WO2018184081A1 - "fertilizer composition having adjuvant properties and use of said fertilizer composition having adjuvant properties" - Google Patents

Abstract

The present invention relates to a novel fertilizer composition that enables greater stability among tank mixes and which can be used together with agrochemicals and other micro/micronutrients. The composition thereof comprises at least one nitrogen-derived component, at least one phosphorus-derived component, at least one ethoxylated ester, at least one ethoxylated alcohol, at least one component selected from polyethylene glycol, diethylene glycol and monoethylene glycol and one siliconized component. The present invention also describes the use of said composition, as well as agrochemical mixtures and/or fertilizers in which said composition can be used. It was noted that said novel composition, in addition to having the necessary nutrients for plant development, is capable of improving the stabilization of mixtures containing herbicides and fertilizers under various conditions.

Description

 "FERTILIZING COMPOSITION WITH ADJUVANT PROPERTY, AND, USE OF FERTILIZING COMPOSITION WITH ADJUVANT PROPERTY"

 Field of the Invention

[001] The present invention relates to a novel adjuvant fertilising composition which allows for greater stability between tank mixtures and may be used in conjunction with herbicides and other micro / macronutrients. This invention also describes the use of this composition.

 Background of the Invention

[002] The need for fertilizer use in agriculture is essential for increasing crop productivity and ensuring food production in view of world population growth. The main elements that make up fertilizer compositions are divided into two main groups: the mineral and non-mineral components.

Non-mineral components are generally composed of hydrogen, oxygen and carbon. Mineral nutrients are divided into macronutrients and micronutrients. Nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg) and sulfur (S) components are named macronutrients. Already the most common micronutrients stand out manganese (Mn), boron (B), cobalt (Co), molybdenum (Mo), nickel (Ni), silicon (Si), zinc (Zn) among others.

[004] As a source of nitrogen we can cite: urea, ammonium sulfate, potassium nitrate, ammonium monophosphate and ammonium diphosphate with their respective acids. For the supply of phosphorus, different sources may be used, such as phosphoric acids or polyphosphates. Potassium usually comes from potassium chloride KCl (60 to 62% K ₂ O and 48% Cl), potassium sulfate K ₂ SO ₄ (50 to 53% K ₂ O and 17% S), potassium nitrate KNO ₃ (44 to 46% K ₂ O and 13 to 14% N) and potassium sulfate and magnesium .2MgS0 K2S0 _{4 4} (22% K ₂ 0, 22% S and l2 to l8% Mg). Among these sources, KC1 represents the largest share of the market, approximately 95% of all potassium used in agriculture.

 Micro / macronutrients are generally used in combination with pesticide mixtures in a single application to optimize time, labor, broaden the spectrum of action and nourish the soil / plant. Due to the large possibilities for spray mix preparation, the formation of incompatible mixtures can lead to precipitation of insoluble solids, resulting in problems such as tank settling, filter and nozzle clogging and non-uniform application.

Among the herbicides used for weed control, the most commonly used is n-phosphomethylglycine, better known as glyphosate. Due to its low toxicity, high efficacy in a wide range of pest species and easy obtaining and synthesis, glyphosate has quickly become popular in the market. Another widely used herbicide is 2,4-dichlorophenoxyacetic acid (2,4-D). Salts of such herbicides are usually prepared by neutralizing the acid with organic bases such as isopropylamine, dimethylamine, among others. The frequently used glyphosate salts are monoisopropylamine (MIPA), potassium hydroxide (KOH), ammonia (NH ₃ ), monoethanolamine (MEA), triethanolamine (TEA) or mixtures thereof in order to become water soluble.

[007] It is known that spray mixtures containing cation mixtures of metal or alkaline earth metals, 2,4-D and glyphosate generally cause precipitation problems and, consequently, affect application.

Due to this problem, it is very common that compositions with 2,4-D already contain adjuvants in their composition for the purpose of avoid incompatibility issues.

 As an example, mention may be made of WO

2008 / 069826A1 reporting an adjuvanted herbicide formulation aimed at reducing the incompatibility problems between glyphosate and 2,4-D. WO 2012 / 027349A1 describes the development of a 2,4-D formulation containing polyethylene amine and / or polyvinyl amine as crystallization inhibitors for cation mixtures present in fertilizers.

 However, the use of herbicides with compatibilizing adjuvants already present in their composition limits the possibility of mixtures, since in this case the order of addition of the products may alter the final result. The development of a solution to be added directly to the spray solution will allow the dosage to be adjusted according to the complexity of the mixture, thus allowing a greater number of combinations. Thus, the Applicant has developed a fertilizer composition which may be added to the spray solution at a rate of 0.1-2.0%, depending on the complexity of the spray solution.

 The use of ammonium sulfate as a water conditioner for mixtures containing glyphosate, 2,4-D and Dicamba is also known. In this case, sulfate anions act by competing with glyphosate for hard water cations, thus reducing the possibility of formation of insoluble glyphosate species. However, it is known that the use of ammonium sulfate in syrups promotes increased volatility of Dicamba, providing losses of the active ingredient during application. Thus, the search for alternative water conditioners has been the focus of many companies holding formulations involving the active ingredient Dicamba.

Publication WO2015 / 061873 teaches a fertilizer formulation containing low oil volume syrup adjuvants (BVO). This composition comprises aliphatic hydrocarbons, fatty acid esters, mixtures of nonionic and ionic surfactants, organosiliconised compounds and compatibilizing agents for the stability of grout. However, it is known that most products currently developed are still intended for application in aqueous syrup, so the solution proposed by this patent document limits the possibility of applications.

 Thus, there is a need for a fertilizer composition that can be used in mixtures containing micro / macronutrients and herbicides such as glyphosate and 2,4-D. Currently these herbicides represent the largest volume of herbicide sales in the world and due to their hydrophilic characteristics are applied in aqueous syrups.

 Further, it is important to obtain a water conditioning product which allows the use of high hardness water soluble salt type compositions avoiding the formation of undesirable solids during application. Finally, it is also desired to find a composition that is completely free of nonylphenol and derivatives, making it a solution consistent with the new standards of the legislation.

 Summary of the Invention

The present invention relates to a novel fertilizer composition which can also be used as an adjuvant to increase the stability of herbicide-fertilizer mixtures. The composition of this invention comprises at least one nitrogen derived component, at least one phosphorus derived component, at least one ethoxylated ester, at least one ethoxylated alcohol, at least one component selected from polyethylene glycol, diethylene glycol and monoethylene glycol and one component. siliconed. Additionally, the composition may further contain calcium (Ca), magnesium (Mg), sulfur (S) manganese (Mn), boron (B), cobalt (Co), molybdenum (Mo), nickel (Ni), silicon (Si), zinc (Zn), iron (Fe), copper (Cu), chlorine (Cl) in the form of cation, oxide or element. This invention also describes the use of this composition as an adjuvant as well as mixtures in which it may be used.

 Brief Description of the Figures

The advantage described above is clearer to those skilled in the art from the accompanying figure:

 [0017] Figure 1 shows the evaluation of spray solution stability in graph form for two different fertilizer compositions.

 Figure 2 presents the photos of the tests performed to evaluate the parameters in Figure 1.

 Figure 3 shows the results of tests between herbicidal mixtures and different concentrations of the fertilizer composition.

 Figure 4 shows the result of testing between the fertilizer composition of the present invention at different concentrations with other fertilizers.

 Detailed Description of the Invention

The novel adjuvant property fertilizer composition described in this invention may be incorporated into spray mixtures containing herbicidal formulations such as 2,4-D salts and glyphosate, including MIPA, potassium, MEA, TEA or your mixtures. It can also be used in mixtures containing fertilizers. Also, the new composition is totally free of nonylphenol and its derivatives.

The composition of this invention comprises at least one nitrogen derived component, at least one phosphorus derived component, at least one ethoxylated ester, at least one ethoxylated alcohol, at least one component selected from polyethylene glycol, diethylene glycol and monoethylene glycol and a silicon component. In one embodiment of the present invention, the adjuvant property fertilizer composition comprises between one and three nitrogen derived components, comprises between one and three phosphorus derived components, comprises between one and three ethoxylated esters, between one and three ethoxylated alcohols, a component selected from polyethylene glycol, diethylene glycol and monoethylene glycol and a silicone component.

 The novel composition to which this invention relates comprises one or more nitrogen source derivatives in the proportion of 2-30% by weight of the composition. In the case of this invention, the components may be: urea, ethoxylated urea, ammonium sulphate, potassium nitrate, ammonium monophosphate and ammonium diphosphate, ethoxylated alkyl etheramines, ethoxylated coconut amine, ethoxylated imidazolines, dimethylated alkyl amine oxides, alkyl dimethyl betaines, alkyl starch propyl amines and ethoxylated alkyl amines.

 More specifically, the nitrogen source is selected from:

 (i). Urea derivatives

 on what:

R ₂ is a C 4 hydrocarbyl,

 x is a number from 1 to 20,

 n is a number from 0 to 20,

 y is a number from 0 to 20,

w is a number between 0 and 20. (ii). Amine Grease Derivatives.

 on what:

 R is an alkylated carbon chain,

 m is a number from 1 to 20,

 n is a number from 0 to 20,

 m + n may result in 10 to 40.

As a source of phosphorus, the new composition may be composed of the components or mixtures thereof. Examples may include: phosphoric acid, polyphosphoric acid, phosphorous acid, phosphate polyethylene glycol monoalkyl ether, phosphate alcohol, phosphate ethoxylated alcohol, phosphate methyl alcohol, phosphate ethoxylated lauryl alcohol, phosphate ethoxylated tridecyl alcohol. These components or mixtures thereof may be present in the composition in the proportion of 10-60% by weight of the composition.

 More specifically, the source of phosphorus is selected from:

 (i). phosphate ethoxylated monoester alcohol

 The

 II

 R- (0CH CH) - 0 - P - OH

 £,. n i

 OH

 on what:

 R may be a branched, aromatic or straight carbon chain

 n is a number from 1 to 20.

 (ii) ethoxylated alcohol phosphate diester

 THE

II

 R- {0CH (CH) -r 0 - P - OH

{OCH ₂ CH ₂ ) ~ _n O R may be a branched or straight carbon chain n is a number from 1 to 20.

 (iii) polyphosphoric acid

HO (P0 ₂ OH)

 on what:

 n is a number from 0.01 to 2.

 (iv) phosphate isodecyl alcohol.

 The new composition also comprises ethoxylated alcohols or mixtures thereof. Examples include: ethoxylated lauryl alcohol, ethoxylated keto-stearyl alcohol, ethoxylated isodecyl alcohol, ethoxylated tridecyl alcohol, ethoxylated caprylic alcohol, among others. These components may be present in the adjuvant fertilising composition in the proportion of 0.1-10% by weight of the composition.

R- (0CH CH) -1 OH wherein:

 R may be a branched or straight carbon chain n is a number from 1 to 30.

It has been observed that the mixture containing the acid with its phosphate ethoxylated surfactant provides the best resistance to pH variations. This behavior is especially important for glyphosate, which may protonate at different pHs affecting its solubility.

 The fertilizer composition with adjuvant assignments further comprises at least one of the following components: polyethylene glycol, diethylene glycol, monoethylene glycol, sorbitan polyethylene, ethoxylated sorbitan esters or mixtures thereof.

More specifically, the composition comprises:

(i) Ethoxylated sorbitan ester % C t ¾ CN, -

 on what:

 R: can be an alkyl, aryl or ester group

 x + y + z = is a number from 10 to 30.

 (ii) Polyethylene glycol

H (OCH ₂ CH ₂ ) OH

 on what:

 n: is a number from 0-20.

Organosiliconised compounds are also present in the present invention in the proportion of 0.1-10%.

 In one embodiment, the present invention discloses an adjuvant-capable fertilizer composition comprising: 2-30 wt% of components as a nitrogen source, 10-60 wt% of components as a phosphorus source and an adjuvant compatibilizer in the proportion 10-60% by weight. This adjuvant contains 1-30 wt% of an ethoxylated ester, 0.1-10 wt% of an ethoxylated alcohol, 5-30 wt% of a polyethylene glycol and an organosiliconised component in the ratio of 0.1-10% by weight. Weight.

 In a preferred embodiment, the adjuvant property fertilizer composition comprises: 10-30 wt% components as nitrogen source, 10-20 wt% components as phosphorus source, 10-30 wt% of an ethoxylated ester, 0.5-5% by weight of an ethoxylated alcohol, 10-20% by weight of a polyethylene glycol and an organosiliconised component in a proportion of 1-5% by weight.

This adjuvant property fertilizer composition may be used in spray mixtures at concentrations ranging from 0, 1 to 2% by weight. Specifically, the composition of the present invention may be used in mixtures containing glyphosate and 2,4-D, in addition to other herbicides of the following chemical classes: aryloxyphenoxypropionates, cyclohexadiones, phenylpyrazines, sulfonylureas, imidazolinones, triazolopyrimidines, pyrimidyl (thio) benzoates , suphonylaminocarbonyltriazolinones, triazines, triazinones triazolinones, uracils, pyridazinones, phenylcarbamates, ureas, amides, nitriles, benzothiadiazinones, phenylpyridazines, diphenylethers, phenylpyrazoles, N-phenylphthalazoles, thiadiazoles, triazinones pyrazoles, benzoic acid, pyridines, nitriles, benzoic acid, phenoxycarboxylic acid, semicarbazones, phthalamates, carbamates, pyridazinones, uracils, among others.

 It can also be used in mixtures containing various types of fertilizers. Examples include: ammonium sulfate, potassium nitrate, monoammonium diamonic phosphate, potassium chloride, potassium sulfate, potassium nitrate, and potassium magnesium sulfate, phosphoric acid, polyphosphoric acid, calcium, magnesium oxide, manganese chloride, manganese oxides, manganese sulfate, zinc oxides, iron oxides, among other micronutrients used as fertilizers.

EXAMPLE

 During the development of the fertilizer composition, various combinations were evaluated in order to find the most efficient formulation for spray mixtures.

 Thus, here are the examples of two fertilizer compositions:

Fertilizer composition 1 comprises 27.0% ethoxylated grease amine, 12.5% phosphate isodecyl alcohol, 1.2% phosphoric acid, 2.0% ethoxylated isodecyl alcohol, 27% ethoxylated sorbitan ester , 16% polyethylene glycol and 1% silicone components. Fertilizer composition 2 comprises 16.5% phosphate ethoxylated tristirylphenol, 1.0% phosphoric acid, 27.0% ethoxylated sorbitan ester, 20.0% polyethylene glycol and 0.5% silicon components.

 Subsequently, the fertilizer compositions were tested under more stressful conditions in order to evaluate the stabilizing power of the syrups. The varied parameters were: temperature (5 ° C, 25 ° C), glyphosate concentration (1.5 kg / hec, 4.0 kg / hec), presence of manganese (yes, no) and presence of zinc and cobalt ( Yes No).

 The evaluations of the syrup stability were made visually and comparatively. When there was no significant change with the addition of the composition, the grade was zero. When there were improvements with addition of composition, the grade was 1. When the improvement was significant was given grade 2. Thus, the best fertilizer compositions had the highest grades.

 As a procedure, the fertilizer compositions were first added to the water and then the spray grouts added. Stirring was standardized using on a shaker table for 15 minutes. Visual assessment was performed after 30 minutes, 2 hours and 24 hours of rest.

 The following parameters were used for the evaluation of spray solution stability for the two different fertilizer compositions: temperature (5 ° C, 25 ° C), concentration of potassium glyphosate solution 480 g / L in the application solution. (1.5 kg / hec, 4.0 kg / hec), presence of 4L / hec manganese fertilizer (yes, no), presence of 0.02 L / hec zinc and molybdenum fertilizer (yes, no ).

 Figure 1 presents a performance graph of the formulations tested.

[0047] Looking at Figure 1, it can be seen that the composition Fertilizer 1 proved to be more robust to spray mix temperature changes.

 [0048] Figure 2 presents the photos of the tests performed to evaluate the parameters in Figure 1. It can be seen the visual evaluations used to compare the compositions when exposed to different temperature conditions, glyphosate concentration and presence of fertilizers. The photos were taken with the pure concentration syrups, ie without fertilizer composition, and with the fertilizer compositions 1 and 2 described above. It is clearly perceived the smallest amount of precipitate formed in the samples using the fertilizer composition 1.

A test was then performed using fertilizer composition 1. This fertilizer composition was added to a mixture containing 1.5 L / hec potassium glyphosate solution 480 g / L el, 5 L / hec solution 2, 4-D 806 g / l.

 The fertilizer composition with adjuvant properties was added at the following concentrations: a) 0.1 wt%, b) 0.2 wt%, c) 0.3 wt% and d) 0.4 wt% of the spray solution. For the elaboration of the tests, it was considered an application syrup of 100 L / hec.

As can be seen from the results presented in the

Figure 3, the addition of the fertilizer composition with adjuvant properties promotes significant decrease of spray solution solids. After the addition of 0.3% of the fertilizer composition 1 it is not possible to visualize precipitates in the syrup.

 [0052] To evaluate the effect of fertilizer composition 1 with other fertilizers, commercial manganese, cobalt and molybdenum soluble liquid samples were used. Figure 4 shows the performance of the different concentrations a), b), c) and d) of the fertilizer composition 1.

It can be seen that the addition of the product has improved considerably the stability of the spray solution thus avoiding solid settling and clogging of filters and nozzles.

 Thus, it is concluded that the adjuvant property fertilizer composition of the present invention, besides having nutrients necessary for plant development, is capable of improving the stabilization of mixtures containing herbicides and fertilizers under different conditions.

Claims

 Fertilizing composition with adjuvant property, characterized in that it comprises at least one nitrogen-derived component, at least one phosphorus-derived component, at least one ethoxylated ester, at least one ethoxylated alcohol, at least one component selected from polyethylene glycol diethylene glycol and monoethylene glycol and a siliconised component.  Fertilizing composition according to claim 1, characterized in that the nitrogen source is selected from at least one of: urea, ethoxylated urea, ammonium sulfate, potassium nitrate, ammonium monophosphate and ammonium diphosphate, alkyl ethoxylated etheramines, ethoxylated fatty amines, ethoxylated coconut amine, ethoxylated imidazolines, alkyl dimethyl amine oxides, alkyl dimethyl betamas, alkyl propyl amine and ethoxylated alkyl amines.  Fertilizing composition according to claim 2, characterized in that the nitrogen source is selected from:  (i) Urea derivatives

 on what: R is a C _2-4 hydrocarbyl,  x is a number from 1 to 20,  n is a number from 0 to 20,  y is a number from 0 to 20,  w is a number between 0 and 20;  or (ii) Amine grease derivative.

 on what:  R is an alkylated carbon chain,  m is a number from 0 to 20,  n is a number from 1 to 20,  m + n may result in 10 to 40.  Fertilizing composition according to claim 1, characterized in that the source of phosphorus is selected from at least one or a combination of more components from: phosphoric acid, polyphosphoric acid, phosphorous acid, phosphate polyethylene glycol monoalkyl ether, phosphate alcohol phosphate ethoxylated alcohol, phosphate methyl alcohol, phosphate ethoxylated lauryl alcohol, phosphate isodecyl alcohol, phosphate ethoxylated tridecyl alcohol.  Fertilizing composition according to Claim 4, characterized in that the source of phosphorus is selected from: (i) Phosphate ethoxylated alcohol

 on what:  R is an alkylated carbon chain,  n is a number from 1 to 20;  (ii) ethoxylated alcohol phosphate diester  THE R- (OCH ₂ CH ₂ ) ^ 0 - P - OH O- {OCH ₂ CH ₂ } ^ 0 R may be a branched or straight carbon chain n is a number from 1 to 20; (iii) polyphosphoric acid HO (P0 ₂ OH) nH  on what:  n is a number from 0.5 to 2.0;  or  (iv) phosphate isodecyl alcohol.  Fertilizing composition according to claim 1, characterized in that the ethoxylated alcohol present in the composition is selected from the group consisting of: ethoxylated lauryl alcohol, ethoxylated cetostearyl alcohol, ethoxylated isodecyl alcohol, ethoxylated tridecyl alcohol, ethoxylated caprylic alcohol , and their mixtures. R- (OCH ₂ CH ₂ ) ₄ OH wherein:  R may be a branched or straight carbon chain n is a number from 1 to 20.  Fertilizing composition according to any one of the preceding claims, characterized in that it further comprises calcium (Ca), magnesium (Mg), sulfur (S) manganese (Mn), boron (B), cobalt (Co), molybdenum ( Mo), nickel (Ni), silicon (Si), zinc (Zn), iron (Fe), copper (Cu), chlorine (Cl) in the form of cation, oxide or element.  Fertilizing composition according to claim 1, characterized in that it comprises ethoxylated sorbitan ester and polyethylene glycol, wherein  (i) Ethoxylated sorbitan ester

on what: R: can be an alkyl or aryl group  x + y + z = is a number from 10 to 20; and  (ii) Polyethylene glycol H (OCH ₂ CH ₂ ) nOH  on what:  n: is a number from 1-20.  Fertilizer composition according to any one of the preceding claims, characterized in that it comprises between one and three nitrogen-derived components, comprises between one and three phosphorus-derived components, comprises between one and three ethoxylated esters, between one and three ethoxylated alcohols, a component selected from polyethylene glycol, diethylene glycol and monoethylene glycol and a silicone component.  Fertilizing composition according to any one of the preceding claims, characterized in that it comprises: 2-30% by weight of components as nitrogen source, 10-60% by weight of components as phosphorus source, 1-30% by weight. weight of an ethoxylated sorbitan ester, 0.1-10% by weight of an ethoxylated alcohol, 5-30% by weight of polyethylene glycol and 0.1-10% by weight of silicone derivatives.  Fertilizer composition according to any one of the preceding claims, characterized in that it comprises: 10-30% by weight of components as a source of nitrogen, 10-20% by weight of components as a source of phosphorus, 10-30% by weight. weight of an ethoxylated sorbitan ester, 0.5-5% by weight of an ethoxylated alcohol, 10-20% by weight of a polyethylene glycol and 1-5% by weight of silicone derivatives. Use of the adjuvant fertilising composition as defined in any one of claims 1 to 13, characterized in that it is used in spray liquids in concentrations ranging from 0.1 to 2% by weight. Use according to claim 14, characterized in that it is used in mixtures containing glyphosate and / or 2,4-D and other herbicides selected from: Aryloxyphenoxypropionates, cyclohexadiones, phenylpyrazines, sulfonylureas, imidazolinones, triazolopyrimidines, pyrimidyl (thio) benzoates, sufonylaminocarbonyltriazolinones, triazines, triazinones triazolinones, uracils, pyridazinones, phenyl carbamates, ureas, amides, nitriles, benzothiadiazinones, phenylpyridines, diphenylethers, phenylpyrazoles, N-phenyladiazole oxidases, triazinones, triazinones tricetones, pyrazoles, benzoic acid, pyridines, nitriles, benzoic acid, phenoxycarboxylic acid, semicarbazones, phthalamates, carbamates and pyridazinones, uracils and mixtures thereof.  Use according to claim 14, characterized in that it is used in mixtures of other fertilizers such as: monoammonium and diammonium phosphate, potassium chloride, calcium nitrate, potassium sulfate, potassium nitrate, and potassium sulfate. and magnesium, phosphoric acid, polyphosphoric acid, calcium oxide, magnesium oxide, manganese chloride, manganese oxides, manganese sulfate, zinc oxides and iron oxides and mixtures thereof.  Use of the fertilizer composition according to any one of claims 14 to 16, characterized in that it is used in spray grouts intended for general agricultural applications.