Fungicidal formulations containing copper compounds

Abstract

To provide an industrially viable and cost-efficient process for large-scale preparation of copper fungicidal compounds selected from copper oxide, copper oxychloride, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper silicate and tribasic copper sulfate.SOLUTION: A fungicidal formulation comprises: at least one copper fungicide having a D50 particle size of 3-20 micrometers; and at least one agrochemically acceptable excipient.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of copper fungicidal compounds. More specifically, the present invention relates to a continuous process for the manufacture of tribasic copper sulfate (TBCS). [Background technology]

[0002] Tribasic copper sulfate (TBCS, represented by the formula Cu(OH)SO) is a well-known copper fungicide that has a variety of applications including, but not limited to, use as a protective fungicide to control bacterial and fungal diseases of fruits, vegetables, nuts, and crops.

[0003] The process for the production of copper compounds disclosed in WO 91 / 01942 comprises the step of contacting metallic copper with an aqueous solution consisting essentially of oxygen or an oxygen-containing gas and water, in which is a soluble ammonium salt up to a concentration of its solubility limit together with an amount of ammonia such that said solution is initially alkaline, whereby as a result of said contacting, said metallic copper is initially dissolved to form copper amines, said amine formation proceeding until a saturation concentration of said amines is reached, whereafter said amines are continuously decomposed to form water-insoluble tribasic salts.

[0004] The process is carried out in a reactor equipped with a high speed (minimum tip speed 500 meters / min) agitator. A grid separates the copper from the stirred suspension. In this process, all steps of the process are carried out in the same reactor / vessel and the use of high speed agitators makes the addition of copper during the reaction difficult. The process requires a large consumption of electrical energy.

[0005] There is a need to develop a simple, cost-effective and commercially viable process for the large-scale preparation of copper compounds.To meet this need, the present invention provides an industrially viable and cost-effective process for the large-scale preparation of copper fungicide compounds, preferably selected from copper oxide, basic copper chloride, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper silicate, and tribasic copper sulfate.This process avoids the use of complicated and expensive methods.The present invention provides an industrially feasible large-scale preparation of copper compounds, particularly TBCS.The present invention also provides formulations containing the copper compounds prepared according to the process of the present invention, kits containing such copper compounds and, optionally, at least one or more fungicides, and methods of use thereof. Summary of the Invention

[0006] In one aspect, the present invention provides a simple and economical process for the production of copper compounds or copper fungicides, which is easily scalable on a commercial scale.

[0007] In another aspect, the present invention provides a process for preparing a copper fungicide, the process comprising lowering the pH of a copper fungicide precursor in the absence of copper metal.

[0008] In another aspect, the present invention provides a process for preparing a copper fungicide, the process comprising: a) reacting metallic copper with a tetraamine copper complex to form a diamine copper complex; b) oxidizing the diamine copper complex to form a copper fungicide precursor; c) adjusting the pH of the copper fungicide precursor in the absence of copper to form the copper fungicide.

[0009] In another aspect, the present invention provides a commercial process for the production of copper compounds, which comprises separate reaction steps for copper corrosion and pH adjustment.

[0010] In another aspect, the present invention provides a method for preparing a copper fungicide, the method comprising lowering the pH of a copper fungicide precursor complex suspension using a pH adjuster.

[0011] In another aspect, the present invention provides a continuous process for preparing a copper fungicide compound comprising reacting metallic copper with a tetraamine copper complex to form a diamine copper complex in a first vessel, oxidizing the copper diamine complex to obtain a copper fungicide precursor as a copper tetraamine complex, continuously extracting the copper fungicide precursor from a suspension of the copper tetraamine complex, and adjusting the pH using a suitable pH adjuster in a second reactor.

[0012] In another aspect, the present invention provides a method for producing a composition comprising: (a) at least one copper fungicide prepared by a process comprising adjusting the pH of a copper fungicide precursor in the absence of copper; (b) at least a pesticidally acceptable excipient.

[0013] In yet another aspect, the present invention provides a process for preparing a fungicidal formulation, the process comprising: a) preparing a copper fungicide by a process comprising adjusting the pH of a copper fungicide precursor in the absence of copper; b) mixing the prepared copper fungicide with at least one pesticidally acceptable excipient to prepare a fungicide formulation.

[0014] In another aspect, the present invention provides a process for preparing a fungicidal formulation, the process comprising: a) preparing a copper fungicide by a process comprising adjusting the pH of a copper fungicide precursor in the absence of copper; b) adding at least another pesticidal substance to the copper fungicide; c) adding at least one pesticidally acceptable excipient to prepare a fungicidal formulation.

[0015] In another aspect, the present invention provides a kit comprising a fungicide formulation, the formulation comprising at least one copper fungicide prepared by a process comprising adjusting the pH of a copper fungicide precursor in the absence of copper, and at least a pesticidally acceptable excipient.

[0016] In another aspect, the present invention provides a kit comprising at least one copper fungicide selected from copper oxide, basic copper chloride, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper silicate, and tribasic copper sulfate produced by the processes described herein. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a process flow diagram according to one embodiment of the present invention. [Diagram 2] FIG. 1 is a general design of a continuous reaction system for producing TBCS according to one embodiment of the present invention. [Diagram 3] 1 is a flow chart of a process according to one aspect of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] These and other features, aspects, and advantages of the present invention may be further understood and / or illustrated in consideration of the following detailed description in conjunction with the accompanying drawings.

[0019] For purposes of the following detailed description, it will be understood that the present invention may assume various alternative modifications and sequence of steps, unless expressly specified to the contrary. Further, other than in any operational examples, or unless otherwise indicated, all numbers expressing amounts of materials / ingredients used herein, for example, should be understood as being modified in all instances by the term "about."

[0020] Therefore, before describing the present invention in detail, it should be understood that the present invention is not limited to the specifically exemplified system or process parameters, which may of course vary. It should be noted that, unless otherwise specified, all percentages given in this specification and the appended claims refer to weight percent of the total composition. It should also be understood that the terms used herein are for the purpose of describing certain embodiments of the present invention, and are not intended to limit the scope of the present invention in any manner. The use of examples anywhere in this specification, including examples of any term discussed herein, is merely illustrative and does not limit the scope and meaning of the present invention or of any exemplified term. Similarly, the present invention is not limited to the various embodiments given herein. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In case of conflict, the present document, including definitions, will control.

[0021] It should also be noted that, as used herein, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits, under particular circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

[0022] As used herein, the terms "comprising," "including," "having," "containing," "involving," and the like, should be understood to be open-ended, i.e., to mean including without limitation.

[0023] As used herein, the term "reactor" is defined as an apparatus used to carry out chemical reactions.

[0024] As used herein, the term "vessel" or "column" is any walled means in which a fluid can be contained and transported.

[0025] The present invention provides a simple, cost-effective and industrially feasible process for the preparation of copper compounds or copper fungicides.

[0026] Thus, in one aspect, the present invention provides a process for the preparation of a copper fungicide, the method comprising adjusting the pH of a copper fungicide precursor in the absence of copper.

[0027] In certain embodiments, adjusting the pH of a copper fungicide precursor comprises lowering the pH of such copper fungicide precursor in the presence of a neutralizing agent.

[0028] In certain embodiments, the copper fungicide is copper oxide and the copper fungicide precursor is a tetramine copper complex.

[0029] In certain embodiments, adjusting the pH of the copper fungicide precursor in the absence of copper is carried out in the absence of a neutralizing agent.

[0030] In one embodiment, the copper fungicide precursor is copper sulfate.

[0031] In certain embodiments, the process is carried out in the presence of a base.

[0032] In certain embodiments, the copper fungicide is basic copper chloride, the copper fungicide precursor is a tetraamine copper complex, and the neutralizing agent is hydrochloric acid.

[0033] In one embodiment, the copper fungicide is copper acetate, the copper fungicide precursor is copper oxide, copper sulfate or copper carbonate, and the neutralizing agent is acetic acid.

[0034] In one embodiment, the copper fungicide is copper carbonate and the neutralizing agent is carbon dioxide or carbon dioxide.

[0035] In one embodiment, the copper fungicide is copper hydroxide and the neutralizing agent is excess water.

[0036] In one embodiment, the copper fungicide is copper naphthenate and the neutralizing agent is naphthenic acid.

[0037] In one embodiment, the copper fungicide is copper oleate and the neutralizing agent is oleic acid.

[0038] In one embodiment, the copper fungicide is copper silicate and the neutralizing agent is silicic acid.

[0039] In certain embodiments, the copper fungicide is tribasic copper sulfate, the copper fungicide precursor is a tetraamine copper complex, and the neutralizing agent is sulfuric acid.

[0040] In some embodiments, the process is carried out in the absence of copper by carrying out the process in a reactor made of a material other than copper.

[0041] In certain embodiments, the tetraamine copper complexes are prepared by reacting a diamine copper complex with oxygen.

[0042] In certain embodiments, the step of preparing a tetraamine copper complex is carried out in a copper vessel.

[0043] In some embodiments, the steps of preparing the copper fungicide and the tetraamine copper complex are carried out separately.

[0044] In certain embodiments, the diamine copper complex is prepared by reacting a tetraamine copper complex with copper.

[0045] In certain embodiments, the step of preparing a diamine copper complex is carried out in a copper vessel.

[0046] In certain embodiments, the process step of preparing the copper fungicide is carried out separately from the process step of preparing the tetraamine copper complex or separately from the process step of preparing the diamine copper complex.

[0047] In some embodiments, the process steps of preparing the tetraamine copper complex and preparing the diamine copper complex are carried out in the same vessel, hi some embodiments, the vessel is a copper vessel.

[0048] In certain embodiments, the reaction vessel is a copper-based column reactor.

[0049] In one embodiment, the process involves injecting the starting material, tetraamine copper complex, into the bottom of a column reactor.

[0050] In some embodiments, the process includes introducing oxygen into the bottom of the column reactor.

[0051] In certain embodiments, any one or all of the process steps are carried out in an ammonium sulfate solution.

[0052] In an embodiment, the present invention provides a process for preparing a copper fungicide, the process comprising: (a) preparing a diamine copper complex by reacting a tetraamine copper complex with copper; (b) reacting the diamine copper complex with oxygen to form a tetraamine copper complex; (c) adjusting the pH of the tetraamine copper complex of step (b) in the absence of copper to form the copper fungicide.

[0053] In one embodiment, steps (a) and (b) are carried out together in a copper vessel.

[0054] In certain embodiments, step (c) is carried out separately in the absence of copper metal.

[0055] In certain embodiments, adjusting the pH of the tetraamine copper complex comprises lowering the pH of the tetraamine copper complex solution in the presence of a neutralizing agent.

[0056] In certain embodiments, step (c) is carried out in the absence of copper by carrying out the step in a reactor made of a material other than copper.

[0057] In one embodiment, the copper fungicide is tribasic copper sulfate and the neutralizing agent is sulfuric acid.

[0058] In another aspect, the present invention provides a process for producing a copper fungicide selected from copper oxide, basic copper chloride, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper silicate, and tribasic copper sulfate, comprising adjusting the pH of a copper fungicide precursor in the absence of copper.

[0059] In another aspect, the present invention provides a commercial process for the manufacture of copper fungicide compounds, which comprises separate steps of copper fungicide precursor preparation and pH adjustment.

[0060] In one embodiment, the present invention provides a process for producing a copper fungicide, which comprises reacting copper with a copper complex and oxidizing in one vessel.

[0061] In another embodiment, the copper fungicide is copper oxide, the copper fungicide precursor is a tetramine copper complex, and the process is carried out in the absence of a neutralizing agent.

[0062] In another embodiment, the copper fungicide is copper hydroxide, the copper fungicide precursor is a tetramine copper complex, and the process is carried out in the absence of a neutralizing agent.

[0063] In certain embodiments, the copper fungicide is basic copper chloride, the copper fungicide precursor is a tetraamine copper complex, and the neutralizing agent is hydrochloric acid.

[0064] In one embodiment, the copper fungicide is copper acetate, the copper fungicide precursor is copper oxide or copper carbonate, and the neutralizing agent is acetic acid.

[0065] In one embodiment, the copper fungicide is copper carbonate and the neutralizing agent is carbon dioxide or carbon dioxide.

[0066] In one embodiment, the copper fungicide is copper naphthenate and the neutralizing agent is naphthenic acid.

[0067] In one embodiment, the copper fungicide is copper oleate and the neutralizing agent is oleic acid.

[0068] In one embodiment, the copper fungicide is copper silicate and the neutralizing agent is silicic acid.

[0069] In one embodiment, the present invention provides a process for producing a copper fungicide, comprising lowering the pH of a copper fungicide precursor with a suitable pH adjuster.

[0070] In another embodiment, adjusting the pH of the copper complex comprises lowering the pH of a suspension containing a copper fungicide precursor using a suitable pH adjuster to obtain the desired copper compound.

[0071] In some embodiments, the pH adjustment of the copper fungicide precursor is carried out in the absence of copper by performing it in a reactor made of a material other than copper.

[0072] In one aspect, the present invention provides a process for preparing a copper fungicide comprising the steps of: a) reacting metallic copper with a copper tetraamine complex to obtain a copper diamine complex; b) oxidizing the copper diamine complex to obtain a copper fungicide precursor; c) adjusting the pH of the copper fungicide precursor in the absence of copper to form the copper fungicide.

[0073] In certain embodiments, the step of adjusting the pH is performed separately.

[0074] In one embodiment, the copper fungicide is tribasic copper sulfate (TBCS).

[0075] In certain embodiments, the copper fungicide precursor is a tetraamine copper complex.

[0076] In one aspect, the present invention provides a process for preparing tribasic copper sulfate.

[0077] In an embodiment, the process for preparing tribasic copper sulfate comprises: a) treating a tetraamine copper complex with metallic copper to obtain a diamine copper complex; b) oxidizing the diamine copper complex to form a tetraamine copper complex; c) adjusting the pH of the tetraamine copper complex to obtain tribasic copper sulfate.

[0078] In one embodiment, steps a) and b) of the process are carried out in a vessel in the presence of copper.

[0079] In certain embodiments, the tetraamine copper complex obtained in step b) is a copper fungicide precursor.

[0080] In certain embodiments, the step c) of adjusting the pH is carried out in the absence of copper. Step (c) is carried out in the absence of copper by carrying out the step in a reactor made of a material other than copper.

[0081] In certain embodiments, adjusting the pH of the tetraamine copper complex comprises lowering the pH of the tetraamine copper complex solution in the presence of a neutralizing agent.

[0082] In one embodiment, the pH of the copper fungicide precursor is reduced to below 7 but above 5 to obtain tribasic copper sulfate.

[0083] In one embodiment, the preparation of tribasic copper sulfate fungicide is triggered by lowering the pH, while tribasic copper sulfate fungicide is produced with recirculation of the copper fungicide precursor at a pH of 8-9. In this embodiment, lowering the pH of the copper fungicide precursor to a pH of 5-7 is the trigger applied to the suspension removed from the first reactor. This trigger results in the production of tribasic copper sulfate with a pH maintained at 8.0-9.0.

[0084] In some embodiments where another copper fungicide is desired, the reduced pH of the copper fungicide may be maintained at a pH of 5.0 to 10.0, preferably 7.0 to 10.0.

[0085] Thus, in one embodiment, the pH of the copper fungicide precursor is maintained at 8-9.

[0086] In some embodiments, the process includes the preparation of tribasic copper sulfate separate from the process steps of preparing the diamine copper complex and the copper fungicide precursor.

[0087] In some embodiments, the reaction to prepare the diamine copper complex and the copper fungicide precursor is carried out in a vessel containing copper metal in any form, e.g., flake, wire, shot, etc., or the vessel is a copper vessel.

[0088] In one embodiment, the preparation of the tetraamine copper complex and the diamine copper complex is carried out in the same vessel at a temperature ranging from about 10 to 100°C, preferably from about 25 to 75°C, and more preferably from about 40 to 60°C.

[0089] The vessel contains copper metal or the reaction vessel is a copper packed column reactor.

[0090] In one embodiment, the process is carried out at a temperature of 50°C.

[0091] In one embodiment, the process for preparing tribasic copper sulfate includes forming copper complexes, i.e., a diamine copper complex and a tetraamine copper complex, and converting the tetraamine copper complex to TBCS.

[0092] In another embodiment, the present invention provides a process for the conversion of a copper fungicide precursor to TBCS, comprising lowering the pH of the copper fungicide precursor using a suitable pH adjuster.

[0093] In certain embodiments, the copper fungicide is tribasic copper sulfate, the copper fungicide precursor is a tetraamine copper complex, and the pH adjuster is an acid.

[0094] In certain embodiments, the copper fungicide is tribasic copper sulfate (TBCS), the copper fungicide precursor is a tetraamine copper complex, and the pH adjuster is sulfuric acid.

[0095] In certain embodiments, the process step of preparing the copper fungicide is carried out separately from the process step of preparing the tetraamine copper complex or separately from the process step of preparing the diamine copper complex.

[0096] In accordance with the present invention, a copper fungicide selected from copper oxide, basic copper chloride, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper silicate, and tribasic copper sulfate is produced by the process described herein.

[0097] In another aspect, the present invention provides a commercial process for preparing tribasic copper sulfate (TBCS), comprising the steps of: (1) subjecting a tetraamine copper complex to copper corrosion to form a diamine copper complex; (2) oxidizing the diamine copper complex; and (3) adjusting the pH of the resulting copper complex using an acid in the absence of copper to obtain TBCS.

[0098] In one embodiment, the first step of the process for preparing tribasic copper sulfate comprises subjecting a tetraamine copper complex to corrosion of copper in a vessel containing copper to form a diamine copper complex, and oxidizing the diamine copper complex in the same vessel to obtain the tetraamine copper complex. In one embodiment, when the target fungicide is tribasic copper sulfate, the tetraamine copper complex is the copper fungicide precursor.

[0099] In certain embodiments, the second step of the process for preparing tribasic copper sulfate comprises adjusting the pH of the tetraamine copper complex in the absence of copper.

[0100] In an embodiment, any one or all of the process steps are carried out in a closed reaction system, preferably in the presence of ammonium sulfate, and preferably at a temperature in the range of about 40-60° C. The pressure in the reactor is maintained at about 0.1-0.4 bar.

[0101] In an embodiment, the reactor system in which the process of the present invention is carried out can include at least three reaction vessels. A first reactor is fed with a suspension containing tetraamine copper complex TBCS and ammonium sulfate. The total copper content in the suspension is in the range of 0.1-20%. In the first reactor, the pH is maintained at 7-10 using a suitable pH adjuster, preferably sulfuric acid, to form TBCS. A second vessel is fed with metallic copper for copper corrosion. The second vessel is provided with an inlet for feeding the suspension of the first reactor, an inlet for oxygen, and an outlet for returning the suspension to the first reactor. The diamine copper complex reacts with oxygen in the second vessel to form tetraamine copper complex. Partial extraction of the tetraamine copper complex from the third reactor and adjustment of the pH using a suitable pH adjuster, preferably sulfuric acid, results in the formation of TBCS.

[0102] Typically, the corrosion reaction for copper is expressed as follows: Cu+Cu(NH3)4=2Cu(NH3)2

[0103] The oxidation of the diamine copper complex is represented as follows: 2Cu(NH3)2+1 / 2O2+H2O+4NH3=2Cu(NH3)4+2OH-

[0104] The above reaction is carried out at a temperature in the range of about 45-55° C., preferably 50° C., and the pH is maintained at 8-9.

[0105] These reactions are carried out in the presence of ammonium sulfate solution.

[0106] Typically, the concentration of ammonium sulfate ranges from 4 to 5%.

[0107] In a further embodiment, the pH adjustment step of the process is carried out at a temperature in the range of about 45-55°C, preferably at a temperature of about 50°C, and the pH is maintained at 5-9, preferably 8-9. The suspension from the neutralization step is returned to the reactor for copper corrosion once the pH has been adjusted. According to one embodiment of the present invention, the process for the preparation of TBCS is represented by the flow diagram in Figure 1.

[0108] In another aspect, the present invention provides a continuous process for producing a desired copper compound, preferably TBCS, wherein the copper corrosion and oxidation reactions of a tetraamine copper complex are carried out in one vessel, adjustment of the pH of the copper complex is carried out in a separate reactor, preferably in the absence of copper, and the reaction products are continuously separated from the reactor and the remaining suspension is recycled to continue the copper corrosion reaction to obtain the desired copper compound.

[0109] In some embodiments, the reaction cycle in the process continues until metallic copper and oxygen are present.

[0110] In one preferred embodiment, the present invention provides a continuous process for the preparation of TBCS, the process comprising: (a) forming a suspension of TBCS, ammonium sulfate, and a tetraamine copper complex in a first reactor and maintaining the pH of the suspension at 8-9; (b) injecting the suspension from the first reactor into a second vessel containing metallic copper for copper corrosion to form a diamine copper complex; (c) providing oxygen into the second vessel for oxidation of the diamine copper complex to form a tetraamine copper complex; (d) returning the suspension from the outlet of the second vessel to the first reactor and maintaining the pH at 8-9 in the presence of sulfuric acid to form TBCS; (e) continuously removing a suspension of TBCS, ammonium sulfate, and tetraamine copper complex from the first reactor to a third reactor; (f) continuously feeding dilute ammonium sulfate to the first reactor; (g) neutralizing the suspension obtained in step 5 with sulfuric acid to obtain TBCS; (h) filtering and washing the product.

[0111] Preferably, in step 7, the conversion of the copper tetraamine complex to TBCS is carried out by lowering the pH to a range of about 5-9.

[0112] The mother liquor obtained in step 8 is fed to the first reactor containing ammonium sulfate and the process is run to continuously produce TBCS.

[0113] During the continuous process, the copper content in the suspension increases. To keep the copper content constant, a continuous dilution is performed by adding ammonium sulfate solution. In addition, the same volume of suspension is removed to keep the volume constant. A typical concentration of solid TBCS in the suspension is about 10% expressed in copper. According to one embodiment of the present invention, the continuous preparation process of TBCS is represented by the flow diagram in FIG. 2.

[0114] In one embodiment, the copper fungicide produced by the present process has a D50 particle size of about 3 to 20 micrometers.

[0115] In one embodiment, the TBCS has a D50 particle size of about 3-20 micrometers.

[0116] In one embodiment, the copper fungicide produced by the present process has a D50 particle size of about 5 to 15 micrometers.

[0117] In one embodiment, the copper fungicide produced by the present process has a D50 particle size of about 8 to 15 micrometers.

[0118] In one embodiment, the copper fungicide produced by the present process has a D50 particle size of less than about 6 micrometers.

[0119] In one embodiment, the copper fungicide produced by the present process has a D80 particle size of less than about 6 micrometers.

[0120] In one embodiment, the copper fungicide produced by the present process has a D80 particle size of less than about 10 micrometers.

[0121] In one embodiment, the copper fungicide produced by the present process has a D85 particle size of less than about 10 micrometers.

[0122] In one embodiment, the copper fungicide produced by the present process has a D90 particle size of less than about 10 micrometers.

[0123] In one embodiment, the copper fungicide is TBCS.

[0124] In one aspect, the present invention provides a method for producing a method for treating a cancer cell comprising: (a) at least one copper fungicide prepared by a process comprising adjusting the pH of a copper fungicide precursor in the absence of copper; (b) at least a pesticidally acceptable excipient.

[0125] In some embodiments, the fungicidal formulation includes at least another pesticidal agent.

[0126] In certain embodiments, the fungicidal formulation comprises at least a second fungicide.

[0127] In one embodiment, the present invention provides a formulation comprising TBCS prepared by the process of the present invention.

[0128] In one embodiment, the present invention provides a water-dispersible and storage stable fungicide formulation of the SC (suspension concentrate), CS (capsule suspension), SE (suspoemulsion) or WG (water-dispersible granule), ZC (mixed form of CS and SC) type, which formulation comprises a copper fungicide prepared by the process described herein.

[0129] In one embodiment, the formulation is a ZC (mixed CS and SC) fungicide formulation.

[0130] In one embodiment, the formulation is a WG (water dispersible granule).

[0131] Typically, the process of preparing fungicide formulations includes the steps of fluidization, grinding, dispersing / wetting agents and blending with inert ingredients.

[0132] In certain embodiments, the formulation may be in the form of a concentrated suspension or wettable granules (spray dried).

[0133] In an embodiment, the present invention provides a process for preparing a fungicidal formulation, the process comprising: (a) preparing a copper fungicide by a process comprising adjusting the pH of a copper fungicide precursor in the absence of copper; (b) mixing the prepared copper fungicide with at least one pesticidally acceptable excipient to prepare a fungicide formulation.

[0134] In another embodiment, the present invention provides a process for preparing a fungicidal formulation, the process comprising: (a) preparing a copper fungicide by a process comprising adjusting the pH of a copper fungicide precursor in the absence of copper; (b) adding at least another pesticidal substance to the copper fungicide prepared in step (a); (c) mixing the prepared copper fungicide with at least one pesticidally acceptable excipient to prepare a fungicide formulation.

[0135] In some embodiments, the second pesticide is a fungicide.

[0136] In certain embodiments, the fungicide formulation comprises a second fungicide selected from: (a) at least one multi-site fungicide selected from: (i) elemental sulfur, (ii) dithiocarbamate fungicides selected from amovam, asomate, azithiram, carbamorph, kufuranib, kuprovam, disulfam, febam, metam, nab, tecoram, thiram, ubacin, ziram, dazomet, ethem, milneb, mancopper, mancozeb, maneb, metiram, polycarbamate, propineb, and zineb; (iii) a phthalimide fungicide selected from folpet, captan, and captafol; (iv) chlorothalonil, (v) sulfamide fungicides selected from dichlorofluanid and tolylfluanid; (vi) a guanidine fungicide selected from dodine, guazatine, and iminoctazine; (vii) anilazine, (viii) dithianone, and (ix) Combinations of these or (b) at least one systemic fungicide selected from the following: (i) a quinone external inhibitor selected from phenamidon, femoxazone, and a strobilurin fungicide selected from the group consisting of azoxystrobin, mandestrobin, cumoxystrobin, enoxastrobin, flufenoxystrobin, pyraoxystrobin, dimoxystrobin, enestrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyrametostrobin, triclopyricarb, phenaminestrobin, pyraclostrobin, and trifloxystrobin; (ii) an internal quinone inhibitor selected from cyazofamid and amisulbrom; (iii) Demethylation inhibitors selected from triflumizole, triforine, pyridinitrile, pyrifenox, fenarimol, nuarimol, and triarimol, as well as climbazole, clotrimazole, imazalil, oxpoconazole, prochloraz, prochlorazmanganese, triflumizole, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, and fenbuconazole. a conazole fungicide selected from the group consisting of fluotrimazole, fluquinconazole, flusilazole, flutriafol, fluconazole, fluconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, pencoconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, perfurazoate and uniconazole-P; (iv) succinate dehydrogenase inhibitors selected from the group consisting of benodanil, flutolanil, mepronil, fluopyram, fenfuram, carboxin, oxycarboxin, thifluzamide, bixafen, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, and boscalid; and (v) Combinations of these.

[0137] In certain embodiments, the formulation comprises at least a third fungicide.

[0138] In one embodiment, the systemic fungicide is a combination of (i) a strobilurin fungicide selected from trifloxystrobin, picoxystrobin, azoxystrobin, or pyraclostrobin, and (ii) a conazole fungicide selected from prothioconazole, tebuconazole, cyproconazole, epoxiconazole, metconazole, and tebuconazole.

[0139] In certain embodiments, a method of controlling fungi in a locus is provided, the method comprising administering to said locus a fungicidal formulation prepared according to the present invention.

[0140] In another embodiment, a kit is provided comprising at least one copper fungicide selected from copper oxide, basic copper chloride, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper silicate, and tribasic copper sulfate produced according to the processes herein.

[0141] Advantages of this invention: 1. The process is economically and commercially viable and is useful in reducing power consumption. 2. The process has improved reliability and stability and avoids the deposition of copper salts on the metallic copper surface. 3. Avoids the risk of direct contact between the stirrer blades and metallic copper. The metallic copper can be easily added into the column. 4. This process can be used to produce various copper compounds, e.g., CuO, Cu2(OH)3Cl or Cu(OH)2).

[0142] The following examples are provided to better illustrate the claimed invention and should not be construed as limiting the scope of the invention. Those skilled in the art may develop equivalent materials and methods without the exercise of the inventive capacity and without departing from the scope of the invention. It is the intention of the present invention that such modifications are included within the scope of the invention. EXAMPLES

[0143] Example 1 Formation of triamine copper complexes as precursors of copper fungicides.

[0144] Step 1: [A] Preparation of the initial suspension containing the tetraamine copper complex TBCS and ammonium sulfate Water (70 kg) was charged to the reactor. The temperature was raised to 50° C. and copper sulfate (7.0 kg) was added. The pH was raised to 8.2 with aqueous ammonia (32%, 3.0 kg). The final copper soluble content determined in the filtrate was 0.5% and the ammonium sulfate concentration was 4.5%. The total copper content in the suspension was 2.3%. All percentages are expressed as m / m.

[0145] [B] Preparation of the initial suspension containing the tetraamine copper complex TBCS and ammonium sulfate Alternatively, the initial suspension was prepared without copper sulfate. This preparation was carried out when the neutral suspension obtained in Example 2 was available. A 4.7% ammonium sulfate solution (80 kg) was charged to the reactor. The neutral suspension (4.44 kg) was added to the reactor and the temperature was raised to 50° C. The pH was raised to 8.2 with aqueous ammonia (32%, 0.59 kg). The final copper soluble content determined in the filtrate was 0.3% and the ammonium sulfate concentration was 5.6%. The total copper content in the resulting suspension was 0.6%.

[0146] Step 2: The suspension obtained in part [A] and / or [B] of step 1 was placed in a reactor and recirculation of the suspension was started through an 83 mm column packed with copper wire (27.14 kg). During recirculation, O2 introduction was started at the bottom of the column. The pH of the suspension in the reactor was maintained at 8-8.2. The pH adjustment was adapted to maintain the soluble copper tetramine copper concentration in the filtrate at 0.3-0.6% (expressed as copper). The temperature was maintained at about 50°C for about 2 hours. The increase in the total copper content in the reactor is shown in the following table:

[0147] [Table 1]

[0148] Step 3: When the total copper content in the suspension reached about 10%, the suspension was diluted with ammonium sulfate solution (5%) and the withdrawal of the suspension from the reactor was started. The control pH was maintained as in step 2. The reaction was carried out at 50° C. for 2 hours. The table below shows the % of copper present in the reactor during the continuous process.

[0149] [Table 2]

[0150] The table below shows the % of copper in the suspension that was removed.

[0151] [Table 3]

[0152] Example 2 Formation of tribasic copper sulfate, a copper fungicide. A reactor equipped with an agitator and a pH measuring device was charged with 79 kg of the suspension taken from the continuous process of step 3 of Example 1. 0.59 liters of sulfuric acid (98%) was added to the reactor at 50° C. to maintain the pH of the suspension containing the tetraamine copper complex at 5-7 to form TBCS.

[0153] The complete conversion of the suspension before and after neutralization is shown in the table below.

[0154] [Table 4]

[0155] After neutralization, the suspension was filtered to obtain 41.3 kg of paste. 33 kg of water was added to wash the paste, and the mixture was stirred and filtered to obtain TBCS with a copper content of 53.6%, which was dried in a drying oven at a temperature of 55° C. The filtrate obtained after the second filtration was added into the ammonium sulfate solution and mixed with the suspension of the reactor of step 3 of Example 1 to produce the copper fungicide precursor, which can be continued in the process.

[0156] Example 3 Formulation (WG 40% copper)

[0157] Step 1: Preparation of fluidized paste from washed paste In a tank equipped with a stirrer, 35.8 kg of the washed paste obtained in Example 2, 1.25 kg of sodium polynaphthalenesulfonate and 1.88 kg of water were added. The mixture was stirred, and after stirring, a fluidized paste was obtained that can be used to prepare WG-type formulations. The analysis of the fluidized paste is as follows: Dry matter: 56.2% Copper content: 28.5% Particle size (D50%): 8μm

[0158] Step 2: Preparation of water-dispersible TBCS granules A tank equipped with an agitator was charged with 25.24 kg of the fluidized paste obtained in step 1, 1.84 kg of water, 1.44 kg of sodium lignosulfonate, 0.40 kg of sodium xylenesulfonate, 0.09 kg of a silicone emulsion-based defoamer, and 1.71 kg of gypsum. The mixture was stirred, and after stirring, the suspension was wet-milled and sent to a drying tower to obtain granules containing 40% copper. The analysis of the WG formulation is as follows: Copper content: 40.3% Suspension:>75% Particle size (D50%): 2.3μm

Claims

[Claim 1] 1. A fungicidal formulation comprising: at least one copper fungicide having a D50 particle size of 3 to 20 micrometers; and at least one pesticidally acceptable excipient.

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