DE102015117551A1 - Phosphonate-based plant tonic - Google Patents

Abstract

In order to provide a plant-strengthening agent which can counteract the high concentration of endogenously formed reactive oxygen species when attacked by a phytopathogenic germ, a mixed-metal phosphonate containing at least two metals selected from Mn, Fe, Cu and Zn is proposed is obtainable by preparing an aqueous solution (I), for which oxidic metal compounds of at least one of the metals selected from Na, K, Mg, Ca, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn and B are selected, together with the elemental form or alloy of at least one of these metals in an aqueous medium containing phosphonic acid and reacting the contained metals or metal compounds in a redox reaction to divalent metal ions with the proviso that at least two of the compounds , elementary forms or alloys used metals (M1, M2, M3 ... Mx) are two different metals, each selected from Mn, Fe, Cu and Zn, then neutralizing the aqueous solution (I) with a basic aqueous alkali hydroxide solution so that the pH of the resulting reaction mixture is maintained in the range of 5 to 8, the phosphonate precipitated and then separated from the reaction solution.

Description

Subject of the invention

The invention relates to a phosphonate-based plant tonic and to a process for its preparation.

Background of the invention

In food production diseases of crops after infestation by phytopathogenic germs regularly lead to significant losses due to quality reduction, yield reduction or even complete crop failure. Among the phytopathogenic germs that cause these diseases include fungi, protists, bacteria and viruses.

The spectrum of plant defense against microbial infections is complex. Part of these reactions are based on the targeted biosynthesis of antimicrobial phytoalexins, defense proteins of molecular function ("pathogenesis-related proteins", PR proteins) or lytic enzymes (chitinases, glucanases, proteases). Further defense mechanisms are the oxidative cross-linking of the cell wall components, the incorporation of lignin into the cell walls as well as the balancing of the antimicrobial reactive oxygen species (ROS, such as hydrogen peroxide H ₂ O ₂ , superoxide anions O ₂ ^- ), which in particular increase under stress situations. , Reactive oxygen species not only act against the pathogenic germ, but also cytotoxic to the plant itself.

In order to assist the plants in their fight against phytopathogenic bacteria, various measures of plant protection have been developed, including the use of the so-called plant tonic, which are to be understood as meaning those substances which are exclusively intended to serve the general health of the plant.

Since the 1990s, phosphonate (syn phosphite), or hydrogen phosphonate (H ₃ PO ₃ , syn hydrogen phosphite) or its acid form, the phosphonic acid (syn phosphorous acid), widely used as a plant tonic. Phosphonates have, in particular against fungi of the class of Peronosporomycetes (formerly called Oomycota or Oomycetes) a plant-strengthening or protective action.

The genus of the fungal or Peronosporomycetes (syn. Oomycetes) includes some saprophytic and pathogenic species. Among the pathogenic Peronosporomycetes, there are devastating plant pathogens, such as various members of the genera Albugo, Bremia, Plasmopara, Peronospora and Phytophthora. Peronosporomycetes cause economically significant damage to various crops. In many regions, e.g. Infections by Phytophthora infestans as the cause of cabbage and brown rot of tomatoes and as late blight in potato cultivation are the most important plant diseases.

Plants attacked by pathogenic fungi react with the formation of local necrosis (cell death) around the site of infection. This prevents a further spread of the disease. At the same time, the plant produces an elicitor (signaling substance), which activates the natural defense mechanisms throughout the plant. This process is called induced resistance as increased, non-genetically anchored plant resistance, also known as Systemic Acquired Resistance (SAR). Due to the systemic spread in the plant, it also offers protection to untreated plant parts, which is of particular importance in new buds and leaves.

It is the subject of science that phosphonic acid, or its salts, the phosphonates, is actively involved in the process of SAR indirectly through the formation of antimicrobial phytoalexins. The term phytoalexins is understood as meaning low molecular weight, antimicrobial compounds which, after a plant has come into contact with a pathogenic microorganism, are synthesized by the cells of the plant and, in particular, accumulate within the acutely affected cells.

Phosphonate applied to the leaf surface is relatively easily absorbed by the plant and distributed throughout the plant. The phosphonate acts as a quasi-signaling agent, which stimulates the formation of antimicrobial phytoalexins in the whole plant and thus strengthens the natural defense process of the plant against infection.

Phosphonic acid, or its salts, the phosphonates, are described as plant-strengthening agents against fungal attack in the prior art. Exemplary uses US 6,338,860 (Taylor et al, 1999) a synergistic mixture of phosphonate PO ₃ - and PO ₄ phosphate salts for the treatment of Solanum tuberosum (potato) and Lycopersicon esculentum (tomato) against the pathogenic fungus Phytophthora infestans.

Most commercially available phosphonates are prepared from phosphonic acid (H ₃ PO ₃ ) by neutralizing the phosphonic acid in aqueous solution, such as in the preparation of potassium phosphite by neutralization of phosphonic acid with potassium hydroxide: H ₃ PO ₃ + KOH → KH ₂ PO ₃ + H ₂ O KH ₂ PO ₃ + KOH → K ₂ HPO ₃ + H ₂ O

The reaction is highly exothermic and, depending on the molar ratio of the potassium hydroxide to the phosphonic acid, the resulting phosphonate solution will contain varying proportions of monopotassium phosphite, dipotassium phosphite and unreacted phosphonic acid. Alternatively, as the base, for example, potassium carbonate may be used in place of the potassium hydroxide. Also, phosphonates can be formed from transition metals; Copper phosphite (CuHPO ₃ ), manganese phosphite (MnHPO ₃ ) or zinc phosphite (ZnHPO ₃ ). The neutralization of the phosphonic acid can be carried out with various bases; such as oxides, hydroxides, carbonates, chlorides, sulfates or nitrates as a counter-anion of the corresponding cationic metals.

A disadvantage of the phosphonates known from the prior art is that the anions are still present in the reaction product as a substance after formation of the metallic phosphonate salts. However, in many applications, the presence of anionic contaminants is critical. As an example may be mentioned that crop plants respond differently tolerant to chlorides in particular. Thus, free ions in the applied solution can cause sheet burns and thus sustainably reduce yield and quality. Particularly sensitive in horticulture are exemplary next to the sowing and cuttings, Azerca (azaleas, Ericen and Camelia), primroses or cyclamen (Cyclamen). Furthermore, any anionic contamination can lead to difficulties in stability and thus efficacy with active ingredients incorporated into the formulation, fungicidal or bactericidal.

A further disadvantage of the phosphonates known from the prior art, which are used for plant strengthening, is that they do not prevent damage to the plant by endogenously formed reactive oxygen species after infestation with a phytopathogenic germ.

The formation of highly reactive oxygen species (ROS) is significantly increased under stress conditions. The commonality of all ROS is to oxidize proteins, lipids and DNA, thereby causing lasting damage to plant tissue. At the same time, however, ROS also serve as signaling molecules in processes such as growth and development, cell cycle, programmed cell death, hormonal signaling pathways, and stress responses. In order to perform these different functions, the balance on ROS must be closely monitored and controlled.

In a normal, non-stressed state of a plant, radical scavengers involved in detoxification of the ROS and proteins that produce ROS commute. However, this balance is disturbed by infestation with a pathogen-induced stress. Thus, in particular in the case of a pathogen attack, an 'oxidative explosion' occurs, in which the amount of ROS increases rapidly. However, the plant-induced increased levels of O ₂ ^- radicals, which serve to defend against an invading pathogen, are also associated with a potential damage to their own tissue.

task

The object of the present invention was to provide an improved plant strengthening agent compared to the prior art. In particular, plant-strengthening phosphonates should be provided which have no plant-degrading anionic product contaminants. In addition, the plant-strengthening phosphonates should be suitable for use particularly in stress situations, such as e.g. to counteract the infestation by a phytopathogenic germ, partly to a high concentration of endogenously formed reactive oxygen species.

Description of the invention

• a) eine wässrige Lösung (I) herstellt, welche wenigstens zwei Metalle, die unter Mn, Fe, Cu und Zn ausgewählt sind, als zweiwertige Kationen enthält, indem man i) wenigstens eine oxidische Metall(II)-, Metall(III)- und/oder Metall(IV)-Verbindung und/oder wenigstens eine Verbindung mit gemischten Oxidationsstufen, ausgewählt unter Hydroxiden, Oxiden, Oxidhydroxiden, Oxidhydraten, Carbonaten und Hydroxidcarbonaten, von wenigstens einem der Metalle (M1, M2, M3 ... Mx) zusammen mit der elementaren Form oder Legierung von wenigstens einem der Metalle (M1, M2, M3 ... Mx) in ein Phosphonsäure enthaltendes wässriges Medium einbringt und die oxidischen Metallverbindungen mit den elementaren Formen oder Legierungen der Metalle (in einer Redoxreaktion) zu den zweiwertigen Metallionen umsetzt, und ii) optional, weiterhin wenigstens ein weiteres der Metalle (M1, M2, M3, ... Mx) in elementarer Form oder als Verbindung von wenigstens einem der Metalle (M1, M2, M3 ... Mx) in der Form einer wässrigen Lösung oder als Feststoff zugibt, wobei die Verbindung vorzugsweise unter Hydroxiden, Oxiden, Oxidhydroxiden, Oxidhydraten, Carbonaten, Hydroxidcarbonaten, Carboxylaten, Sulfaten, Chloriden oder Nitraten der Metalle (M1, M2, M3, ... Mx) ausgewählt ist,

mit der Massgabe, dass wenigstens zwei der in den Stufen i) und ii) in Form von Verbindungen, elementaren Formen oder Legierungen eingesetzten Metalle (M1, M2, M3 ... Mx) zwei verschiedene Metalle sind, die jeweils unter Mn, Fe, Cu und Zn ausgewählt sind,

• b) gegebenenfalls enthaltene Feststoffe von der phosphonsauren wässrigen Lösung (I) abtrennt,
• c) die wässrige Lösung (I) mit einer basischen wässrigen Alkalihydroxidlösung so neutralisiert, dass der pH-Wert des erhaltenen Reaktionsgemisches einen Bereich von 5 bis 8, vorzugsweise 6 bis 7, erreicht, wobei das Phosphonat vom Typ (M1 M2 M3 ... Mx)HPO₃·aH₂O ausgefällt wird,
• d) das ausgefällte Phosphonat von der Reaktionslösung abtrennt.

This object of the invention is achieved by a plant strengthening agent containing at least one mixed metallic phosphonate of the type (M1 M2 M3... Mx) HPO ₃ .aH ₂ O where 0 ≤ a ≤ 9, where (M1, M2, M3) Mx) represent the metals of the mixed metallic phosphonate and are selected from Na, K, Mg, Ca, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al and B with the proviso that the phosphonate is at least two Contains metals selected from Mn, Fe, Cu and Zn, wherein the at least one phosphonate is preparable or prepared by

• a) preparing an aqueous solution (I) which contains at least two metals selected from Mn, Fe, Cu and Zn as divalent cations by reacting i) at least one oxidic metal (II), metal (III) and / or metal (IV) compound and / or at least one compound having mixed oxidation states, selected from hydroxides, oxides, oxide hydroxides, hydrated oxides, carbonates and hydroxide carbonates, of at least one of the metals (M1, M2, M3 ... Mx) together with the elemental form or alloy of at least one of the metals (M1, M2, M3 ... Mx) in an aqueous medium containing phosphonic acid and the metal oxide compounds with the elemental forms or alloys of the metals (in a redox reaction) to the divalent metal ions and ii) optionally further comprising at least one further of the metals (M1, M2, M3, ... Mx) in elemental form or as a compound of at least one of the metals (M1, M2, M3 ... Mx) in the mold a was the compound is preferably selected from hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides or nitrates of the metals (M1, M2, M3,... Mx),

with the proviso that at least two of the metals used in steps i) and ii) in the form of compounds, elemental forms or alloys (M1, M2, M3 ... Mx) are two different metals, each of Mn, Fe, Cu and Zn are selected

• b) optionally separating solids from the phosphonic acid aqueous solution (I),
• c) the aqueous solution (I) is neutralized with a basic aqueous alkali metal hydroxide solution so that the pH of the resulting reaction mixture reaches a range of 5 to 8, preferably 6 to 7, wherein the phosphonate of the type (M1 M2 M3 ... Mx) HPO ₃ · aH ₂ O is precipitated,
• d) separating the precipitated phosphonate from the reaction solution.

This plant strengthening agent, which contains at least one mixed metallic phosphonate of the type (M1 M2 M3... Mx) HPO ₃ .aH ₂ O with 0 ≤ a ≤ 9, is hereinafter also referred to as "variant A" of the plant strengthening agent according to the invention.

The mixed-metal phosphonate for the purposes of the present invention is a phosphonate of the type (M1 M2 M3... Mx) HPO ₃ .aH ₂ O where 0 ≤ a ≤ 9, wherein the formula notation (M1 M2 M3... Mx) is two or more represents various metals, at least two of which are selected from Mn, Fe, Cu and Zn. The remaining metal (s) may be selected from Na, K, Mg, Ca, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn and B except those metals already selected from Mn, Fe, Cu and Zn ,

In a preferred embodiment of the plant strengthening agent according to variant A, at least 3 different metals (M1 M2 M3 ... Mx) and preferably not more than 10 different metals (M1 M2 M3 ... Mx) are contained in the plant strengthening agent.

• i) wenigstens eine oxidische Metall(II)-, Metall(III)- und/oder Metall(IV)-Verbindung und/oder wenigstens eine Verbindung mit gemischten Oxidationsstufen, ausgewählt unter Hydroxiden, Oxiden, Oxidhydroxiden, Oxidhydraten, Carbonaten und Hydroxidcarbonaten, von wenigstens einem der Metalle (M1, M2, M3 ... Mx) zusammen mit der elementaren Form oder Legierung von wenigstens einem der Metalle (M1, M2, M3 ... Mx) in ein Phosphonsäure enthaltendes wässriges Medium einbringt und die oxidischen Metallverbindungen mit den elementaren Formen oder Legierungen der Metalle (in einer Redoxreaktion) zu den zweiwertigen Metallionen umsetzt, und
• ii) optional, weiterhin wenigstens ein weiteres der Metalle (M1, M2, M3, ... Mx) in elementarer Form oder als Verbindung von wenigstens einem der Metalle (M1, M2, M3 ... Mx) in der Form einer wässrigen Lösung oder als Feststoff zugibt, wobei die Verbindung vorzugsweise unter Hydroxiden, Oxiden, Oxidhydroxiden, Oxidhydraten, Carbonaten, Hydroxidcarbonaten, Carboxylaten, Sulfaten, Chloriden oder Nitraten der Metalle (M1, M2, M3, ... Mx) ausgewählt ist,

mit der Massgabe, dass wenigstens zwei der in den Stufen i) und ii) in Form von Verbindungen, elementaren Formen oder Legierungen eingesetzten Metalle (M1, M2, M3 ... Mx) zwei verschiedene Metalle sind, die jeweils unter Mn, Fe, Cu und Zn ausgewählt sind.The object of the invention is further achieved by a plant strengthening agent which comprises an aqueous solution (I) containing cations of different metals (M1, M2, M3 ... Mx), the metals (M1, M2, M3, ... Mx) in the aqueous solution are selected from Na, K, Mg, Ca, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn and B with the proviso that the solution contains at least two metals which are present under Mn, Fe, Co and Ni are selected, wherein the aqueous solution (I) can be prepared or prepared by:

• i) at least one oxidic metal (II), metal (III) and / or metal (IV) compound and / or at least one compound having mixed oxidation states selected from hydroxides, oxides, oxide hydroxides, hydrated oxides, carbonates and hydroxide carbonates at least one of the metals (M1, M2, M3 ... Mx) together with the elemental form or alloy of at least one of the metals (M1, M2, M3 ... Mx) in an aqueous medium containing phosphonic acid and the oxide metal compounds with the elemental forms or alloys of the metals (in a redox reaction) to the divalent metal ions, and
• ii) optionally, further at least one further of the metals (M1, M2, M3, ... Mx) in elemental form or as a compound of at least one of the metals (M1, M2, M3 ... Mx) in the form of an aqueous solution or as a solid, wherein the compound is preferably selected from hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides or nitrates of the metals (M1, M2, M3, ... Mx),

with the proviso that at least two of the metals used in steps i) and ii) in the form of compounds, elemental forms or alloys (M1, M2, M3 ... Mx) are two different metals, each of Mn, Fe, Cu and Zn are selected.

This plant strengthening agent comprising an aqueous solution (I) containing cations of various metals (M1, M2, M3 ... Mx) will hereinafter also be referred to as "variant B" of the plant strengthening agent of the present invention.

In a preferred embodiment of the plant strengthening agent according to variant B, in the solution (I) at least 3 different metals (M1 M2 M3 ... Mx) and preferably not more than 10 different metals (M1 M2 M3 ... Mx) are included.

The metals Mn, Fe, Cu and Zn introduced into solution (I) in the preparation of a plant-strengthening agent according to the invention according to variants A and B are also referred to herein as "main metals". The further optionally introduced into the solution (I) metals selected from Na, K, Mg, Ca, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn and B are also referred to herein as "doping metals" , The doping metals may be in the form of the divalent metal ions in the solution, but they may also be in the form of the trivalent or tetravalent metal ions in the solution.

The background for the specific selection of at least two metals from the group Mn, Fe, Cu and Zn is the correlation of this selection recognized by the inventors of the present application with their positive influence on the defense reaction of a plant in the case of an infestation with a phytopathogenic germ. In combination with the above-described phosphonate protection mechanism, the selected metals have a complementary effect in terms of plant fortification. In particular, Fe, Mn, Cu and Zn are both activators and components of enzymes for the detoxification of oxygen free radicals.

As already mentioned above, the plant-induced increased amounts of O ₂ ^- radicals, in order to defend against an invading pathogen, are accompanied by a potential damage to their own tissue. To prevent this, plants respond to ROS-induced stress with enzymatic and non-enzymatic antioxidant processes. The most important enzymes of the antioxidant protection system are superoxide dismutase (SOD), catalase, ascorbate peroxidase (APx), monodehydroascorbate reductase (MDAR), dehydroascorbate reductase (DHAR) and glutathione reductase (GR).

An important class of antioxidant enzymes are the already mentioned superoxide dismutases (SOD). For example, it has been found that in the presence of a deficiency of Cu and / or Zn, the activity of some superoxide dismutases in the chloroplastic and cytoplasmic compartments of the leaf cells is greatly reduced. The decrease in SOD activity in the presence of Zn deficiency is particularly critical due to the concomitant increase in O ₂ ^- formation.

Thus, a plant stressed by an acute pathogen infestation has a particular need for the trace elements Fe, Mn, Cu and Zn. This need is met by the plant strengthening agent according to the invention by containing at least two of these metals which are essential in this respect. In a preferred embodiment of the invention, even at least three of these essential metals are included. More preferably, all four of these essential metals are included.

In an alternative embodiment of the invention, at least the metals Fe and Mn are included. In a further alternative of the invention at least the metals Fe and Cu are included. In another alternative of the invention at least the metals Fe and Zn are included. Other alternatives include at least the combination of Mn and Cu, at least the combination of Mn and Zn, or at least the combination of Cu and Zn.

The embodiments of the invention containing at least three of these essential metals include the alternatives wherein at least the combination of Fe, Mn and Cu, at least the combination of Fe, Cu and Zn, at least the combination of Fe, Mn and Zn or at least the combination of Mn, Cu and Zn is present.

The preparation of the product according to the invention is simple and inexpensive. The particular advantage is that the aqueous phosphonic acid solution (I) prepared in a first reaction stage contains only the desired metal cations and phosphonate anions or phosphonic acid and no or substantial amounts of non-phosphonate anions, such as sulfates, nitrates or chlorides, which are often undesirable , If doping metals in the form of sulfates, nitrates or chlorides are introduced, which is within the scope of the invention, this usually takes place in very small amounts which do not significantly affect the purity of the product. The product according to the invention is therefore characterized by a high purity, making it ideally suited as a plant tonic on its own or in complex mixtures with other agents for the treatment of plants.

The invention provides a highly flexible reaction principle capable of representing a variety of phosphonate systems of the type described herein, for example (pseudo) binary, (pseudo) ternary, and (pseudo) quaternary systems.

The preparation of the mixed-metal phosphonate according to variant A of the invention described herein offers the possibility, by suitable choice of the precipitation conditions, such as pH, concentrations, temperature, etc., certain material parameters, such as crystal phase and cation distribution, morphology, crystallite and secondary particle size and chemical purity of the products obtained.

In the preparation of the product according to the invention according to variants A and B, in a first reaction stage, the oxidic metal (II), metal (III) and / or metal (IV) compounds with elemental metal or alloys in phosphonic acid aqueous medium in one Redox reaction reacted to the divalent metal ions. The course of the described redox reaction between the elemental metals and the oxidic components depends on their respective specific surface areas, since the electron transfer takes place at the interface. As a competing side reaction to transfer electrons from the elemental metal forms to the oxide metal forms, the formation of hydrogen gas must be considered. This results in the transfer of electrons from the elemental metal forms to protons with the formation of radicals, which form hydrogen gas by radical combination. The particle sizes of the elemental and oxidic metal forms used should therefore be matched to suppress the side reaction and to take maximum advantage of the dissolution of the inexpensive oxide metal mold. Generally, the finer the elemental metal form, the more likely the side reaction is favored if the oxide form does not provide a sufficiently high active surface area.

Depending on the composition of the reaction solution, unreacted components may remain as solid residues in the solution. If solids are still present in the resulting reaction solution, they are preferably separated off from the phosphonic acid aqueous solution in the preparation of the plant strengthening agent according to variant A. The separation of solids can be carried out by any suitable known methods for the separation of liquids and solids, for example filtration, centrifugation, sedimentation, etc.

If the product to be produced according to the invention according to variants A and B, in addition to the metals introduced into solution (I) in the first reaction stage (redox reaction), should contain further metals (doping metals) selected from among (M1, M2, M3... Mx), at least one compound of at least one of the metals (M1, M2, M3... Mx) in the form of an aqueous solution or as a solid in the form of a salt is added to the aqueous solution (I) after the first reaction stage (redox reaction), wherein the at least one compound is preferably selected from hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides or nitrates of the metals. The addition of these metals is advantageously carried out after optionally contained solids were separated from the phosphonic acid aqueous solution (l). Alternatively, the described addition of the metals can also be carried out immediately after the preparation of the solution (I) in the first reaction stage (redox reaction) and before the separation of optionally contained solids. The separation of optionally contained solids then takes place after the addition of the doping metals. For certain applications, separation of contained solids may not be required. The separation is then not carried out. Such a variant is included in the present invention.

By adding suitable metal salts (doping metals) in the form mentioned, the desired metal content or the ratio of the metals to one another in the product to be produced is very high set exactly. This is especially true for metals that are used in relatively small quantities. Conveniently, metal compounds should be introduced which do not introduce interfering anions into the mixture to ensure the highest level of purity of the product. In particular, such metal compounds are hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates and hydroxide carbonates which react or decompose to form water under the prevailing acidic conditions. If necessary, buffers familiar to those skilled in the art can be used to prevent undesirable premature or uncontrolled precipitation. Carboxylates may also be suitable if the remaining organic acid in the mixture does not later disturb or decompose or degrade. The addition of the metals in the form of their sulfates, chlorides or nitrates may also be suitable for dopants, if the content of sulfates, chlorides or nitrates in the product does not exceed certain limits which are still considered acceptable for the particular application.

The template solution (II) for the subsequent precipitation of the phosphonate used in the above-described preparation of the mixed metallic phosphonate of the plant strengthening agent according to variant A is likewise a phosphonate solution with a pH value buffered in the range from 5 to 8. The template solution is prepared either from an aqueous phosphonic acid solution by neutralization with an aqueous alkali hydroxide solution or directly from an aqueous solution of one or more alkali metal phosphonates. For the precipitation of the phosphonates according to the invention, the aqueous solution (I) is added to the initial solution (II). Due to the low pH of the phosphonic acid solution (I), a basic aqueous alkali metal hydroxide solution is metered in at the same time in order to keep the pH of the resulting reaction mixture in the range from 5 to 8. A too low pH of the template solution (II) or the resulting reaction mixture under a pH of 5 has the disadvantage that in addition to the desired crystal phase according to the invention also other crystal phases can form. A too high pH of the template solution (II) above a pH of 8 has the disadvantage that traces of metal hydroxides can form which represent an undesirable contamination in the products according to the invention, which are sparingly soluble and therefore poorly available as a nutrient , The basic aqueous alkali metal hydroxide solution is preferably added in such a way that a pH in the range from 6 to 7 is established during the metered addition of the solution (I) in the reaction mixture. This has the advantage that only the crystal phase according to the invention forms.

After precipitation of the phosphonate according to the invention this is separated from the reaction solution. This is also done again by methods known per se, for example filtration, centrifugation, sedimentation, etc. The phosphonate separated from the reaction solution is then expediently dried, ie dewatered. The drying can be carried out either under ambient atmosphere, under a protective gas atmosphere and / or under reduced pressure and / or elevated temperature (above room temperature, 25 ° C). The methods suitable for this purpose are familiar to the person skilled in the art and require no further description. In addition, reference is made to the following examples. During drying, free water is removed from the residue separated from the reaction solution. Depending on the desired product but also bound water of crystallization is removed by drying up to a desired hydrate level of the product. Preferably, the product is up to a hydrate stage (M1 M2 M3 ... Mx) HPO ₃ · aH ₂ O with 0 ≤ a ≤ 8, more preferably up to a hydrate stage (M1 M2 M3 ... Mx) HPO ₃ · aH ₂ O with 0 ≤ a ≤ 3, dried. Drying up to a hydrate stage with 0 ≤ a ≤ 3 has the advantage over higher hydrate stages that it is a hydrate stage which is stable over a wide temperature range and thus there are no problems with the subsequent handling of the products according to the invention.

The invention has significant advantages over the prior art in the production of mixed metal phosphonates in terms of efficiency, process cost, energy consumption, and product purity achievable. In addition, the proportions of the various metals in the mixed metal phosphonate can be adjusted very easily and accurately. Furthermore, by suitably selecting the precipitation conditions, such as pH, concentrations, temperature, etc., the method according to the invention allows certain material parameters, such as crystal phase and cation distribution, morphology, as well as the chemical purity of the products obtained to be controlled. This is not possible in such a simple manner or only to a limited extent in the known processes in which phosphonates and other metal salts are mixed and precipitated. In addition, alternative production methods require a higher washing effort and are therefore usually associated with a much higher energy and resource consumption.

The mixed metal phosphonate may theoretically contain any number of different metals within the range set forth herein. Preferably, however, the mixed metal phosphonate does not contain more than 10 different metals (M1 M2 M3 ... Mx), more preferably no more than 6 different metals. In most cases, it will be convenient to use a mixed metal phosphonate according to the invention with two, three or four different metals. It is often desirable to produce a mixed metallic phosphonate containing two different metals in high proportions as so-called. Major metals and one or more metals in each case small amounts as so-called doping metals or dopants. For example, it is advantageous for a phosphonate according to the invention containing manganese and iron as main metals to contain a small proportion of a further metal, for example Ca, Mg, Zn or Cu.

For the reasons mentioned above, the provision of a plant strengthening agent has a crucial importance for strengthening plants against infestation with pathogenic germs. The importance of the quantitative and relative composition of the essential trace elements or nutrients has already been demonstrated. In addition, the importance of phosphonic acid or its salts (metal phosphonates) in the field of crop protection was shown.

The product according to the invention can be used in all areas of crop protection, for example in agriculture, horticulture or forestry in numerous plant crops. A preferred use of the metal phosphonates of this invention is in combination with macronutrients such as nitrogen, potassium and phosphate, with secondary nutrients such as calcium, sulfate, magnesium and supplemental micronutrients (iron, manganese, copper, etc.).

The metal phosphonates prepared according to the process of the present invention may be used in combination with multi-nutrient fertilizers, organic fertilizers or soil conditioners known to those skilled in the art of agrochemistry. This can also take place, for example, in the form of coatings or ingredients of granulated fertilizer forms, in controlled-release formulations (CRF) and slow-release formulations (SRF) or in so-called condensed fertilizer forms.

The products according to the invention can be used in particular in the field of crop watering (fertigation), which include, for example, systems of drip irrigation, microirrigation or hydroponics. The product can be used in soil application and foliar application. Furthermore, the product in the field of seed treatment, in the synthesis of fertilizer products, eg. As polymeric structures based on ammonium phosphate or phosphate-silicate frits can be used.

The metal phosphonates prepared on the basis of the processes according to the invention can be used as such or in their formulations also in admixture with fungicides, bactericides, acaricides, nematicides or insecticides known to the person skilled in the art, as well as so-called safeners (substance added to a plant protection product) phytotoxic) can be used, for example to broaden the spectrum of action or to prevent development of resistance. In many cases, synergistic effects are obtained. The substances according to the invention are particularly suitable in addition to fungicidal active substances for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as Peronospora species, Phytophthera species, Plasmopara viticola, Pseudoperonospora species and Pythium species.

The metal phosphonates according to the invention are used in particular in resistance management or for effective spectrum extension as a mixing or application partner for controlling various plant pathogens. The following list of plant protection products, with which the metal phosphonates according to the invention can be applied, is intended to explain but not limit the possibility of combination. Exemplary protective contact fungicides (bracketed the associated CAS number) such as sulfur (7704-34-9) and copper compounds (copper oxide (1317-39-1), copper (II) oxychloride (1332-40-7)) can be used as examples. and Bordeaux broth or dithiocarbamates such as Mancozeb (8018-01-7), Propineb (9016-72-2), Zineb (12122-67-7), Maneb (12427-38-2), Thiram (137-26-8 ), Ferbam (14486-64-1), metiram (9006-42-2), ziram (137-30-4) or polyram (9016-72-2); N-trihalomethylthio derivatives (syn phthalimide derivatives) such as captan (133-06-2) or folpet (133-07-3), captafol (2425-06-1), dichlofluanid (1085-98-9), tolylfluanid (731- 27-1) or other contact fungicides: Dodine (2439-10-3), mepanipyrim (110235-47-7), oxycarboxine (5259-88-1), dithianone (3347-22-6), nitrothal isopropyl (10552- 74-6), fenpiclonil (74738-17-3), fludioxonil (131341-86-1), chlorothalonil (1897-45-6), cymoxanil (57966-95-7), diclomezine (62865-36-5), Ferric zone (89269-64-7), pencycuron (66063-05-6), phthalides (27355-22-2), quintozene (82-68-8), etridiazoles (2593-15-9), dichlorophene (97-23 -4), quinomethionate (2439-01-2), triazoxides (72459-58-6). Furthermore, systemic active substances can be used. Examples are fungicidal active substances of the superordinate groups of organophosphates, such as Iprobenfos (26087-47-8), edifenphos (17109-49-8), pyrazophos (13457-18-6); Benzimidazoles such as benomyl (17804-35-2), fuberidazole (3878-19-1), Carbendazine (10605-21-7); Phenylamidine derivatives such as metalaxyl (57837-19-1), benalaxyl (71626-11-4), ofurace (58810-48-3), oxadixyl (77732-09-3), furalaxyl (57646-30-7); Triazoles such as Bitertanol (55179-31-2), Bromoconazole (116255-48-2), Cyproconazole (94361-06-5), Difenoconazole (119446-68-3), Epoxiconazole (106325-08-0), Fenbuconazole (114369 -43-6), fluquiconazole (136426-54-5), flusilazole (85509-19-9), flutriafol (76674-21-0), hexaconazole (79983-71-4), metconazole (125116-23-6) , Myclobutanil (88671-89-0), penconazole (66246-88-6), prothioconazole (60207-90-1), tebuconazole (80443-41-0), triadimefon (43121-43-3), triadimenol (55219- 65-3); Imidazoles such as prochloraz (67747-09-5), imazalil (35554-44-0), triflumizole (68694-11-1); Anilinopyrimidines such as pyrimethanil (53112-28-0), fenarimol (60168-88-9) or cyprodinil (121552-61-2); Amine derivatives such as dodemorph (31717-87-0), fenpropimorph (67564-91-4), fenpropidin (67306-00-7), spiroxamine (118134-30-8), tridemorph (24602-68-6); Strobilurins such as azoxystrobin (131860-33-8), dimoxystrobin (149961-52-4), fluoxastrobin (361377-29-9), kresoxim-methyl (143390-89-0), metominostrobin (133408-50-1), orysastrobin (248593-16-0), picoxystrobin (117428-22-5), pyraclostrobin (175013-18-0) or trifloxystrobin (141517-21-7); Dicarboximides such as iprodione (36734-19-7), procymidone (32809-16-8), vinclozolin (50471-44-8); Heterocyclic compounds such as carbendazim (10605-21-7), famoxadone (131807-57-3), fenarimol (60168-88-9), isoprothiolane (50512-35-1), probenazole (27605-76-1), pyrifenox ( 88283-41-4), pyroquilone (57369-32-1), quinoxyfen (124495-18-7).

The use of the metal phosphonates furthermore comprises herbicides as mixture or application partners, such as, for example, glyphosate (1071-83-6), glufosinate-ammonium (77182-82-2), imazamox (114311-32-9) or imazethapyr (81335-77 5), but also insecticides such as, for example, fipronil (120068-37-3), imidacloprid (105827-78-9), carbofuran (1563-66-2) or cypermethrin (52315-07-8). Furthermore, growth regulators (or growth factors) such as abscisic acid (21293-29-8), naphthalene acetic acid (86-87-3), gibberellic acid (77-06-5), chlormequat (999-81-5) or prohexadione-calcium ( 127277-53-6) as mixing or application partners. Other substances from the field of application of agrochemicals which can be used as mixing or application partners with metal phosphonates are acaricides, bactericides, molluscicides, nematicides, rodenticides, virucides, but also biological preparations, defoliants (defoliants). These and other active substances are obvious to the expert in crop protection and agrochemistry as mixing or application partners and can be found in the literature ( 'Pesticide Manual', 13th Ed. 2003, The British Crop Protection Council, London; Ullmann's Agrochemicals, Vol. 1 and 2; Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 ).

The plant strengthening agent from the production process according to the invention and for use in agrochemical applications is in the form of a cation-containing phosphonic acid or as one of its salts, the so-called metal phosphonates. The present invention relates to metal phosphonates of phosphonic acid, but in particular also formulations containing metal phosphonates of phosphonic acid and at least one, but possibly also 2 to 10 active and / or nutrient substances of the above-mentioned groups. In the event that two or more active and / or nutrient substances are used, the substances mentioned can be administered simultaneously, sequentially or in combination. Each active and / or nutrient substance can be applied separately as a single component or in a mixture with more than one mixing or application partner. An active substance, or a nutrient substance can consist of a condensed mixed crystal and thus contain several active and nutrient substances.

The plant strengthening agents of the present invention can be used against phytopathogenic organisms, especially the class of the Peronosporomycetes (syn. Oomycetes), the Eumycota ("true fungi") and bacteria infecting above-ground plant parts or attacking the plants from the ground, as well as seed-borne pathogens. Such plant strengthening agents are of particular practical importance as seed dressing agents against phytopathogenic organisms which are transmitted with the seeds or occur in the soil and attack the crop plants therefrom. These are germinal diseases, root rot, stem, stalk, leaf, flower, fruit and seed diseases, which are caused in particular by Peronosporomycetes (syn. Oomycetes). Due to the systemic effect of the metal phosphonate, the plants are often protected for a long time after treatment, for example in the form of a dressing, against pathogens that can attack various parts of the shoot. The plant-strengthening agents according to the invention can be used as mordants for the treatment of seeds (fruits, tubers, grains) and plant cuttings. They can also be used as a soil treatment agent against phytopathogenic fungi and act against root rot caused, for example, by pathogens of the genus Pythium and Phytophthora. However, the plant-strengthening agents according to the invention also show excellent action on direct application to the above-ground parts of plants against pathogens on various crops, such as Phytophthora species, Peronospora species, Plasmopara species, Pseudoperonospora species, Sclerospora species. Advantageously, the plant-strengthening agents according to the invention are suitable for controlling the following plant diseases of the class Oomycetes. The following list of plant pathogens against the compounds of the invention can be used together to explain the possible combinations, but not limit.

• – Gattung Aphanomyces: A. raphani (Rettichschwärze), A. euteiches (Wurzelfäule an Erbse und anderen Leguminosen), A. cochlioides, A. laevis (Wurzelbräune, Auflaufkrankheit an Beta-Rüben, Mangold, Spinat).

Order Saprolegniales, family Saprolegniaceae:

• - genus Aphanomyces: A. raphani (radish black), A. euteiches (root rot on peas and other legumes), A. cochlioides, A. laevis (root tan, casserole on beet, chard, spinach).

• – Gattung Pythium („damping off“ und „root rot“): P. debaryanum (Auflaufkrankheiten bei Gemüsearten und Beta-Rüben), P. ultimum (Keimlingssterben bei Erbsen, Tomaten, wässrige Wundfäule an Kartoffelknollen, schwarze Wurzelfäule an Erdbeeren), P. aphanidermatum (Wurzelbrand bei Erbsen und Gräsern), P. irregulare (Gelbsucht der Zuckerrübe), P. arrhenomanes (Wurzelfäule an Gramineen), und
• – Gattung Phytophthora („late blight“ und „root rot“): P. infestans (Kraut- und Knollenfäule der Kartoffel, Blatt- und Fruchtfäule an Tomaten), P. cactorum (unter anderem Wurzel-, Stamm- und Fruchtfäule an Apfel, Birne, Aprikose, Kirsche, Pfirsich), P. cinnamomi (unter anderem Erikasterben), weitere Fäuleerkrankungen wie P. cryptogea, P. capsici, P. cambivora, P. erythroseptica, P. fragariae, P. palmivora, P. citrophthora, P. nicotianae, P. parasitica, P. phaseoli, P. syringae oder P. megasperma.

Order Peronosporales, Family Pythiaceae:

• - genus Pythium ("damping off" and "root red"): P. debaryanum (casseroles on vegetables and beetroots), P. ultimum (pollen seedling, tomato, aqueous rot on potato tubers, black root rot on strawberries), P aphanidermatum (root blight on peas and grasses), P. irregulare (jaundice of sugar beet), P. arrhenomanes (root rot on gramineae), and
• - genus Phytophthora ("late blight" and "root red"): P. infestans (late blight of potato, leaf and fruit rot on tomatoes), P. cactorum (including root, stem and fruit rot on apple, Pear, apricot, cherry, peach), P. cinnamomi (among other things Erikasterben), further rot diseases such as P. cryptogea, P. capsici, P. cambivora, P. erythroseptica, P. fragariae, P. palmivora, P. citrophthora, P nicotianae, P. parasitica, P. phaseoli, P. syringae or P. megasperma.

• – Gattung Basidiophora: B. entospora (Falscher Mehltau auf Kompositen),
• – Gattung Sclerospora („downy mildews“): S. graminicola (Falscher Mehltau der Hirse), S. philippinensis und S. maydis (Falscher Mehltau am Mais), S. sacchari (Falscher Mehltau an Zuckerrohr), S. sorghi (Falscher Mehltau an Sorghum)
• – Gattung Plasmopara („downy mildews“): P. viticola (Falscher Mehltau an Weinrebe), P. halstedii (Falscher Mehltau an Kompositen und Sonnenblumen), P. nivea (Falscher Mehltau an Möhren)
• – Gattung Peronospora („downy mildews“), P. destructor, P. schleideni (Falscher Mehltau der Küchenzwiebel), P. tabacina (Blauschimmel an Tabak), P. parasitica (Falscher Mehltau an Cruciferen), P. pisi (Falscher Mehltau an Erbsen), P. arborescens (Falscher Mehltau an Mohn), P. effusa (Falscher Mehltau an Spinat), P. antirrhini (Falscher Mehltau an Lippenblütlerartige Gewächse, Lamiales), P. schachtii (Falscher Mehltau an Beta-Rüben), P. sparsa (Falscher Mehltau an Rosen), P. manshurica (Falscher Mehltau an Soja), P. trifoliorum (Falscher Mehltau an Klee und Luzerne)
• – Gattung Pseudoperonospora („downy mildews“), P. humuli (Falscher Mehltau des Hopfens), P. cubensis (Falscher Mehltau an Gurken, Melonen), P. celtidis (Falscher Mehltau an Celtis-Arten (hackberry)
• – Gattung Bremia („downy mildews“): B. lactucae (Falscher Mehltau an Kopfsalat, Endivien, Chicoree, Artischoken)

Order Peronosporales, family Peronosporaceae:

• - genus Basidiophora: B. entospora (downy mildew on composites),
• - genus Sclerospora ("downy mildews"): S. graminicola (millet downy mildew), S. philippinensis and S. maydis (downy mildew on maize), S. sacchari (downy mildew on sugarcane), S. sorghi (downy mildew on sorghum)
• - genus Plasmopara ("downy mildews"): P. viticola (downy mildew on grapevine), P. halstedii (downy mildew on composites and sunflowers), P. nivea (downy mildew on carrots)
• - genus Peronospora ("downy mildews"), P. destructor, P. schleideni (false mildew of the kitchen onion), P. tabacina (blue tobacco), P. parasitica (downy mildew on cruciferae), P. pisi (downy mildew) Peas), P. arborescens (downy mildew on poppy), P. effusa (downy mildew on spinach), P. antirrhini (downy mildew on labiates, Lamiales), P. schachtii (downy mildew on beta beets), P. sparsa (downy mildew on roses), P. manshurica (downy mildew on soya), P. trifoliorum (downy mildew on clover and alfalfa)
• - genus Pseudoperonospora ("downy mildews"), P. humuli (downy mildew of hops), P. cubensis (downy mildew on cucumbers, melons), P. celtidis (downy mildew on Celtis species (hackberry)
• - genus Bremia ("downy mildews"): B. lactucae (downy mildew on lettuce, endives, chicory, artichokes)

• – Gattung Albugo: A. candida (Weißer Rost an Cruciferen), A. tragopogonis an Schwarzwurzel und Sonnenblumen, A. portulaca an Portulak, A. bliti an Amaranthaceen.

Order Peronosporales, Family Albuginaceae:

• - Albugo genus: A. candida (white rust on crucifers), A. tragopogonis on salsify and sunflower, A. portulaca on purslane, A. bliti on amaranthaceae.

Slime fungi and other fungus-like organisms such as the fungal hymenoids (Oomycota) or Hypochytriomycota, formerly known as "low fungi", are nowadays no longer classified as mushrooms. Thus, the biological behavior of Peronosporomycetes (syn. Oomycetes) also differs significantly from that of the "real mushrooms", because Oomycetes are biologically more related to algae than fungi. Therefore, findings on the fungicidal activity of drugs against Peronosporomyceten (syn. Oomyceten) only very limited to "real fungi", such as Zygomycetes, Ascomycetes, Deuteromycetes (syn. Fungi imperfecti) and Basidiomycetes transferable. Nevertheless, an effect of the plant strengthening agents prepared on the basis of the processes according to the invention on "true fungi" and furthermore on the classes of the Plasmodiophoromycetes and Chytridiomycetes is not excluded and is included in the scope of the invention.

This also applies to the suitability of the plant strengthening agents according to the invention or their combinations for the control of harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. An effect of the plant strengthening agents produced on the basis of the processes according to the invention on phytopathogenic bacteria and general bacterial harmful organisms is likewise not excluded and included within the scope of the invention.

Advantageously, the plant-strengthening agents according to the invention or combinations thereof are suitable for controlling the following phytopathogenic prokaryotes, in particular bacteria. The following list of plant pathogens can be used together against the compounds according to the invention should illustrate, but not limit, the possible combinations:
Order Pseudomonadales, family Pseudomonadaceae, genera Pseudomonas: P. phaseolicola (broad bean stain), P. tabaco (wildfire on tobacco), P. syringae persicae, P. syringae lachrymans (bacterial leaf spot disease of cucumber), P. syringae tomato, P. mors prunorum (bark sting of stone fruit), P. solanacearum), other genera of the family Pseudomonadaceae: Acidovorax, Ralstonia, Rhizobacter, Rhizomonas, Xylophilus. Genus Xanthomonas (X. campestris campestris (blackness of cabbage), X. campestris citri, X. campestris malvacearum, X. campestris oryzae, X. geranii). Order Eubacteriales, family Rhizobiaceae, genus Agrobacterium: A. tumefaciens, root crop on fruit species beetroot, grapevine), another genus of the family Rhizobiaceae: Rhizobium.

Order Eubacteriales, family Enterobacteriaceae, genus Erwinia: E. amylovora (fire blight on pear, apple and quince), E. carotovora (blackleg, cocci on potato), E. chrysanthemi (Chrysanthemum stem necrosis virus), other genera of the family Enterobacteriaceae: Pantoea , Serratia, Sphingomonas.

Order Eubacteriales, family Corynebacteriaceae, genus Corynebacterium: C. michiganense (bacterial wilt of tomatoes), C. sepedonicum (bacterial ring rot of potato).

Furthermore proteabacteria of the genus Xylella and Candidatus liberobacter. Gram-positive bacteria of the class Firmibacteria, genus Bacillus and Clostridium and the class Thallobacteria with the genera Arthrobacter, Clavibacter, Curtobacterium, Leifsonia, Rhodococcus and Streptomyces, especially S. scabies (potato scab on potato).

The plant strengthening agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the plant strengthening agents in the form of a suitable formulation or the use form prepared therefrom by further dilution. Examples of formulations are: water-soluble concentrates (SL, LS), dispersible concentrates (TLC), emulsifiable concentrates (EC), emulsions (EW, EO, ES), suspensions (SC, OD, FS), water-dispersible and water-soluble granules (WG, SG), water-dispersible and water-soluble powders (WP, SP, SS, WS), gel formulations (GF), dusts (DP, DS), granules (GR, FG, GG, MG), ULV solutions (UL).

In particular for seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible or water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF), as well as others Applications Active substance-impregnated natural and synthetic substances, encapsulations in polymeric substances and in encapsulants and used as Controlled Release or Slow Release formulations. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing. This list does not represent a limitation. The actual application form depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.

The formulations used are prepared in a manner known to those skilled in the art, e.g. by mixing the plant strengthening agents optionally with the addition of customary auxiliaries, such as, for example, fillers, carriers, diluents and / or solvents, furthermore using various surface-active agents, ie wetting agents, tackifiers, dispersants or emulsifiers and / or foam-forming agents. The formulations mentioned can, according to the known manner of their preparation, further beneficial processing and formulation auxiliaries such as organic or inorganic thickeners, stabilizers, gelling agents, evaporation accelerators, defoamers, adhesives, antifreeze, siccatives, UV stabilizers and optionally dyes and pigments, as well as bactericides and antifreeze, etc. The formulation auxiliaries are added to the compound in the ratio of 30: 1 to 1:30, if desired.

When using the plant strengthening agents according to the invention, the application rates can be varied within a relatively wide range, depending on the mode of application. The active and nutrient concentrations of the forms of use for controlling undesired pathogenic organisms such as fungi of the genus Peronosporomycetes may be from 0.01 to 95% by weight of active and nutrient, preferably between 0.1 and 90% by weight and especially 1 to 80% by weight of plant tonic. The application is done in a custom forms adapted to the application forms.

The plant-strengthening agents according to the invention are used by directing the pathogens directly, by indirect action on their environment, habitat or storage space or the plants, seeds, plants, materials or the soil to be protected against pathogen infestation with a pathogenically effective amount of the plant strengthening agents Combinations by pouring, dipping, spraying, spraying, atomizing, vaporizing, injecting, slurrying, brushing, dusting, spreading, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting, or in the case of propagating material, in particular for seeds and vegetative parts of plants. or multilayer coating, treated before or after sowing, or planting or before or after emergence of the plants. The application can take place both before and after the infection of the materials, plants or seeds by the pathogens. The plant strengthening agents can be applied simultaneously together or separately or in succession, the sequence when applied separately generally having no effect on the control success.

The levels of plant strengthening agents of the use forms prepared from the commercial formulations may vary widely. The "effective amount" generally encompasses an agrochemical quantitative composition of the plant tonic which results in the control and / or suppression of pathogenic organisms below an economic threshold of damage to crops or which economically increases the yield based on a nutritional-physiological action. The "effective amount" can vary within a wide range and is determined by numerous factors, such as the weather and climate, the culture's growth stage or the pathogenic pest pressure. Accordingly, the "effective amount" can not be limited by definition. Nevertheless, the following information is given:
To the plant strengthening agents, oils of various types, wetting agents, adjuvants (additive additives), herbicides, fungicides, other pesticides, bactericides, if appropriate also only immediately before application (tank mix), can be added. These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 10: 1.

The possibility of adapting the solubility of the metal phosphonates to the specific application leads to an extraordinarily good plant tolerance of the plant strengthening agents in the concentrations necessary for controlling plant diseases and permits treatment of aboveground plant parts, of planting and seed, and of the soil.

According to the invention, all plants and plant parts can be treated with the plant tonic. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic (genetically engineered) plants and including the plant varieties protectable or non-protectable plant varieties. Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds. As examples of transgenic plants, the important crops, such as cereals (wheat, rice), maize, soya, potato, cotton, rapeseed, will be particularly emphasized.

Of particular importance are the plant strengthening agents for the control of a variety of pathogens on various crops such as cereals (wheat, barley, rye, triticale, oats, rice, sorghum), beets (sugar and feed beet), pome, stone and berry fruit (apple , Pears, plums, peaches, almonds, cherries, raspberries, bromeliads, prunes, jellies, spiny or strawberries), legumes (peas, beans, lentils, soybeans), oil crops (mustard, oilseed rape, poppy, olives, Sunflowers, flax, coconut, oil palm, castor, cocoa, peanuts), cucurbits (cucumbers, melons, squash), fibrous plants (cotton, flax, hemp, jute), citrus fruits (oranges, lemons, tangerines, grapefruit), vegetable crops (cabbage) and lettuce, asparagus, spinach, carrots, onions, potatoes, tomatoes, peppers), laurel family (avocados, cinnamon or camphor), other plants such as bananas, corn, vines, sugarcane, nuts, coffee, tea, tobacco, hops, and energy and commodity plants such as Ma is, soy, wheat, oilseed rape, sugar beet, sugar cane, oil palm or poplar and willow trees and also ornamental and forest plants (annual and perennial shrubs, conifers, composites, shrubs, trees) and grass as lawn and on the propagation material, for example Seeds and the crop of these plants. This list is not a limitation.

The advantage of the plant strengthening agent of the invention is the ability to theoretically combine mixed metal phosphonates with any number of different metals within the range defined herein. In addition, doping metals can be specifically incorporated. The analytical effort in the precise production of complex nutrient mixtures is reduced significantly, since the essential components are present in a defined compound. The products according to the invention enable the optimally coordinated combination and subsequent analysis of various elements in order to meet the requirements of plant and animal nutrition as well as industrial microbiology. The plant strengthening agent of the present invention may contain a single mixed metal phosphonate, but it may also contain a mixture of two or more mixed metallic phosphonates, whereby the plant strengthening agent can be further adapted to the requirements of the particular plant being treated. A plant strengthening agent of the type according to the invention can thus also be put together according to a kit of parts from a plurality of mixed-metallic base phosphonates in order to meet the requirements of the respective treated plant.

In a further preferred embodiment of the plant strengthening agent according to variant A according to the invention, the precipitation of the phosphonate in stage e) is carried out at a temperature in the range from 5 to 105.degree. The temperature can be kept constant by a suitable control unit in the range +/- 5 ° C to the desired point. Higher temperatures generally lead to a more pronounced crystallinity or accelerate the growth of the crystallites of the products. More preferably, the precipitation of the phosphonate is carried out at a temperature in the range of 10 to 40 ° C, which generally results in no need for heating and / or cooling in favor of the economy and ecology of the process.

In a further preferred embodiment of the plant strengthening agent according to variant A according to the invention, a surface-active substance such as wetting agent, penetrating agent or adhesive (vegetable oils, rapeseed methyl ester, protein derivatives, ionic and nonionic wetting agents) is dispersed in the aqueous solution (l) before addition to the initial solution (II) , Organosilikone, polymers, waxes, etc.), or already mentioned active agents, such as formulation auxiliaries (surfactants, emulsifiers, thickeners, defoamers, o. Ä.), Synthetic and organic chelates, complexing or sequestering products, acidulants, pesticides (incl. Safeners thereof), inhibitors, vitamins which improve the quality and efficacy of the products of the invention in later use, as well as expand the potential field of application. The illustrated list of said surfactant and formulation auxiliaries which can be used together with the compounds according to the invention is intended to illustrate, but not limit, the possible combinations.

To increase the dispersion stability of the inventive plant strengthening agent according to variant A in a liquid phase, it may be advantageous to finely distribute the product according to the invention by the action of mechanical forces in the liquid phase. In addition to known methods for introducing high shear forces, the use of agitator ball mills is particularly suitable for this purpose. Through the use of a stirred ball mill, in addition to the fine distribution of the products according to the invention, their mean particle size or agglomerate size can also be modified. For example, the mean grain size can be reduced to <500 nm. The specific surface area (according to the BET method) can be between 2-90 m ² / g, preferably 30-60 m ² / g. The resulting dispersions are very stable and have little tendency to sedimentation of the solid even after several days. It is known to the person skilled in the art that the stability of the dispersion can advantageously be improved by the addition of surface-active substances.

In a further preferred embodiment of the plant strengthening agent according to variant A, the phosphonate is precipitated as described, but subsequently not isolated. Instead, use is made of a molar excess of phosphonic acid, which is preferably predominant in the solution, in order to feed the reaction solution after the precipitation with further cations in the form of alkali metal hydroxide, alkaline earth metal hydroxide or ammonia, with the formation of ammonium ions, until the reaction solution has a conductivity minimum. It may be convenient to add potassium hydroxide to the solution for neutralization since potassium is an essential growth factor for plants. The resulting mixture, consisting of the solid of the phosphonate according to the invention, phosphonate anions, potassium cations and / or ammonium cations, is then dehydrated under elevated temperature and / or reduced pressure, whereby a product is formed, which in addition to the nutrients according to the invention additionally plant available potassium and / or ammonium in Contains form of phosphonates.

In further embodiments, different substances are involved in the precipitation process. Preferred substances are ammonium and / or potassium thiosulfate, organic acids and their Salts, or esters (eg, amino acids, such as glutamic and aspartic acid, other dicarboxylic acids, such as oxalic, succinic, tartaric, malic, phthalic, maleic or fumaric acid, and also hydroxycarboxylic acids, such as salicylic acid (o-hydroxybenzoic acid), Malic acid, 2-hydroxy-4-methylmercaptobutyric acid, glycolic acid, isocitric acid, tartaric acid or citric acid, furthermore ascorbic acid, folic acid, fulvic acids, humic acids or lignosulfonate.

In a further preferred embodiment of the plant strengthening agent according to variant A, the template solution (II) contains the phosphonate ions, calculated as P ₂ O ₅ , in a concentration in the range from 0.35 to 1.85 mol / L. A phosphonation concentration below 0.35 mol / LP ₂ O ₅ has the disadvantage that it would unnecessarily dilute the reaction mixture and, in the case of a commercial application, would have to treat an unnecessarily large volume of filtrate. A phosphonation concentration above 1.85 mol / LP ₂ O ₅ has the disadvantage that the reaction mixture can not be optimally mixed due to a high solids content and the resulting high viscosity. This can lead to local concentration gradients, which can negatively affect the formation of the desired crystal phase. The plant strengthening agent according to the variants A according to the invention may further contain acidic components (acidulant) which releases the composition together with the nutrients contained therein. The plant strengthening agent according to the invention offers the possibility of integrating acidulants of various types, such as elemental sulfur or its oxidized forms, for example sulfate, into the product according to the invention.

The concentration of phosphonic acid in the aqueous solution (I) prepared in the preparation of the plant strengthening agent according to variants A and B is expediently from 5% to 85%, preferably from 10% to 40%, particularly preferably from 15% to 30%, very particularly preferably 25% to 30%, based on the weight of the aqueous solution (I). In a further preferred embodiment of the invention according to variants A and B, the reaction of the oxidic metal compounds with the elemental forms or alloys of the metals in the solution (I) at a temperature in the range of 5 ° C to 105 ° C, preferably in Range of 10 ° C to 75 ° C, particularly preferably in the range of 20 ° C to 50 ° C, by.

Furthermore, it is advantageous to carry out the reaction of the oxidic metal compounds with the elemental forms or alloys of the metals in the solution (I) according to variants A and B with thorough mixing in order to achieve a uniform reaction and to avoid local excess concentrations within the reaction solution , Expediently, the reaction of the oxidic metal compounds with the elemental forms or alloys of the metals in solution (I) according to variants A and B is carried out for a period of from 1 minute to 240 minutes, preferably from 5 minutes to 120 minutes, more preferably from 30 through to 90 min. The reaction time required for a sufficiently complete reaction depends on the reactants and the reaction conditions and can be easily determined by the skilled person by a few simple experiments. If the reaction time is too short, the reaction will generally not be sufficiently complete and will yield too much unreacted starting materials. The reaction time should also not be too long, since the process is then less economical. A complete reaction is also advantageous to obtain a defined metal composition. As described, it is possible, if appropriate, to improve it by adding suitable metal salts, which, however, unnecessarily increases the cost of the process or increases the risk of intolerable anion contamination.

In a further embodiment of the invention, the plant strengthening agent according to variants A and B comprises one or more surface-active substances (surfactants) in an amount of 0.01 to 10 wt.%, Preferably 0.1 to 5 wt.%, Particularly preferably 0 , 5 to 4 wt .-%, based on the weight of the plant strengthening agent. The advantages of this embodiment are described hereinabove. The surface-active substances can be added directly to the reaction mixture, for example to the solution (I) or to the preparation obtained after the precipitation of the phosphonates. Alternatively, the surfactants may also be added to the isolated filter cake prior to its drying or to the product after drying by mixing, spraying or in granulation processes.

The use of the phosphonates according to the invention in a plant strengthening agent has the advantage over the use of known nutrients that the various desired metal cations are already present in ideally isotropically distributed form in a high purity compound which is clearly characterized in terms of composition and morphology by simple and known methods.

Examples

1. Presentation of FeMnZnHPO ₃

200 g (2.44 mol) of H ₃ PO _{3 were dissolved} in 300 g (16.7 mol) of demineralized water (demineralized water) and the solution was heated to 45 ° C. After addition of 26 g (0.16 mol) of Fe ₂ O ₃ and 16 g (0.29 mol) of Fe, the reaction mixture heated to above 60 ° C by an exothermic reaction. After the reaction had ceased, the temperature was maintained at 60 ° C and successively added 6.3 g (0.11 mol) of Mn and 3.75 g (0.06 mol) of Zn. After 15 minutes, it was filtered and the filtrate neutralized with an aqueous 50% KOH solution to give an olive green precipitate. This was filtered off after 10 min, washed with 1 l of deionized water and dried in air for 12 h at 100 ° C.

2. Presentation of FeMnCuHPO ₃

200 g (2.44 mol) of H ₃ PO _{3 were dissolved} in 300 g (16.7 mol) of demineralized water (demineralized water) and the solution was heated to 45 ° C. After addition of 32.4 g (0.14 mol) of Fe ₃ O ₄ and 8.6 g (0.14 mol) of Cu, the reaction mixture heated to above 60 ° C by an exothermic reaction. After the reaction had ceased, the temperature was maintained at 60 ° C and 7.9 g (0.14 mol) of Mn was added. After 15 minutes, it was filtered and the filtrate neutralized with an aqueous 50% KOH solution to give an olive green precipitate. This was filtered off after 10 min, washed with 1 l of deionized water and dried in air for 12 h at 100 ° C.

3. Presentation of FeMnCuZnHPO ₃

200 g (2.44 mol) of H ₃ PO _{3 were dissolved} in 300 g (16.7 mol) of demineralized water (demineralized water) and the solution was heated to 45 ° C. After addition of 27 g (0.117 mol) of Fe ₃ O ₄ and 8.9 g (0.14 mol) of Cu, the reaction mixture warmed by an exothermic reaction to above 60 ° C. After the reaction had ceased, the temperature was maintained at 60 ° C and 7.7 g (0.14 mol) of Mn was added. Subsequently, 20 g (0.07 mol) of ZnSO ₄ .7H ₂ O were added. After 15 minutes, it was filtered and the filtrate neutralized with an aqueous 50% KOH solution to give an olive green precipitate. This was filtered off after 10 min, washed with 1 l of deionized water and dried in air for 12 h at 100 ° C.

4. X-ray fluorescence analysis (XRF)

Tables 1-3 below show the XRF data of the products analyzed according to Preparation Examples 1-3 (see above). Table 1: XRF analysis of FeMnZnHPO ₃ according to Preparation Example 1 feature Result Ratio of metals CuO <0.1% K ₂ O 16% P ₂ O ₅ 43% ZnO 2% 8th% MnO 5% 15% Fe ₂ O ₃ 26% 77%

From the results of the XRF data given in Table 1 above, the following composition (Fe _0.77 Mn _0.15 Zn _0.08 ) HPO _{3 is} determined for the product investigated. Table 2: XRF analysis of FeMnCuHPO ₃ according to Preparation Example 2 feature Result Ratio of metals K ₂ O 12% P ₂ O ₅ 42% ZnO <0.1% CuO 1% 3% MnO 9% 26% Fe ₂ O ₃ 29% 71%

From the results of the XRF data given in Table 2 above, the following composition (Fe _0.71 Mn _0.26 Cu _0.03 ) HPO _{3 is} determined for the product investigated. Table 3: XRF analysis of FeMnCuZnHPO ₃ according to Preparation Example 3 feature Result Ratio of metals Fe ₂ O ₃ 28% 60% MnO 10% 24% CuO 2% 5% ZnO 4% 11% K ₂ O 7% P ₂ O ₅ 49%

From the results of the XRF data given in Table 3 above, the following composition (Fe _0.60 Mn _0.24 Cu _0.05 Zn _0.11 ) HPO _{3 is} determined for the product investigated.

5. Analysis (XRD)

In the attached 1 . 2 and 3 XRD diffractograms of the products analyzed according to Preparation Examples 1, 2 and 3 (see above) are shown.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 6338860 [0010]

Cited non-patent literature

• 'Pesticide Manual', 13th Ed. 2003, The British Crop Protection Council, London; Ullmann's Agrochemicals, Vol. 1 and 2; Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 [0049]

Claims (16)

Plant strengthening agent containing at least one mixed metallic phosphonate of the type (M1 M2 M3 ... Mx) HPO ₃ · aH ₂ O with 0 ≤ a ≤ 9, where (M1, M2, M3 ... Mx) represent the metals of the mixed metallic phosphonate and Na, K, Mg, Ca, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al and B are selected with the proviso that the phosphonate contains at least two metals selected from Mn, Fe , Cu and Zn, wherein the at least one phosphonate is preparable or prepared by a) preparing an aqueous solution (I) containing at least two metals selected from Mn, Fe, Cu and Zn as divalent cations in that i) at least one oxidic metal (II), metal (III) and / or metal (IV) compound and / or at least one compound having mixed oxidation states selected from hydroxides, oxides, oxide hydroxides, hydrated oxides, carbonates and Hydrocarbon carbonates, of at least one of the metals (M1, M2, M3 ... Mx) together with the elemental form or alloy of at least one of the metals (M1, M2, M3 ... Mx) in an aqueous medium containing phosphonic acid and the oxidic metal compounds with the elemental forms or alloys of the metals (in a redox reaction) to the bivalent Reacting metal ions, and ii) optionally, further at least one further of the metals (M1, M2, M3, ... Mx) in elemental form or as a compound of at least one of the metals (M1, M2, M3 ... Mx) in the Form of an aqueous solution or as a solid, wherein the compound is preferably selected from hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides or nitrates of the metals (M1, M2, M3, ... Mx), with the proviso that at least two of the metals used in steps i) and ii) in the form of compounds, elemental forms or alloys (M1, M2, M3 ... Mx) are two different metals, each of which s are selected from Mn, Fe, Cu and Zn, b) optionally separated solids from the phosphonic acid aqueous solution (I), c) the aqueous solution (I) with a basic aqueous alkali metal so neutralized that the pH of the obtained Reaction mixture reaches a range of 5 to 8, preferably 6 to 7, wherein the phosphonate of the type (M1 M2 M3 ... Mx) HPO ₃ · aH ₂ O is precipitated, d) the precipitated phosphonate is separated from the reaction solution. Plant strengthening agent according to Claim 1, characterized in that the precipitated and separated from the reaction solution phosphonate is dried, preferably up to a hydrate stage (M1 M2 M3 ... Mx) ₃ (PO ₄ ) ₂ · aH ₂ O with 0 ≤ a ≤8 , particularly preferably up to a hydrate stage (M1 M2 M3 ... Mx) ₃ (PO ₄ ) ₂ · aH ₂ O with 0 ≤ a ≤3. Plant strengthening agent according to one of claims 1 or 2, characterized in that the phosphonate contains at least three metals selected from Mn, Fe, Cu and Zn. Plant strengthening agent according to one of claims 1 or 2, characterized in that the phosphonate contains at least the four metals Mn, Fe, Cu and Zn. Plant strengthening agent according to one of the preceding claims, characterized in that the phosphonate contains not more than 10 different metals (M1 M2 M3 ... Mx). Plant strengthening agent according to one of the preceding claims, characterized in that the precipitation of the phosphonate of the type (M1 M2 M3 ... Mx) ₃ (PO ₄ ) ₂ · aH ₂ O in step e) at a temperature in the range of 5 to 105 ° C, preferably in the range of 10 to 40 ° C. Plant strengthening agent according to one of the preceding claims, characterized in that the template solution (II) contains the phosphonate ions, calculated as P ₂ O ₅ , in a concentration in the range from 0.35 to 1.85 mol / L. Plant strengthening agent comprising an aqueous solution (I) containing cations of different metals (M1, M2, M3 ... Mx), said metals (M1, M2, M3 ... Mx) being selected from Na, K, Mg, Ca , Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn and B are selected with the proviso that the solution contains at least two metals selected from Mn, Fe, Cu and Zn, wherein the aqueous solution (I) can be prepared or prepared by reacting i) at least one oxide metal (II), metal (III) and / or metal (IV) compound and / or at least one compound having mixed oxidation states selected from hydroxides, oxides , Oxide hydroxides, oxide hydrates, carbonates and hydroxide carbonates, of at least one of the metals (M1, M2, M3 ... Mx) together with the elemental form or alloy of at least one of the metals (M1, M2, M3 ... Mx) in an aqueous medium containing phosphonic acid and the oxidic metal compounds with the elemental forms or alloys of the metals (in a redox reaction) to the bivalent Reacting metal ions, and ii) optionally, further at least one further of the metals (M1, M2, M3, ... Mx) in elemental form or as a compound of at least one of the metals (M1, M2, M3 ... Mx) in the Form of an aqueous solution or as a solid, wherein the compound is preferably selected from hydroxides, oxides, oxide hydroxides, oxide hydrates, carbonates, hydroxide carbonates, carboxylates, sulfates, chlorides or nitrates of the metals (M1, M2, M3, ... Mx), with the proviso that at least two of the metals used in steps i) and ii) in the form of compounds, elemental forms or alloys (M1, M2, M3 ... Mx) are two different metals, each of which s are selected from Mn, Fe, Cu and Zn. Plant strengthening agent according to claim 8, characterized in that the solution (I) contains at least three metals selected from Mn, Fe, Cu and Zn. Plant strengthening agent according to claim 8, characterized in that the solution (I) contains at least the four metals Mn, Fe, Cu and Zn. Plant strengthening agent according to one of claims 8 to 10, characterized in that the solution preferably contains not more than 10 different metals (M1 M2 M3 ... Mx). Plant strengthening agent according to one of the preceding claims, characterized in that the aqueous medium containing phosphoric acid for the preparation of the aqueous solution (I) the phosphoric acid in a molar excess of the sum of the molar amounts of the metal cations of the oxidic metal to be introduced into the solution Contains compounds and to be introduced in elemental form or as an alloy metals. Plant strengthening agent according to one of the preceding claims, characterized in that the reaction of the oxidic metal compounds with the elemental forms or alloys of the metals in step a) at a temperature in the range of 5 ° C to 105 ° C, preferably in the range of 10 ° C. to 75 ° C, more preferably in the range of 20 ° C to 50 ° C, and / or with intensive mixing and / or for a period of 1 min to 240 min, preferably from 5 min to 120 min, more preferably from 30 min to 90 minutes. Plant strengthening agent according to one of the preceding claims, characterized in that the concentration of phosphoric acid in the aqueous solution (I) 5% to 85%, preferably 10% to 40%, particularly preferably 15% to 30%, most preferably 20% to 25 %, based on the weight of the aqueous solution (I). Use of a mixed metallic phosphonate of the type (M1 M2 M3 ... Mx) ₃ (PO ₄ ) ₂ · aH ₂ O with 0 ≤ a ≤ 9, as defined in any one of claims 1 to 7 and 12 to 14, or use aqueous solution (I) containing cations of various metals (M1, M2, M3 ... Mx) as defined in any one of claims 8 to 11 for the preparation of a plant strengthening agent.  A method of producing a plant strengthening agent, the plant strengthening agent having the features and the method comprising the steps of any one of claims 1 to 15.

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