阅读说明：本技术 微量营养素组合物和系统及其使用方法 (Micronutrient compositions and systems and methods of use thereof ) 是由 D·布朗 J·德兰杰德 于 2016-09-29 设计创作，主要内容包括：本发明涉及微量营养素组合物和系统及其使用方法。农业喷雾可以通过混合柠檬酸和谷氨酸与金属盐和农药或含有能沉淀混合物中的金属盐的成分的其它农用化学品来生产。柠檬酸和谷氨酸与金属盐螯合从而提供稳定性和相容性增强组合物,进而防止了金属盐在混合物中形成不溶性的固体。这样的组合物可通过以摩尔比约为6.8:0.5至1:0.29混合柠檬酸和谷氨酸而制得。该组合物可以包括摩尔比约为1:6.8:0.5至1:1:0.29的金属盐、柠檬酸和谷氨酸以及农药。(The present invention relates to micronutrient compositions and systems and methods of use thereof. Agricultural sprays can be produced by mixing citric acid and glutamic acid with a metal salt and a pesticide or other agrochemical containing ingredients capable of precipitating the metal salt in the mixture. Citric acid and glutamic acid are chelated with the metal salt to provide a stability and compatibility enhancing composition, thereby preventing the metal salt from forming an insoluble solid in the mixture. Such compositions may be prepared by mixing citric acid and glutamic acid in a molar ratio of about 6.8:0.5 to 1: 0.29. The composition may include a metal salt, citric acid and glutamic acid, and a pesticide in a molar ratio of about 1:6.8:0.5 to 1:1: 0.29.)

1. A method of increasing uptake in a foliar application comprising:

spraying the leaves with a mixture comprising citric acid, glutamic acid, a metal salt comprising zinc, and one or more agrochemicals;

wherein citric acid and glutamic acid form a chelate with the metal salt, thereby preventing the metal salt from forming an insoluble solid in the mixture,

wherein citric acid and glutamic acid are present in the agricultural spray in a molar ratio of about 14:1 to about 0.9:0.5, and

wherein the uptake of the metal salt comprising zinc by the leaves is enhanced by the chelated mixture.

2. The method of claim 1, wherein the citric acid and glutamic acid are present in a molar ratio of about 2: 1.

3. The method of claim 2, wherein the metal salt comprising zinc is present with the citric acid and the glutamic acid in a molar ratio of about 2:2: 1.

4. The method of claim 3, wherein the metal salt comprising zinc is zinc oxide.

5. The method of claim 1, wherein the molar ratio of the metal salt comprising zinc to citric acid is about 1:1, or wherein the molar ratio of the metal salt comprising zinc to glutamic acid is about 2: 1.

6. The method of claim 1, wherein the one or more agrochemicals comprises monosaccharides.

7. The method of claim 1, wherein the one or more agrochemicals comprises a fungicide.

8. The method of claim 7, wherein the one or more agrochemicals comprises monosaccharides.

9. The method of claim 7, wherein the one or more agrochemicals comprises one or more pesticides, the one or more pesticides comprising one or more of: n- (phosphonomethyl) glycine, 4-dichlorophenoxyacetic acid, bentazone, 3, 6-dichloro-o-anisic acid, 3, 6-dichloro-2-methoxybenzoic acid, 1-chloro-3-ethylamino-5-isopropylamino-2, 4, 6-triazine, amide herbicides, arsenic-containing herbicides, carbamate and thiocarbamate herbicides, carboxylic acid herbicides, dinitroaniline herbicides, heterocyclic nitrogen-containing herbicides, organophosphate compounds, urea herbicides, and quaternary ammonium salt herbicides, 5- [ 2-chloro-4- (trifluoromethyl) phenoxy ] -N- (methylsulfonyl) -2-nitrobenzamide, tebo trione, or esters of pesticides.

10. A method of making an agricultural spray comprising:

mixing citric acid, glutamic acid, a metal salt comprising zinc, and one or more agrochemicals;

wherein citric acid and glutamic acid are mixed in a molar ratio of about 14:1 to about 0.9: 0.5;

wherein citric acid, glutamic acid and metal salt form chelate; and is

Wherein the agricultural spray is a liquid that remains stable, non-precipitating for 72 hours, or

Wherein the mixture does not exhibit at least one of flocculation, sludge, gelation, agglutination, separation, or non-dispersing oil for at least one week.

11. The method of claim 10, wherein the metal salt comprising zinc is zinc oxide.

12. The method of claim 10, further comprising, prior to the step of mixing, the steps of: compositions are provided that include citric acid, glutamic acid, and a metal salt.

13. An agricultural spray comprising:

a zinc-containing metal salt, citric acid, and glutamic acid in a molar ratio of about 2:14:1 to about 1:0.9:0.5, wherein the citric acid, glutamic acid, and metal salt included form a chelate; and

one or more agrochemicals;

wherein the agricultural spray is a liquid that remains stable, non-precipitating for at least 72 hours, or

Wherein the mixture does not exhibit at least one of flocculation, sludge, gelation, agglutination, separation, or non-dispersing oil for at least one week.

14. The agricultural spray of claim 13, wherein the citric acid and glutamic acid are present in a molar ratio of about 2: 1.

15. The agricultural spray of claim 14, wherein the metal salt comprising zinc is present with citric acid and glutamic acid in a molar ratio of about 2:2: 1.

16. The agricultural spray of claim 15, wherein the metal salt comprising zinc is zinc oxide.

17. The agricultural spray of claim 13, wherein the molar ratio of the metal salt comprising zinc to citric acid is about 1:1, or wherein the molar ratio of the metal salt comprising zinc to glutamic acid is about 2: 1.

18. The agricultural spray of claim 13, wherein the one or more agrochemicals comprises a monosaccharide.

19. The agricultural spray of claim 13, wherein the one or more agrochemicals comprises a fungicide.

20. The agricultural spray of claim 19, wherein the one or more agrochemicals comprises one or more pesticides, the one or more pesticides comprising one or more of: n- (phosphonomethyl) glycine, 4-dichlorophenoxyacetic acid, bentazone, 3, 6-dichloro-o-anisic acid, 3, 6-dichloro-2-methoxybenzoic acid, 1-chloro-3-ethylamino-5-isopropylamino-2, 4, 6-triazine, amide herbicides, arsenic-containing herbicides, carbamate and thiocarbamate herbicides, carboxylic acid herbicides, dinitroaniline herbicides, heterocyclic nitrogen-containing herbicides, organophosphate compounds, urea herbicides, and quaternary ammonium salt herbicides, 5- [ 2-chloro-4- (trifluoromethyl) phenoxy ] -N- (methylsulfonyl) -2-nitrobenzamide, tebo trione, or esters of pesticides.

Technical Field

The present invention relates to products, systems and methods for improving the stability and compatibility of agricultural products, in particular, micronutrients in agricultural mixtures, using compositions.

Background

Crop protection involves the use of herbicides, insecticides, fungicides, collectively known as pesticides, to control the growth of weeds, and the damage of harmful insects and plant diseases to crops. Without these techniques, food production will fall, many fruits and vegetables will be in short supply, and the price of food will rise. In addition, as farmers lose their income from pests and diseases, the fiber in textile manufacturing, such as cotton, will be reduced.

Pesticides are often used in conjunction with adjuvants to enhance the performance of the pesticide. The adjuvant is in pesticide form or added into spray tank to improve pesticidal activity or use property. In addition, micronutrients may be used in combination with pesticides and adjuvants. Micronutrients include elements essential for plant growth including boron (B), copper (Cu), iron (Fe), chlorine (Cl), manganese (Mn), molybdenum (Mo) and zinc (Zn). For example, boron is essential for seed and fruit development to help plants use and regulate other nutrients, help plants produce sugars and carbohydrates. Copper is important for reproductive growth of plants, and helps in root metabolism and protein utilization. Chlorine helps the plant metabolism. Iron is an essential trace element in the formation of chlorophyll. Manganese is utilized by plant enzyme systems and is involved in carbohydrate breakdown and nitrogen metabolism. Molybdenum assists in the utilization of nitrogen. Zinc is required by plants to regulate growth and metabolize carbohydrates and sugars. Some trace elements are present in the soil, while others are not; some trace element levels in soil may not be sufficient for plant growth.

However, many pesticides contain phosphates that bind to the metal ions of the micronutrients and render the micronutrients insoluble solids prior to absorption by the plant, thereby rendering the micronutrients ineffective. In previous methods, ethylenediaminetetraacetic acid (EDTA) was used as a chelating compound for binding metal ions of micronutrients, preventing phosphates from converting micronutrients to insoluble solids. Although EDTA may prevent phosphate from binding metal ions, the metal ions exhibit reduced reactivity. Furthermore, EDTA is not accepted as a chelating agent in all countries. Other chelating compounds include organic acids and amino acids, as described in U.S. patent 5504055 and U.S. patent application publication 2005/239673, which are incorporated herein for any purpose.

Disclosure of Invention

Embodiments of the present invention provide compositions that can be used with agrochemicals that include ingredients that can precipitate micronutrients (e.g., metal salts) and methods of using these compositions.

According to certain embodiments, a method of spraying an agricultural spray comprises mixing a composition comprising citric acid and glutamic acid with a metal salt and a pesticide comprising a phosphate salt, wherein the citric acid and glutamic acid are chelated with the metal salt, thereby preventing the metal salt from reacting with the phosphate salt to form an insoluble solid.

In various embodiments and alternatives, the molar ratio of citric acid to glutamic acid in the composition is about 6.8:0.5 to 1: 0.29; the molar ratio of metal salt to citric acid and glutamic acid is about 1:6.8:0.5 to 1:1: 0.29; the metal salt is a metal salt of one or more of the following: zinc, boron, copper, iron, chloride, manganese, molybdenum, cobalt, magnesium, calcium or nickel; the metal salt is a metal oxide; the metal oxide is zinc oxide; the pesticide comprises N- (phosphonomethyl) glycine and/or one or more salts, esters or derivatives thereof.

According to another embodiment, a method of making a composition includes mixing a composition including citric acid and glutamic acid in a molar ratio of about 6.8:0.5 to 1: 0.29.

In various embodiments and alternatives, the method further comprises mixing the composition with a metal salt to produce a chelating composition, wherein the chelating composition has a molar ratio of metal salt, citric acid, and glutamic acid of about 1:6.8:0.5 to 1:1: 0.29; the chelating composition is mixed with a pesticide or a fertilizer to prepare an agricultural spray. Such pesticides may include one or more of the following: n- (phosphonomethyl) glycine, 4-dichlorophenoxyacetic acid, bentazone, 3, 6-dichloro-o-anisic acid, 3, 6-dichloro-2-methoxybenzoic acid, 1-chloro-3-ethylamino-5-isopropylamino-2, 4, 6-triazine, amide herbicides, arsenic-containing herbicides, carbamate and thiocarbamate (tiocarbamate) herbicides, carboxylic acid herbicides, dinitroaniline (dinitronaine) herbicides, heterocyclic nitrogen-containing herbicides, organophosphate compounds, urea herbicides, quaternary ammonium salt herbicides, 5- [ 2-chloro-4- (trifluoromethyl) phenoxy ] -N- (methylsulfonyl) -2-nitrobenzamide; teboltriketone or a derivative thereof.

According to yet another embodiment, a mixture of the composition includes a metal salt, citric acid and glutamic acid, and a pesticide in a molar ratio of about 1:6.8:0.5 to 1:1: 0.29.

In various embodiments and alternatives, the metal salt is a metal salt of one or more of the following: zinc, boron, copper, iron, chlorine, manganese, molybdenum, cobalt, magnesium, calcium or nickel; the metal salt is a metal oxide, such as zinc oxide; and the pesticide may include any of the above pesticides alone or in combination.

Drawings

Fig. 1A is a photograph of a composition disclosed in the prior art.

Figure 1B (left) is a photograph of a chelating composition of the invention and (right) a photograph of a composition disclosed in the prior art.

Detailed Description

To summarize: the compositions of the present invention comprise a proportion of organic acids and amino acids that bind to (e.g., chelate) the metal ions of the micronutrients, thereby preventing salts (e.g., phosphates) typically present in agrochemicals from converting the micronutrients to insoluble solids, while at the same time preventing fouling of the agricultural spray equipment or the pesticide. Thus, these compositions provide stability and compatibility to micronutrients in pesticides.

The metal ions often used in conjunction with the stability and compatibility-enhancing compositions include the transition metal of period 4. These transition metals include, but are not limited to: vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc. The 4 th cycle transition metal includes six chelating sites. The disclosed compositions include coordination sites that chelate to such transition metals. For example, citric acid has three coordination sites for chelation, and glutamic acid has four coordination sites for chelation.

While prior methods have used citric acid as a chelating agent to bind metal ions, it has been found that the use of citric acid chelating agents causes problems when mixed with agricultural sprays such as orthophosphate-based fertilizers including 9-18-9 fertilizers (i.e., 9% nitrogen-18% phosphoric acid-9% potassium) and 7-23-5 fertilizers. For example, when used with glyphosate, e.g., duranogo DMA, citric acid is incompatible with glyphosate and causes salt precipitation, thereby clogging the screens and spray heads in agricultural spray applications. Citric acid breaks the emulsion state when used with 2, 4-dichlorophenoxyacetic acid (2,4-D) and glyphosate, e.g., Enlist Duo. In addition, some products containing unchelated micronutrients are problematic for use in combination with agricultural sprays. For example, when micronutrients such as boron, zinc, manganese are mixed with various forms of glyphosate (e.g., glyphosate salts) and bentazon herbicides, amide herbicide nitrophenolate ethers, including 5- (2-chloro-4- (trifluoromethyl) phenoxy ] -N- (methylsulfonyl) -2-nitrobenzamide (e.g., fomesafen), and orthophosphate-based fertilizers (e.g., 9-18-9 and 7-23-5 fertilizers), the combination results in precipitation of metal ions.

Description of the embodiments: it has been found that a combination of citric acid and glutamic acid in a molar ratio of about 1:0.29 to 6.8:0.5 (wherein citric acid comprises 192.1g/mol and glutamic acid comprises 147.1g/mol) provides a stability and compatibility-enhancing composition that is very effective in preventing the reaction of micronutrients with phosphate in agricultural compositions such as pesticides and fertilizers, while at the same time preventing fouling of agricultural spray equipment or pesticides. In particular embodiments, the composition may include citric acid and glutamic acid in a molar ratio of about 14:1,13:1,12:1,10:1,9:1,8:1,7:1,6:1,5:1,4:1,3:1,2:1, or 1: 1. In some embodiments, a preferred citric acid to glutamic acid molar ratio is 2:1 or 0.9: 0.5.

The compositions of the present invention may be used, or may include, a variety of micronutrients in the form of metal ions, including water-soluble salts of zinc, boron, copper, iron, chloride, manganese, molybdenum, cobalt, magnesium, calcium, and nickel, or mixtures thereof. For example, the metal salt may include a water-soluble salt, sulfate, nitrate, hydroxide, acetate, carbonate, chloride, phosphate, or a mixture thereof. In some embodiments, preferred metal salts include zinc salts such as zinc sulfate (ZnSO)₄) Zinc nitrate (Zn (NO)₃)₂) Zinc oxide (ZnO), zinc chloride (ZnCl)₂) Zinc chlorate Zn (ClO)₃)₂Zinc phosphate (Zn)₃(PO₄)₂) Zinc molybdate (ZnMoO)₄) Zinc chromate (ZnCrO)₄) Zinc fluoride (ZnF)₂) Zinc bromide (ZnBr)₂) And zinc cyanide (Zn (CN)₂). Other preferred metal salts may include metal sulfates, such as zinc sulfate (ZnSO)₄)。

More specifically, the disclosed compositions may be chelating compositions that provide stable micronutrient formulations that are also compatible with soil and foliar nutrient and/or pesticide mixtures. In some embodiments, the chelating composition may comprise a molar ratio of about 1:6.8:0.5 to 1:1:0.29 metal oxide, citric acid and glutamic acid. In particular implementations, the chelating composition can include a molar ratio of about 2:14:1,2: 13:1,2: 12:1,2: 10:1,2: 9:1,2: 8:1,2: 7:1,2: 6:1,2: 5:1,2: 4:1,2: 3:1,2: 2:1,1: 0.9:0.5, or 1:1:0.29 metal salt: citric acid: glutamic acid. In some embodiments, it is preferred that the zinc oxide: citric acid: the molar ratio of glutamic acid is 2:2:1,1: 0.9:0.5, or 1:1:0.29 (e.g., with 81.4 g/mol ZnO: 192.1g/mol citric acid: 147.1g/mol glutamic acid).

According to some embodiments, the compositions of the present invention may be free of other chelating agents such as ethylenediaminetetraacetic acid (EDTA) and variants thereof, such as its conjugate base ethylenediaminetetraacetic acid (e.g., tetrasodium ethylenediaminetetraacetic acid). In particular, the combination of citric acid and glutamic acid is effective in binding the metal ions of the micronutrient and preventing the phosphate from converting the micronutrient to an insoluble solid without the need to use other well known chelating agents such as EDTA. The use of the EDTA-free organic acids of the present invention may also be used to avoid phytotoxicity, such as burning. Additionally or alternatively, the chelating agent in the composition of the invention may consist of or consist essentially of glutamic acid and citric acid. Such chelating agents may be chelated with one or more metal ions and/or may be present in excess in the mixture. Other components, such as water, antifoam, sugar sources, surfactants, biocides, propylene glycol, sodium hydroxide, may be present in the disclosed compositions, such as those necessary to produce and dispense stability and compatibility-enhancing products without affecting the effectiveness of the chelating component.

Many pesticides, such as herbicides, insecticides and/or fungicides, are compatible with the compositions of the present invention. Such herbicides include, but are not limited to: various forms of N- (phosphonomethyl) glycine, for example, glyphosate, including forms of salts, esters or other derivatives thereof. Examples of glyphosate products include, but are not limited to: potassium salt forms (e.g., Roundup PowerMax and Touchdown Total), dimethylamine salt forms (e.g., duranogo DMA), and isopropylamine salts (e.g., Cornerstone 5+), glyphosate in combination with other pesticides such as 2, 4-dichlorophenoxyacetic acid (2,4-D) (e.g., Enlist Duo) and dicamba (e.g., Mon 76832 and Roundup xten).

Other compatible herbicides include, but are not limited to: the sodium salt of bentazon (3- (1-methylethyl) -1H-2,1, 3-benzothiadiazin-4 (3H) -one 2, 2-dioxide) (e.g., bentazon herbicide); diglycolamine salts of 3, 6-dichloro-o-anisic acid (e.g., Sterling Blue); 3, 6-dichloro-2-methoxybenzoic acid (e.g., dicamba, engini); 2, 4-dichlorophenoxyacetic acid (2, 4-D); 1-chloro-3-ethylamino-5-isopropylamino-2, 4, 6-triazine (atrazine); amide herbicides; an arsenic herbicide; carbamate and thiocarbamate herbicides; a carboxylic acid herbicide; a dinitroaniline herbicide; a nitrogen-containing heterocyclic herbicide; an organic phosphorus compound; urea herbicides; and quaternary ammonium salt herbicides; 5- [ 2-chloro-4- (trifluoromethyl) phenoxy ] -N- (methylsulfonyl) -2-nitrobenzamide (fomesafen); cyclic sultone (e.g., Laudis).

Weeds that can be controlled using the herbicidal composition include, but are not limited to: cockspur grass, green bristlegrass, wild oat, sunflower, piemarker, annual morning glory, water chestnut, chenopodium album, sparrow wheat.

According to certain embodiments, compatible herbicides may contain the elements nitrogen, phosphorus, and potassium in a ratio such that the composition can be used as both a herbicide and a fertilizer. Fertilizers compatible with the compositions of the present invention include, but are not limited to: N-P-K fertilizers, such as 9-18-9 and 10-34-0 fertilizers, and atrazine-containing fertilizers.

Additionally or alternatively, the herbicide may comprise a pesticide and/or a fungicide. Insecticides compatible with the compositions of the present invention include, but are not limited to: pyrethroid insecticides (e.g., bifenthrin); pyrethrins or other plants (e.g., D-limonene, linalool, ryanodine, rotenone, eugenol (clove oil), nicotinoyl chloride, essential oils (e.g., citronella, piperita, rosemary, cinnamon, sesame, thyme, cedar oil, and capsaicin), neem oil (e.g., azadirachtin), nicotine, microbial products (e.g., Bacillus thuringiensis and Beauveria bassiana), oxadiazines (e.g., indoxacarb), phthalamides (e.g., chlorantraniliprole), juvenile hormone mimics (e.g., fenoxycarb, pyriproxyfen, methoprene, and hydroprene), pyrroles (e.g., chlorfenapyr), phenylpyrazoles (e.g., fipronil), organophosphates (e.g., malathion and chlorpyrifos), inorganic substances (e.g., sulfur and dormant and horticultural oils), insect growth regulators such as chitin synthesis inhibitors (e.g., hexaflumuron; a polyfluorourea; diflubenzuron; a buprofezin pesticide purity standard substance; cyromazine; and halofenozide); acaricides such as acaricides (e.g., abamectin) and acaricides alone or in any combination with the compositions of the present invention. Fungicides compatible with the compositions of the present invention include, but are not limited to: fluxapyroxad, pyraclostrobin, propiconazole, trifloxystrobin, prothioconazole, 1, 2-propanediol, azoxystrobin (e.g., Priaxor, On Set, Topaz, Headline amp, Headline sc, Stratego, Quadris), alone or in any combination with the compositions of the invention.

In addition, a separate fertilizer (e.g., not necessarily present in the pesticide) may be compatible with the compositions of the present invention and may include, but is not limited to: nitrogen phosphorus potassium fertilizers such as 9-18-9 and 10-34-0 fertilizers.

The compositions of the present invention differ from the process disclosed in the us 5504055 patent (the' 055 patent), in which the zinc oxide/citrate/glutamate chelate is prepared by: water was degassed and zinc oxide, citric acid and glutamic acid (i.e., 81.4 g of zinc oxide, 30 g of citric acid, 294.2 g of glutamic acid in a molar ratio of 1:0.16: 2) were mixed at a weight ratio of 3:1:10 to form an aqueous solution, which was then dried to form a zinc amino acid chelate. However, when used in combination with plant nutrients, the chelate of the '055' patent is described as enhancing the performance of plants compared to controls that do not use such zinc amino acid chelates, but studies have shown that the chelate is unstable and therefore cannot be used in an agricultural environment. Specifically, FIGS. 1A and 1B (right) are pictures of a zinc oxide/citrate/glutamic acid mixture prepared according to the method described in example XI of the' 055 patent at a molar ratio of 1:0.16: 2; while the left side of fig. 1B, labeled AGM14032 vessel, was zinc oxide in a 2:2:1 molar ratio: citric acid: images of the inventive composition of glutamic acid. FIG. 1A is a picture taken after stirring the mixture of the '055' patent for 24 hours, but before filtration. The opaque layer is zinc ions converted to an insoluble white solid and the transparent layer is citric acid in water. Prolonged stirring is desirable to dissolve the components in the solution. In fig. 1B, a picture of the mixture of the '055' patent was taken 24 hours after filtration and shows an opaque mixture with precipitated solids under the clear layer. Thus, the molar ratio is 1:0.16:2 zinc oxide/citrate/glutamic acid did not form a stable composition. In contrast, the left side of fig. 1B shows a 1:1:1 molar ratio zinc oxide/citric acid/glutamic acid mixture after 24 hours of mixing, in which citrate and glutamic acid have been chelated with zinc ions, whereby the mixture becomes transparent orange due to the fact that zinc is not precipitated in the mixture. The mixture remained in this stable, non-settling state for more than 42 days.

Production of stability and compatibility-enhancing compositions

To produce the chelating compositions of the invention, the metal oxide (e.g., zinc oxide), glutamic acid, citric acid, and an amount of sodium hydroxide necessary to raise the pH to 7.5 are mixed with water and stirred at about 130 ° F until all of the starting materials are dissolved, and the mixture is colorless and transparent. Water may be added to obtain the desired volume and the mixture stirred until the product reaches a homogeneous state. The metal oxide, glutamic acid, and citric acid may be added in any order. In one embodiment, the mixture may contain 7.5% zinc oxide, 18.4% citric acid, 7.1% glutamic acid (e.g., in a 2:2:1 molar ratio). The mixture of components produces an exothermic reaction and the temperature of the mixture is monitored and maintained below 165 ° F, preferably below 165 ° F. During production, the pH of the mixture is acidic (e.g., pH about 3) and can be adjusted to about 7.5. The final pH of the product after 24 hours was about 8.0.

The chelating composition may be converted into a solid, such as a water-soluble powder, granules and/or pellets. Additionally or alternatively, the composition may be combined with micronutrients and the chelate may be converted to a solid.

The chelating compositions of the present invention are stable under a variety of conditions, including but not limited to: more than five cycles under freezing/thawing conditions (-18 ℃ C. + -. 2 ℃ C.), more than 3 months under refrigerator conditions (0 ℃ C. + -. 2 ℃ C.), and five weeks at higher temperature (54 ℃ C. + -. 2 ℃ C.), which is equivalent to more than 12 months at room temperature. In particular, according to the ASTM protocol, under oven conditions at 54 ℃, the mixture is stable for two weeks, equivalent to having a shelf life of 12 months at room temperature, which means that the composition of the invention, which is stable over five weeks, has a shelf life of more than 12 months.

In addition, the chelating compositions of the present invention are compatible with disclosed pesticides, including but not limited to: glyphosate, 2,4-D, sterling blue, bentazon, atrazine, engini, Enlist duo and derivatives thereof. Specifically, the mixture of the composition of the invention and the pesticide exhibits no flocculation, sludge, gelling, agglutination, precipitation, separation, or no dispersion of oil over a typical test period such as 15 minutes, 2 hours, 6 hours, or 24 hours or more, such as 72 hours or at least one, two, three, four, five or six weeks.

Application method

The compositions of the present invention may be used in agricultural spraying techniques, such as application to seeds, soil, leaves and fruits of plants. Such sprays can be broadcast using both ground and air techniques.

Prior to use, the disclosed compositions may be mixed with, for example, water, micronutrients, pesticides, antimicrobial compositions, antifoaming agents, adjuvants (e.g., alkyl polyglycosides), monosaccharides (e.g., high fructose corn syrup), disaccharides, formulation aids (e.g., propylene glycol), surfactants (e.g., cationic, anionic, and/or nonionic), and pH adjusting agents. The mixing may be carried out under stirring and may be at ambient temperature, for example aboutOr may occur at elevated temperatures above 90F. Stability and compatibility-enhancing compositions (e.g., chelated compositions) have a pH of about 8.0 prior to mixing.

The performance of the compositions of the present invention is similar or better than EDTA-containing chelating products with respect to plant uptake of micronutrients without phytotoxicity. In addition, these compositions also provide benefits over the use of EDTA due to environmental issues associated with the use of EDTA.

Examples

Stability of

Stability tests were performed on stability and compatibility-enhancing compositions having a molar ratio of zinc oxide, citric acid and glutamic acid of 2:2:1 using a procedure modified from CIPAC MT39 and CIPAC MT46.3, involving freeze/thaw, refrigerator, oven stability tests.

Materials and methods

The apparatus used in the stability test includes: a 120mL graduated jar; a flashlight; an oven controlled to a specified temperature (+ -2 ℃); and a refrigerator controlled to a prescribed temperature (+ -2 ℃).

The test procedure for freeze/thaw stability involved transferring a quantity of product to a graduated jar; putting the bottle into a refrigerator with the temperature of-18 +/-2 ℃; after 24 hours of freezing, the samples were removed from the freezer and allowed to warm to room temperature; once room temperature was reached, the product underwent one cycle. The samples were subjected to a total of 5 cycles.

Freeze/thaw evaluations were performed after each cycle and observed for any changes in product formulation including, but not limited to, phasing, creaming, sedimentation, crystal growth, precipitation, color change, and/or container discoloration. A flashlight was used to view the darker formulation. If a change in formulation is observed, it is desirable to record the number of inversions to obtain homogeneity of the product. The test is considered to have failed if the inversion of the product does not homogenize the product.

Testing stability using refrigeration involves transferring the product to a graduated jar; putting the wide-mouth bottle into a refrigerator at 0 +/-2 ℃; the product was checked for any changes on a daily basis for four weeks. After four weeks, the product was checked once a week. The product testing time lasted three months.

Evaluation of the refrigeration stability was performed at each product inspection and observed and recorded according to the methods described in the evaluation on freezing/thawing.

An oven was used to participate in the stability test at high temperature. A quantity of product was transferred to a graduated jar and placed in a 54 c 2 c oven. The product was checked for any changes on a daily basis for four weeks. After four weeks, the product was inspected once a week. The product was allowed to remain in the oven for 3 months.

The stability test at high temperature was performed at each product inspection and observed and recorded according to the described method in connection with the freeze/thaw test.

Results

The results of the stability test show that: the composition remains stable under freeze/thaw conditions for more than five cycles; stable under refrigerator conditions for more than three months; and remains stable over more than five weeks of heating, which corresponds to a shelf life of more than 12 months.

Compatibility

Testing stability and compatibility-enhancing the compatibility of a composition with a pesticide, said composition comprising a molar ratio of 2:2:1 zinc oxide, citric acid and glutamic acid, the improved method adopted being from ASTM E1518-05(2012), standard practice for testing the physical compatibility of pesticides in tank mixtures using dynamic vibration methods, ASTM international, western conschheken, PA, 2012. The pesticides tested included: various forms of glyphosate, Roundup Power Max, Durango, Cornerstone 5+, Touchdown Total, 2,4-D, Sterling Blue, Basagaran, Atrazine, Enginia, Enlist duo, and Roundup Xtend.

Materials and methods

The apparatus used in the compatibility test comprises: 1.120mL graduated cylinder; 2. a pipette; 3. a balance with the precision of +/-0.01 g; 4. sieve, U.S. standard, 50 mesh (300 μm) with a diameter of 3 inches; and 5. a flashlight. Reagent grade chemicals and water used in all tests had a purity level of form IV relative to the reagents used. The synthetic water was prepared according to CIPAC handbook part F, MT 18.

The final configuration of the compatibility test was at or about 100mL and the desired rate was calculated for application of 10 gallons per acre to 100mL per acre. At room temperature, 70% of the water required for the compatibility test was added to the cylinder. The remaining ingredients were added for the beaker test according to WALES and DALES unless the product label was otherwise stated. The application rate was used from the product label. The liquid product is transferred using a pipette or weighed as a solid product. After each individual product was added, the jar was capped and hand swirled until the product became homogeneous. After all the product was added, the remaining water was added. The entire mixture was stirred for a period of not less than 30 seconds.

The tests and evaluations were performed 0.25, 2,6, 24, and 72 hours after stirring the mixture. The evaluations were classified into seven categories, flocculation, sludge, gelation, coagulation, sedimentation, separation, and nondispersed oils, respectively. Each category employs a ranking of 1-5 (1 being the case of none, 5 being the one with the most presence).

Results

The results of the compatibility test showed that the composition did not have any flocculated, sludged, gelled, agglomerated, precipitated, separated, or non-dispersible oils after 42 days. For each herbicide tested, all classes were scored as 1 over this time period.

Absorption/efficiency

The zinc foliar absorption test was conducted during the corn growth phase of 2015 in rifflers, wisconsin and rossmont, mn. The assay was performed according to a fully randomized block design in quadruplicate. The cell area is 10 feet by 30 feet. Using four different products analyzed in brackets, 0.11 pounds/acre equivalent of zinc was applied to corn foliage at a total application rate of 10 gallons/acre for each plot: the stability and compatibility-enhancing composition of the present invention (0-0-0-6.0Zn) contains zinc oxide/citric acid/glutamic acid in a molar ratio of 1:1: 0.5; Ultra-Chezinc 9% EDTA (7-0-0-9Zn) (derived from ethylenediaminetetraacetic acid diammonium Zinc (EDTA)); and Citri-Chezinc 10% (6-0-0-10Zn) (derived from Zinc chloride, Zinc oxide, Zinc EDTA, citric acid and ammonium hydroxide). All products tested were chelated. The compositions of the present invention were free of EDTA and its derivatives, whereas the two compositions tested contained chelated EDTA.

Prior to foliar application of the zinc-containing product, complex tissue samples were collected at the test area, including the uppermost fully developed maize leaf. This sample establishes the existing zinc content of the corn plant.

Foliar application of the compositions of the invention applied to corn at the growth stage of V4 was tested for zinc uptake by plant tissue analysis. Plant tissue samples were collected from each plot 6 days after application. The sample was the uppermost fully developed maize leaf collected from each plant in the middle two rows of the plot. The center two rows are the only rows used to ensure that the sampled plants receive even coverage during product application and eliminate the possibility of spray overlap. Corn tissue was analyzed by the midwestern laboratory (13611B street, omaha, nebraska, 68144).

Results

The results in table 1 demonstrate that the performance of the disclosed compositions is similar or superior to that of EDTA-chelated products.

Although the methods disclosed herein have been described and illustrated with reference to particular operations performed in a particular order, it will be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present invention. Accordingly, unless specifically noted herein, the order and grouping of the operations should not be construed as limiting.

Similarly, it should be appreciated that in the foregoing description of exemplary embodiments, various features are sometimes grouped together in a single embodiment or description for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claims require more features than are expressly recited in a single claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment, and each embodiment described herein may contain multiple inventive features.

While the present disclosure has been particularly shown and described with reference to embodiments thereof, it will be understood by those skilled in the art that various other changes in form and details may be made therein without departing from the spirit and scope of the disclosure.