids, if appropriate molecular weight regulators, if appropriate buffer systems and if appropriate subsequent pH adjustment using bases or acids.

[0057] Suitable molecular weight regulators are sulfhydryl compounds such as alkyl mercaptans, e.g. n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycerol, thioglycolic acid and esters thereof (e.g. 2-ethylhexyl thioglycolate), mercaptoalkanols such as mercaptoethanol. The necessary amount of the molecular weight regulators is in the range from 0 to 5% by weight based on the amount of (co)monomers to be polymerized. If regulators are used, the amount employed is preferably in the range from 0.05 to 2% by weight, particularly preferably 0.1 to 1.5% by weight. The monomer, or the monomer mixture are introduced together with the initiator, which is generally present in solution, into a stirred reactor at the polymerisation temperature (batch process) or if appropriate metered continuously or in a plurality of consecutive stages into the polymerisation reactor (feed process). It is usual in the feed process for the reactor to be charged, before the start of the actual polymerisation , besides the solvent (in order to make stirring of the reaction mixture possible) also with partial quantities, rarely the total quantity intended for the polymerisation, of the starting materials such as emulsifiers, protective colloids, monomers, regulators etc, or partial quantities of the feeds (generally monomer feed or emulsion feed and initiator feed).

[0058] The polymerisation can be carried out both under atmospheric pressure and in a closed reactor under elevated pressure. In this case it is possible to polymerize either under the pressure set up during the reaction, or the pressure can be adjusted by injecting a gas or evacuating. The pressure can also be controlled by partial decompression of the reactor into the condenser.

[0059] After the polymerisation it is possible to employ generally known processes for reducing residual monomers. Examples of such processes are further addition of an initiator at the end of the polymerisation, hydrolysis of vinyl lactam monomers by adding acids, treatment of the polymer solution with solid phases such as ion exchangers, feeding in a monomer which copolymerizes well, membrane filtration, polymer precipitation and further customary methods.

[0060] Auxiliary Components

[0061] Furthermore, compositions of the invention may contain other auxiliaries that function in various ways either in the formulation itself or when it is diluted with water, or when the product is applied.

[0062] Suitable auxiliaries include liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, adhesion agents, humectants, repellents, attractants, feeding, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

[0063] Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries.

[0064] Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyl isothiazolinones and benzisothiazolinones.

[0065] Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

[0066] Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

[0067] Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0068] Uses of the Composition

[0069] DC and EC formulations are intended for use on dilution with water. Traditional dispersants based on carboxylic acids can exhibit sensitivity towards high pH. Surprisingly it has been found that the polymers of the current invention are effective at pH 7 and above.

[0070] Accordingly, there is provided the use of the described formulation in a high pH solution, preferably from 8 to 14, to reduce crystal growth. Accordingly, there is provided a method of preparing a composition as defined herein and its use for the treatment of weeds, pests, and / or fungi.

[0071] In a second aspect of the invention there is provided the use of a polymer consisting of two monomers represented by the following formulae wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomer wherein

[0072] R1is selected from hydrogen or methyl;

[0073] R2is a C1-6 alkyl group,

[0074] R3is selected from hydrogen or methyl;

[0075] R4is selected from

[0076] -CONHm(Ci-6 alkyl)nwhere m = 0,1 or 2 n = 0, 1 or 2

[0077] -Cs heterocyclic ketone

[0078] -C(O)O(CH2CH2O)PH wherein p = 1 to 50

[0079] -C(O)O(CH2CH2O)PR5wherein p = 1 to 20

[0080] R5is C1-6 alkyl for inhibiting crystal growth formation of active ingredients.

[0081] Preferably the described polymer is used upon dilution in water, advantageously in an alkaline solution, such as solution with a pH from 8 to 14.

[0082] Unless otherwise stated all percentages are given as percentages by total weight and all embodiments and preferred features may be combined in any combination.

[0083] The invention is described by the following non-limiting Examples. Examples

[0084] Copolymers

[0085] Six copolymers according to the present invention were synthesised as below.

[0086] Polymer 1 (P1) synthesis:

[0087] To a 50 ml round-bottomed flask, MMA (5.00 g, 0.05 mol) and DMA (5.03 g, 0.05 mol) monomers were added, along with a suitable reaction solvent (dioxane, 25.01 g). To this, a suitable initiator such as azobisisobutyronitrile (AIBN, 164 mg, 1 mmol) was added, followed by a chain-transfer agent 4,4'-thiobisbenzenethiol (252 mg, 1 mmol). The flask was then equipped with a rubber septum, cooled to 0 °C (ice bath), and sparged with nitrogen gas for 20 minutes. 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).

[0088] Polymers 2 and 4 (P2, P4) were also synthesised according to the protocol used for Polymer 1 above, except the molar ratios were adjusted accordingly.

[0089] Polymer 3 (P3) synthesis:

[0090] To a 50 ml round-bottomed flask, MMA (5.00 g, 0.05 mol) and DMA (5.03 g, 0.05 mol) monomers were added, along with a suitable reaction solvent (dioxane, 24.1 g). To this, a suitable initiator (AIBN, 33 mg, 0.2 mmol) was added, followed by a RAFT agent, for example 2-(butylthiocarbonothioylthio) propanoic acid (239 mg, 1 mmol). The flask was then equipped with a rubber septum, cooled to 0 °C (ice bath) and sparged with nitrogen gas for 20 minutes. 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).

[0091] Polymer 5 (P5) synthesis:

[0092] To a 50 ml round-bottomed flask, MMA (5.00 g, 0.05 mol) and NVP (5.55 g, 0.05 mol) monomers were added, along with a suitable reaction solvent (dioxane, 25.01 g). To this, a suitable initiator such as (AIBN, 164 mg, 1 mmol) was added, followed by a chain-transfer agent, for example 4,4'-Thiobisbenzenethiol (252 mg, 1 mmol). The flask was then equipped with a rubber septum, cooled to 0 °C (ice bath) and sparged with nitrogen gas for 20 minutes. 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). Polymer 6 (P6) synthesis:

[0093] Polymer 6 was synthesised according to a two-step protocol, as outlined below.

[0094] Step 1 - preparation of a PM MA precursor.

[0095] To a 50 ml round-bottomed flask, MMA (15.00 g, 0.15 mol) monomer was added, along with a suitable reaction solvent (24 g, toluene / isopropyl alcohol, 1 :1 v / v). To this, Al BN (49 mg, 0.3 mmol) was added, followed by a RAFT agent, 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4- cyanopentanoic acid (0.92 g, 3 mmol). The flask was then equipped with a rubber septum, cooled to 0 °C (ice bath) and sparged with nitrogen gas for 20 minutes. The flask was then sealed and heated to 70 °C for 6 h. The resulting copolymer was then purified by precipitation into methanol (10 fold excess).1H NMR analysis indicated a mean PMMA DP of 50.

[0096] Step 2 - chain extension of PMMA50 precursor with DMA

[0097] To a 50 ml round-bottomed flask PMMA50 macromolecular chain-transfer agent (macro-CTA) was added (4.45 g, 0.92 mmol), along with a suitable reaction solvent (20.5 g, toluene). To this, azobisisobutyronitrile (AIBN, 30 mg, 0.19 mmol) was added, followed by DMA (4.56 g, 46 mmol). The flask was then equipped with a rubber septum, cooled to 0 °C (ice bath) and sparged with nitrogen gas for 20 minutes. 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).

[0098] The polymers are summarised in Table 1.

[0099] Table 1

[0100] PDMA = poly(N’N’ dimethyl acrylamide), PMMA = poly(methyl methacrylate) and PVP = poly(N vinyl pyrrolidone). For comparative purposes the commercially available Atlox 4913 was used. This is a copolymer of methyl methacrylate, methacrylic acid and polyethylene glycol methacrylate, with the structure:

[0101] Formulations

[0102] The following formulations were prepared.

[0103] Dispersion Concentrate (DC) formulations

[0104] Dispersion Concentrate (DC) formulations comprising polymers P1 to P5 were analysed for three different active ingredients: Pydiflumetofen [Al 1], Cyflufenamid [AI2] and Mandipropamid [Al 3] . A comparative formulation comprising the commercially available dispersant Atlox 4913 was also prepared.

[0105] The formulations are listed as DC 1 to DC 9 as set out in Table 2 with the values given as percentage by weight.

[0106] Dilutions of each formulation were prepared in deionized water (1 % v / v). The dilutions were allowed to stand unstirred for the duration of the experiment. Observations were made over 24 hours to monitor changes in appearance and homogeneity, as well as analysed via optical microscopy to determine whether crystals were present. The results are set out in Tables 3.1 and 3.2. Table 2

[0107] DML=Dimethyl lactamide

[0108] Emuls.= Tristyrylphenol Ethoxylate Phosphate Ester

[0109] Table 3. 1 Table 3.2

[0110] Pydiflumetofen DC formulations FA111

[0111] In formulations containing Atlox 4913 as a CGI, crystallization was obvious after 24 h. The formulations were inhomogeneous after approx. 5 h and sedimented. Optical microscopy revealed the presence of oval-shaped crystals.

[0112] However, when using either polymers 1 , 4 or 5, no change in formulation appearance occurred over 24 h. In addition, optical microscopy confirmed that no crystals were present in the sample. Polymers 1 , 4 and 5 had successfully inhibited the crystallization of the Pydiflumetofen over the duration of the experiment.

[0113] Cyflufenamid DC formulations [AI21

[0114] In formulation containing Atlox 4913 as a CGI, crystallization was obvious after 24 h. The formulations were inhomogeneous after approx. 5 h and sedimented. Optical microscopy revealed the presence of needle-like crystals.

[0115] However, when using polymer 2 in place of Atlox 4913, no change in formulation appearance occurred over 24 h. In addition, optical microscopy confirmed that no crystals were present in the sample. Polymer 2 had successfully inhibited the crystallization of the cyflufenamid over the duration of the experiment. Mandipropamid DC formulations [A 13]

[0116] In formulation containing Atlox 4913 as a CGI, crystallization was obvious after 24 h. The formulation was inhomogeneous after approx. 5 h and sedimented. Optical microscopy revealed the presence of needle-like crystals.

[0117] However, when using polymer 3 in place of Atlox 4913, no change in formulation appearance occurred over 24 h. In addition, optical microscopy confirmed that no crystals were present in the sample. Polymer 3 had successfully inhibited the crystallization of the Mandipropamid over the duration of the experiment.

[0118] Emulsifiable Concentrate (EC) Formulations

[0119] Polymers 1 and 5 were further investigated in model Pydiflumetofen [AI1] EC formulations. Their compositions can be seen in Table 6. Formulations were prepared with and without polymer. The polymer concentration was 7%w / w.

[0120] The formulations were prepared with a water immiscible solvent of anisaldehyde and the results set out in Table 4.

[0121] Table 4

[0122] In the formulation containing no polymer, crystallization was obvious after 24 h. Large white crystals were present in the sample. However, when using polymers 1 and 5, no change in formulation appearance occurred over 24 h and Polymers 1 and 5 provided CGI activity for these EC formulations.

[0123] Test at high pH levels

[0124] Atlox 4913 comprises a significantly number of carboxylic acid units and can exhibit sensitivity when used in high pH conditions.

[0125] Two Oxithiapiprolin [AI4] DC formulations DC 10 and 11 were prepared to test the effectiveness of the described dispersants at high pH (300 ppm bicarbonate solution, pH = 8). Their compositions can be seen in Table 5 where the levels of Polymer 1 and Atlox 4913 were kept at 5.9%w / w.

[0126] Table 5 In the formulation containing Atlox 4913 (DC 10), crystallization was obvious after 48 hours, the dilution was inhomogeneous and large oval-shaped crystals were observed under the optical microscope. However, when using polymer 1 no change in formulation appearance occurred over 48 h and crystal growth was prevented.

[0127] It can be seen that the compositions according to the invention demonstrate improved crystal growth inhibition compared to those in the art.

[0128] The invention is defined by the claims.

Claims

Claims1 . An agrochemical composition comprising: a copolymer consisting of two monomers represented by the following formulae wherein(I) is a hydrophobic monomer and (II) is a hydrophilic monomerwhereinR1is selected from hydrogen or methyl;R2is a C1-6 alkyl group;R3is selected from hydrogen or methyl;R4is selected from:-CONHm(Ci-6 alkyl)nwhere m = 0,1 or 2, n = 0, 1 or 2,-Cs heterocyclic ketone,-C(O)O(CH2CH2O)PH wherein p = 1 to 50, -C(O)O(CH2CH2O)PR5wherein p = 1 to 20 and where R5is C1-6 alkyl.

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

3. A composition according to any of claims 1 or 2, wherein the polymer is the ratio of monomer (I): monomer (II) from 80:20 to 20:80 %w / w.

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

5. A composition according to any of the preceding claims, further comprising of a surfactant, preferably wherein the surfactant is a non-ionic surfactant and / or an anionic surfactant.

6. A composition according to claims 5, wherein the surfactant is present in an amount from 0.01 to 20 %w / w.

7. A composition according to any of the preceding claims wherein the composition comprises an active ingredient.

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

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

10. A composition according to any of the preceding claims comprising a non-aqueous solvent.

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

12. A method of preparing a composition according to claims 1 to 10.

13. Use of a polymer consisting of two monomers represented by the following formulae wherein (I) is a hydrophobic monomer and (II) is a hydrophilic monomerwhereinR1is selected from hydrogen or methyl;R2is a C1-6 alkyl group,R3is selected from hydrogen or methyl;R4is selected from:-CONHm(Ci-6 alkyl)nwhere m = 0,1 or 2 n = 0, 1 or 2,-Cs heterocyclic ketone,-C(O)O(CH2CH2O)PH wherein p = 1 to 50,-C(O)O(CH2CH2O)PR5wherein p = 1 to 20 and where R5is C1-6 alkyl for inhibiting crystal growth formation of active ingredients.

14. Use according to claim 13 where the polymer is diluted in water, preferably in a solution with a pH from 8 to 14.

15. Use of a composition as defined in claims 1 to 10 for the treatment of weeds, pests, and / or fungi.