WO2005018325A1

WO2005018325A1 - Fungicidal method

Info

Publication number: WO2005018325A1
Application number: PCT/GB2004/003456
Authority: WO
Inventors: Leslie Francis May; Patrick Joseph Mulqueen
Original assignee: Syngenta Limited
Priority date: 2003-08-19
Filing date: 2004-08-10
Publication date: 2005-03-03
Also published as: GB0319933D0

Abstract

A method of combating phytopathogenic diseases on plants and harvested food crops which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a fungicidal polymer obtained by the polymerization of a monomer of the general formula (1): wherein X is O or NR4, Y is a C1-5 aliphatic hydrocarbyl group, R1 is H or CH3, and R2, R3 and R4 are independently H or C1 -7 aliphatic hydrocarbyl groups is disclosed.

Description

FUNGICIDAL METHOD

This invention relates to a method of combating phytopathogenic diseases on plants and harvested food crops. More particularly, it relates to the use of certain polymers as plant and food crop fungicides and to fungicidal compositions containing these polymers. The biocidal use of certain polymers known as sustainable active microbicidal (SAM)-Polymers is described in an article in GIT Labor-Fachzeitschrift (2002), 46(4), 452, 454-456. These polymers are said to be suitable for incorporation into paints, coatings and plastic products. Examples of such polymers are described in WO 01/18077 and are commercially available under the trade names AML A T 100 and LEVLAGO T 100. (SAM-polymers, AMENTA and LLMAGO are registered trade marks of CREAVIS Gesellschaft fur Technologie und Innovation mbH). Biocides are substances that kill or inhibit the growth of microorganisms such as bacteria, moulds, slimes, fungi, etc. They are normally used in situations where they are not a danger to plants or animals, for example, on ships' hulls, building facades and plastics surfaces and in paints and varnishes. It is, therefore, unnecessary for them to act specifically against their target organisms and they are often phytotoxic, toxic to humans, skin sensitisers or irritants. Consequently, most biocides are not suitable for use as plant fungicides. In any case, they are targeted at different organisms and would not be expected to be suitable for use as plant fungicides or have an acceptable toxicological profile. Most commercial synthetic fungicides are monomeric organic compounds or organometallic compounds. It has not been known before to use polymers as plant fungicides. As plants build resistance to constantly used fungicides, there is a continuing need for alternative fungicides and preferably ones that have a new mode of action. The present invention is concerned with the provision of alternative plant fungicides and alternative methods of combating phytopathogenic fungi. According to the present invention, there is provided a method of combating phytopathogenic diseases on plants and harvested food crops which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a fungicidal polymer obtained by the polymerization of a monomer of the general formula (1):

(1 ) wherein X is O or NR⁴, Y is a C_1-5 aliphatic hydrocarbyl group, R¹ is H or CH₃, and R², R³ and R⁴ are independently H or Cι_-7 aliphatic hydrocarbyl groups. The hydrocarbyl groups may be branched or unbranched. Typically they are alkyl groups or, in the case of Y, an alkylene group. For instance, R² and R³ are independently H or C alkyl and Y is C_1- alkylene. Examples of Y are ethylene and w-propylene and examples the alkyl value of R and R are methyl, ethyl, n-propyl, wo-propyl, w-butyl, sec-butyl, zso-butyl and tert- butyl. Thus, in one embodiment of the monomer of formula (1), X is O, Y is Cι_-3 alkylene (typically ethylene or propylene), R¹ is H or CH₃ and R² and R³ are independently H or C_1- alkyl (typically R² is H and R³ is tert-butyl or R² and R³ are both methyl or both ethyl). In another embodiment of the monomer of formula (1), X is NH, Y is C_1-3 alkylene (typically ethylene or propylene), R¹ is H or CH₃ and R² and R³ are independently H or CM alkyl (typically R² is H and R³ is tert-butyl or R² and R³ are both methyl or both ethyl). Examples of the monomer of the formula (1) are 2-(tert-butylamino)efhyl mefhacrylate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)methyl mefh- acrylate, 2-(tert-butylamino)efhyl acrylate, 3-(dimethylamino)propyl acrylate, 2-(diethyl- amino)ethyl acrylate, 2-(dimethylamino)ethyl acrylate, N-(3-dimefhylaminopropyl)- methacrylamide, N-(3-diethylaminopropyl)methacrylamide, 7V-(3-dimethylaminopropyl)- acrylamide and V-(3-diethylaminopropyl)acrylamide. The fungicidal polymers of the invention are prepared by the homopolymerization of the monomer of formula (1) using conventional free radical- or irradiation-initiated polymerization chemistry. The preparation is more fully described and exemplified in, for example, WO 01/18077 and US 2002/0168473. The weight-average molecular weight of the polymers is from 10,000 to 7,000,000, for example from 20,000 to 5,000,000 and typically from 30,000 to 500,000. The fungicidal polymer used in the invention may be prepared as a solution in a suitable solvent, as a solid in powdered granular form or as an aqueous dispersion and formulated for use as a fungicide using formulation techniques well established in the art and described in more detail later. Alternatively it may be prepared by emulsion polymerization as described in WO 02/069709. The emulsion polymerization is carried out by polymerizing one or more monomers of the formula 1 and optionally one or more other monomers in water with an emulsifier using a thermal or photochemical radical starter. Ionic or nonionic compounds, such as polyethylene glycol derivatives, polyethylene glycol ether, especially 4-octylphenol polyethoxylate (sold under the trade name 'Triton'), alkylbenzol sulphonates, alkylsulphates, alkyl sulphonates, ethoxylated fatty alcohols, alkyl phenols and fatty acids may be used as emulsifiers. The fungicidal polymers prepared in this way tend to have higher molecular weights than polymers prepared by solution or substance polymerization. Specific examples of polymers used in the invention, which are commercially available, are Amina® T100, in the form of a white powder, and Limago® T100, in the form of an aqueous dispersion. Both are polymers formed from the monomer 2-{tert- butylamino)ethyl methacrylate and both are obtainable from Creavis Technologies & Innovation, Paul-Baumann-Strasse 1, 45764 Marl, Germany. The fungicidal polymers may be formulated for plant fungicidal use either alone or in admixture with other polymers, for example, polyurethanes, PVCs, polyolefins such as polyethylenes or polypropylenes, polysiloxanes, polystyrenes, other polyacrylates or polymefhacryates or other synthetic materials such as polyamides or polyterephthalates. When mixed with other polymers the amount of the fungicidal polymer obtained from the monomer of formula (1) will normally be present in amounts of from 0.2 to 90 % by weight, preferably from 40 to 90% by weight, of the total polymer content. The compositions of this invention may also contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity. The addition of another active ingredient may provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the fungicidal polymer, or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of fungicidal compounds which may be included in the composition of the invention are AC 382042 (N-(l-cyano-l,2-dimethylpropyl)-2-(2,4-dichlorophenoxy) propionamide), acibenzolar-S-mefhyl, alanycarb, aldimorph, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, biloxazol, bitertanol, blasticidin S, boscalid (new name for nicobifen), bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA 41396, CGA 41397, chinomefhionate, chlorbenzthiazone, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquino- late, copper sulphate, copper tallate, and Bordeaux mixture, cyamidazosulfamid, cyazofamid (IKF-916), cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1,1 '-dioxide, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O, O-di-wo-propyl-5-benzyl thiophosphate, dimefluazole, dimetconazole, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethyl (Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β- alaninate, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil (AC 382042), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LYl 86054, LY211795, LY 248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metalaxyl M, metconazole, metiram, metiram-zinc, metominostrobin, metrafenone, MON65500 (N-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3- carboxamide), myclobutanil, NTN0301, neoasozin, nickel dimethyldithiocarbamate, nitrothale-isopropyl, nuarimol, ofurace, organomercury compounds, orysastrobin, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosphorus acids, phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, silthiofam (MON 65500), S-imazalil, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, tiadinil, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb, ziram, zoxamide and compounds of the formulae:

The fungicidal polymers are active fungicides in their own right and may be used to control one or more of the following pathogens: Pyricularia oryzae {Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia triticina (or recondita), Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Blumeria (or Erysiphe) graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. Pyrenophora spp.), Rhynchosporium spp., Mycosphaerella graminicola (Septoria tritici) and Leptosphaeria nodorum (Phaeosphaeria nodorum, Stagonospora nodorum or Septoria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat, cucurbits and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Stemphylium spp.

{Pleospora spp.) on apples, pears, onions and other hosts; summer diseases (for example bitter rot {Glomerella cingulatά), black rot or frogeye leaf spot {Botryosphaeria obtusa), Brooks fruit spot {Mycosphaerella pomi), Cedar apple rust {Gymnosporangium juniperi- virginianae), sooty blotch {Gloeodes pomigena), flyspeck {Schizothyrium pomi) and white rot {Botryosphaeria dothidea)) on apples and pears; Plasmopara viticola on vines; other downy mildews, such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythium spp. (including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf and other Rhizoctonia spp. on various hosts such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila and Stereum hirsutum; other pathogens on trees (for example Lophodermium seditiosum), notably Cephaloascus fragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; and fungal vectors of viral diseases (for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV) and Polymyxa betae on sugar beet as the vector of rhizomania). The fungicidal polymers show particularly good activity against Plasmopara species, e.g.Plasmopara viticola, against Leptosphaeria nodorum and against Fusarium graminearum. The invention therefore provides the use of the fungicidal polymers of the invention for combating phytopathogenic diseases on plants and harvested food crops. The term "plant" as used herein includes seedlings, grasses, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments. The term "harvested food crops" means the edible product of any plant stored for human or animal consumption, including grain, fruit and seed. The fungicidal polymers are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition. In order to apply a fungicidal polymer of the invention to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other growth medium, the polymer is usually formulated into a composition which includes, in addition to the polymer, a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals that are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of the fungicidal polymer. The composition is generally used for the control of fungi such that the fungicidal polymer is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare. When used in a seed dressing, the fungicidal polymer is used at a rate of 0.0001 g to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed. When used to treat harvested crops, such as oranges, grapefruit and apples, by dipping or rolling the crop in a liquid medium, typically in an aqueous medium, the concentration of the polymer in the liquid medium will be in the range of O.Olg to 5,000g, usually in the range of 0.2g to 2,000g, for example 0.2g to 200g, and typically in the range of from 25g to 50g of polymer in 100 litres of liquid. In another aspect the present invention provides a fungicidal composition comprising a fungicidally effective amount of a polymer of the invention and an agriculturally acceptable carrier or diluent therefor. In a still further aspect the invention provides a method of combating and controlling fungi at a locus, which comprises treating the fungi, or the locus of the fungi with a fungicidally effective amount of a composition comprising a fungicidally effective amount of a polymer as defined in claim 1 and an agriculturally acceptable carrier. The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the fungicidal polymer. Dustable powders (DP) may be prepared by mixing the fungicidal polymer with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder. Soluble powders (SP) may be prepared by mixing the fungicidal polymer with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG). Wettable powders (WP) may be prepared by mixing the fungicidal polymer with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG). Granules (GR) may be formed either by granulating a mixture of the fungicidal polymer and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing the fungicidal polymer (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing the fungicidal polymer (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsoφtion include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent). Dispersible Concentrates (DC) may be prepared by dissolving the fungicidal polymer in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank). Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving the fungicidal polymer in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone), alcohols (such as benzyl alcohol, fiirfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N- octylpyrrolidone), dimethyl amides of fatty acids (such as C₈-Cιo fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining the fungicidal polymer either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents that have a low solubility in water. Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a fhermodynamically stable isotropic liquid formulation. The fungicidal polymer is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion. Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of the fungicidal polymer. SCs may be prepared by ball or bead milling the solid fungicidal polymer in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the polymer. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, the fungicidal polymer may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product. Aerosol formulations comprise the fungicidal polymer and a suitable propellant (for example w-butane). The fungicidal polymer may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps. The fungicidal polymer may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the polymer. The compositions may provide for controlled release of the fungicidal polymer and they may be used for seed treatment. The fungicidal polymer may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the polymer. A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of the fungicidal polymer. Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of the fungicidal polymer). The fungicidal polymer may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS) or a solution (LS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier). Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type. Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts. Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecyl- benzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-wøpropyl- and tri-wøpropyl-naphfhalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3- carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphos- phoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates. Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins. Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite). The fungicidal polymer may be applied by any of the known means of applying fungicidal compounds. For example, it may be applied, formulated or unformulated, to any part of the plant, including the foliage, stems, ears, seed heads, fruits, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally or paddy water), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or smoke or applied through distribution or incoφoration of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment. The fungicidal polymer may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems. Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the fungicidal polymer, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs and WGs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts the fungicidal polymer (for example 0.0001 to 10%, by weight) depending upon the puφose for which they are to be used. The fungicidal polymer may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the fungicidal polymer. The invention therefore also provides a fertiliser composition comprising a fertiliser and a fungicidally effective amount of a fungicidal polymer of the invention. The fungicidal polymer may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases. Another active ingredient may be used in admixture with the fungicidal polymer of the invention that has significantly different physical, chemical or biological properties to the polymer such that it does not easily lend itself to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one of the active ingredient and polymer is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid ingredient as a suspension (using a preparation analogous to that of an SC) and dispersing the liquid ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation. EXAMPLE This Example illustrates the fungicidal properties of the fungicidal polymers of the invention. The polymers Amina® T100 and Limago® T100 (obtained from Creavis Technologies & Innovation) were tested against a variety of fungal foliar, seed, fruit and post harvest diseases of food crops. The techniques employed were as follows. Plants were either grown in John Innes Potting Compost No. 2 in 4cm diameter, 3.5cm depth minipots or on an artificial, cellulose based growing medium. For tests on fruit the fruit (or fruit pieces) were washed/surface sterilised and placed in sterile multi well plates for the duration of the tests. For tests on wheat ear diseases the plants were grown in 10cm pots. Liquid culture tests were conducted in 96 well plates using artificial media (Vogel's minimal media) inoculated with spores/mycelial fragments of the pathogens being evaluated. The test polymers were individually formulated as a solution either in acetone or acetone/ethanol (1 : 1 by volume), which was diluted in reverse osmosis water, to the required concentration immediately before use. When foliar sprays were applied to monocotyledonous crops, TWEEN 20 (0.05% by volume) was added. TWEEN is a registered trade mark. Individual polymers were applied as a foliar application (where the chemical solution was applied to the foliage/ears of the test plants by spraying the target to maximum droplet retention); as a surface application (where the fruit was dipped or rolled in the chemical solution); or as a liquid culture application (where the chemical was dispensed into a 96 well microtitre plate and diluted to the appropriate rate with a mixture of fungal inoculum and media). Whole plant tests were carried out against Plasmopara viticola (PLASVI) on vines; Phytophthora infestans lycopersici (PHYTIN) on tomatoes; Blumeria graminis f.sp. tritici (ERYSGT), Stagonospora nodorum (LEPTNO) and Puccinia triticina (PUCCRT), on wheat. Ear disease tests were carried out against Fusarium graminearum (GL3BZE) on ears of wheat that had entered the flowering stage. Chemical applications to whole plants were made 6-24 hours before inoculation. Surface application tests were carried out using "plugs" of oranges or whole pea fruit. Pathogens evaluated were Penicillium expansum (PENTEX) and Botrytis cinerea (BOTRCI). The plants / fruits were inoculated with a calibrated fungal spore suspension 4-24 hours after chemical application. Each treatment was applied to two or more replicate plants/fruits. Liquid culture tests were carried out against Septoria tritici (SEPTTR), Phytophthora infestans (PHYTL ) and Fusarium graminearum (GD3BZE). Microtitre plates were prepared by adding chemical samples dissolved in acetone at the appropriate rates to sterile media. After 24 hours plates were inoculated by adding a mixture of fungal inoculum (spores/mycelium), dispersed in sterile media, to individual wells. After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. For Plasmopara viticola, the plants were reincubated under high humidity conditions for 24hours prior to assessment. The time period between chemical application and assessment varied from five to fourteen days according to the disease and environment. However, each individual disease was assessed after the same time period for all polymers. At assessment, liquid culture assays were assessed visually. Wells containing treatments were compared to control wells and scored as either 0, 55 or 100% disease control. Results for individual replicates were meaned to provide mean disease control values. For tests on plant material the disease level present (that is, the percentage leaf area, ear area or fruit surface area covered by actively sporulating disease) or percentage of infected plants, ears or fruit per pot or test unit was assessed visually. For each treatment, the assessed values for all replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by the method described hereinafter, providing a PRCO (Percentage Reduction from Control) value. METHOD This method uses banded assessment values. The mean disease values are banded in the manner shown below. If the disease level value falls exactly mid-way between two of the points, the result will be the lower of the two points. 0 = 0% disease present 10 = 5.1-10%) disease present 1 = 0.1-1%) disease present 20 = 10.1-20%) disease present 3 = 1.1-3% disease present 30 = 20.1-30% disease present 5 = 3.1-5% disease present 60 = 30.1-60%) disease present 90 = 60.1-100% disease present

An example of a typical banded calculation is as follows:

Mean disease level for treatment A = 25 % Therefore banded mean disease level for treatment A = 30 Mean disease level on untreated controls = 85%> Therefore banded mean disease level on untreated controls = 90

PRCO = 100 - { Banded mean disease level for treatment A } x 100 {Banded mean disease level on untreated controls}

100 - (30 x 100) 66.7 90

The PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 67. Example results, derived as described above, are shown below. TABLE 1 : Tests on Whole Plants

Key to Table 1 : * 300ppm rate was evaluated in a separate test series PLASVI = Plasmopara viticola PUCCRT = Puccinia triticina LEPTNO = Leptosphaeria nodorum

TABLE 2: Tests in Liquid Media

Key to Table 2:

GIBBZE = Fusarium graminearum TABLE 3: Tests on Wheat Ears

Key to Table 3: GLBBZE = Fusarium graminearum

Claims

CLAΓMS

1. A method of combating phytopathogenic diseases on plants and harvested food crops which comprises applying to a plant, to the seed of a plant, to the locus of the plant or seed or to a harvested food crop a fungicidally effective amount of a fungicidal polymer obtained by the polymerization of a monomer of the general formula (1):

(1 ) wherein X is O or E , Y is a C_1-5 aliphatic hydrocarbyl group, R¹ is H or CH₃, and R², R³ and R⁴ are independently H or Cι_-7 aliphatic hydrocarbyl groups.

A method according to claim 1 wherein X is O, Y is Cι_-3 alkylene, R¹ is H or CH and R² and R³ are independently H or C alkyl.

3. A method according to claim 1 wherein X is NH, Y is Cι_-3 alkylene, R 1 i ^■s H or CH and R² and R³ are independently H or C_M alkyl.

4. A method according to claim 1 wherein the monomer of the formula (1) is selected from the group consisting of 2-(tert-butylamino)efhyl methacrylate, 2- (diethylamino)ethyl methacrylate, 2-(dimethylamino)methyl methacrylate, 2-{tert- butylamino)efhyl acrylate, 3-(dimefhylamino)propyl acrylate, 2-(diethylamino)- ethyl acrylate, 2-(dimethylamino)ethyl acrylate, N-(3-dimefhylaminopropyl)- mefhacrylamide, N-(3-diethylaminopropyl)methacrylamide, 7V-(3-dimethyl- aminopropyl)acrylamide are N-(3-diethylaminopropyl)acrylamide.

5. A method according to any one of the preceding claims wherein the fungicidal polymer is used in admixture with one or more other polymers selected from the group consisting of polyurefhanes, PVCs, ployolefins, polysiloxanes, polystyrenes, polyacrylates, polymethacryates, polyamides or polyterephthalates.

6. A method according to any one of the preceding claims wherein the fungicidal polymer is used in admixture with one or more other compounds having biological activity.

7. A method according to claim 6 wherein the other compound is another fungicide.

8. A plant fungicidal composition that comprises a fungicidally effective amount of a polymer as defined in claim 1 and an agriculturally acceptable carrier or diluent.

9. A composition according to claim 8 which additionally comprises another active ingredient.

10. A composition according to claim 9 wherein the other active ingredient is a fungicidal compound.

11. The use of a polymer as defined in claim 1 for combating phytopathogenic diseases on plants and harvested food crops.