Herbicidal combinations for agricultural use

Abstract

The present invention relates to a herbicidal formulation comprising a herbicide and a polymer, wherein the polymer is a polyferulate with an average molecular weight of more than 400 g / mol, and the weight ratio of the herbicide to the polymer is 1:10 to 1000:1. Furthermore, the herbicide is from the chemical families of phenylpyrazole, triazolinone, glycine, triazolopyrimidine, cyclohexanedione, pyridinium, sulfonylurea, carbamate, benzofuran, benzoic acid, bipyridylium, dinitroaniline, diphenyl ether, oxyacetamide, phenoxycarboxylic acid, phosphinic acid, pyridine carboxylic acid, pyridine carboxamide, uracil or carboxylic acid. The present invention also relates to the use of the formulation. The present invention further relates to a method of applying the herbicidally effective amount of the herbicidal formulation, controlling weeds or aiding the harvest (desiccant).

Description

[Technical field]

[0001] The present invention relates to herbicide enhancers.

[0002] In a second aspect, the present invention relates to a herbicide formulation.

[0003] In a third aspect, the present invention also relates to methods for broadleaf weed and grass control in various crops, as well as industrial vegetation or crop management (defoliants and desiccants to aid harvest), in which the herbicidal formulations are applied in herbicidally effective amounts.

[0004] In another aspect, the present invention also relates to the use of said herbicide formulation. [Background technology]

[0005] Weeds cost farmers billions of dollars each year in crop losses and the costs of weed control efforts. Weeds also act as hosts for crop diseases and pests. Losses from weeds in agricultural production environments include reduced crop yields, reduced crop quality, increased irrigation costs, increased harvesting costs, reduced land value, injury to livestock and crop damage from weed-borne insects and diseases.

[0006] Chemical herbicides have provided an effective method of weed control for many years. Herbicides may generally be applied pre-emergent and / or post-emergent. Pre-emergent herbicides are applied to the field before the crop emerges from the soil. Such applications are usually applied to the soil before, simultaneously with, or soon after planting the crop. Such applications may kill weeds growing in the field before the crop emerges and may also prevent or reduce germination of weeds present in the soil. Post-emergent herbicides are usually used to kill weeds after the crop emerges in the field.

[0007] There is a need for compositions that reduce the amount of herbicide required to obtain sufficient weed control while minimizing damage to crop plants. As more weeds become resistant to herbicides, alternative compositions with high weed control are desired. Furthermore, as no-till farming continues to become more popular, there is an increased need for effective herbicides. Compositions with effective weed control and low dosages increase crop plant yields and reduce environmental, human and mammalian health concerns.

[0008] Researchers are trying to find synergies between herbicides to reduce the amount of herbicide needed. U.S. Patent Application Publication No. 2011 / 065579 discloses mixtures of many herbicides.

[0009] Spanish Patent No. 2713176 describes the herbicide florpilaxifen, the properties of which are allegedly improved when mixed with ammonium glyphosate.

[0010] China Patent Publication No. 111018697 describes a plant extract herbicide. The invention discloses a method for extracting trans-p-hydroxycinnamic acid from corn stalks and applying it as a herbicide. The method includes extraction with ethanol and ethyl acetate, and separation by chromatography column.

[0011] US Patent No. 10,342,228 describes a biocide-enhancing composition comprising a polyelectrolyte complex of a polyanion and a polycation and at least one biocide. The polyelectrolyte complex provides a synergistic effect with the biocide. In a preferred composition, lignosulfonate is mixed with chitosan. Antioxidants, surfactants, waxes, stabilizers and thickeners can also be added to the composition.

[0012] Japanese Patent Application Laid-Open No. 2002-003386 describes an agent for increasing cyclic AMP concentration in animal cells or an inhibitor of cyclic nucleotide phosphodiesterase, which contains a ferulic acid polymer.

[0013] Known formulations often have manufacturing processes that cause environmental pollution, do not have reduced toxicity, are not plant-based, require frequent reapplication, are ineffective, or are difficult to manufacture.

[0014] Biological weed control (biohesicides) is an innovative strategy that utilizes natural enemies, natural substances or biological agents to suppress the germination and growth of weed populations to economic threshold levels. However, the inconsistency of the efficacy of bioherbicides is a major obstacle to their widespread use.

[0015] The present invention aims to solve at least some of the problems and drawbacks mentioned above. It is an object of the present invention to provide a formulation which overcomes at least some of these drawbacks. Summary of the Invention [Problem to be solved by the invention]

[0016] The present invention and its embodiments serve to provide a solution to one or more of the above-mentioned shortcomings. To this end, the present invention relates in a first aspect to a herbicide enhancer for increasing the efficiency of a herbicide, comprising a polyferrate having an average molecular weight of more than 400 g / mol.

[0017] In a second aspect, the present invention relates to a herbicide formulation comprising a chemical family of: phenylpyrazole, triazolinone, glycine, triazolopyrimidine, cyclohexanedione, pyridinium, sulfonylurea, carbamate, benzofuran, benzoic acid, fatty acid, nonanoic acid, bipyridylium, dinitroaniline, diphenyl ether, oxyacetamide, phenoxycarboxylic acid, phosphinic acid, pyridine carboxylic acid, pyridine carboxamide, uracil dicarboxylic acid, inorganic compound, phenylurea, phosphate ester or carboxylic acid; and a polymer, said polymer being a polyferulate having an average molecular weight of more than 400 g / mol, and the weight ratio of herbicide to polymer is between 1:10 and 1000:1.

[0018] The compositions described herein are particularly advantageous because polyferulate is bio-based, safe to use, highly bioavailable, and further helps to effectively combat weeds in plant crops without adversely affecting plant growth and / or yield.

[0019] A preferred embodiment is set forth in any one of claims 3 to 12.

[0020] In a third aspect, the present invention relates to a method for controlling pests or aiding the harvest (desiccant), said method comprising application of a herbicide from the following chemical families: phenylpyrazole, triazolinone, glycine, triazolopyrimidine, cyclohexanedione, pyridinium, sulfonylurea, carbamate, benzofuran or carboxylic acid at 2-98% of the recommended dose when applied alone, and application of 1-500 g / ha of polyferulate simultaneously with the herbicide or during a period of 10 days before or after application of the herbicide.

[0021] A preferred embodiment of the method is set forth in claim 14.

[0022] In a fourth aspect, the present invention relates to the use according to claim 15. The composition can be used in-can (co-formulated product) or tank-mix, whereby polyferulate is formulated as an adjuvant in the tank-mix, added to the herbicide or applied in a premix concentrate. The use of the formulations described herein results in products that are easy to apply. [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 shows an overlay of SEC chromatograms of ferulic acid (starting reaction) and polyferulate (final product). [Diagram 2] FIG. 1 shows the UV spectra of ferulic acid and polyferulate. [Diagram 3]FIG. 1 shows FT-IR spectra of ferulic acid and polyferulate.

[0024] Text description of the illustration image024.gif. Figure 1 shows an overlay of SEC chromatograms obtained using a Sephacryl S-200 column. The high molecular weight polyferulate elutes from the column first. Monomeric ferulic acid elutes afterwards. The lack of overlap between the two chromatograms confirms the absence of monomeric ferulic acid residues in the final product.

[0025] The difference in structure between the initial product (ferulic acid) and the final product (polyferulate) was confirmed by UV analysis, as shown in Figure 2. In the UV absorption spectrum of polyferulate, it was observed that the band at 344 nm was shifted by about 44 nm relative to ferulic acid. This shift is undoubtedly due to the formation of polymeric bonds between the ferulate units.

[0026] Figure 3 shows the FTIR spectra of polyferulate and ferulic acid, which are significantly different from each other. The broadening of the signal at 3400 cm-1 in the polyferulate spectrum indicates the presence of more labile protons due to carboxylic and phenolic groups in polyferulate, while the smaller signal at 3000 cm-1 characteristic of the stretching of C-H bonds of aromatic groups is slightly stronger and more resolved due to the large amount of aromatic rings in polyferulate. In addition, the signal at 1700 cm-1 characteristic of carboxyl groups is much weaker in polyferulate. This is likely due to the three-dimensional arrangement of polyferulate, which limits the possibility of vibration of the C=0 double bond. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The EPA defines a herbicide as a chemical used to manipulate or control undesirable vegetation. Herbicides are most often applied before or during planting to minimize other vegetation and maximize crop productivity. They may also be applied to crops in the fall to improve yields (harvest aids - desiccants). Herbicides are also used in forest management to prepare cleared land for reforestation; in suburban and urban areas, herbicides are applied to lawns, parks, and golf courses, and to water bodies to control aquatic weeds.

[0028] The potential impact of a herbicide is strongly influenced by its toxic mechanism of action and the method of application. Although the site of action of a molecule is difficult to predict because no structural relatedness has been identified, the mechanism of action has been established. Herbicides can act by inhibiting cell division, photosynthesis or amino acid production, or by mimicking natural plant growth hormones and causing malformations. Methods of application include foliar sprays, application to soil and direct application to water systems.

[0029] However, herbicides can also be toxic to humans and the environment. They can cause adverse health effects, such as cancer, reproductive, immune or nervous system effects. Therefore, societal concerns about herbicide use have emerged as a major issue in recent years. Reducing herbicide use has attracted the interest of multiple stakeholders. This interest is driven by farmers, environmentalists and consumers due to the economic, environmental and health impacts of herbicide use.

[0030] Strategies for herbicide reduction range from organic farming, which does not use herbicides, to conventional farming, which seeks to exploit opportunities for herbicide reduction that arise by chance. Several authors argue that the adoption of sustainable agricultural practices, such as herbicide reduction, is most likely when the strategies fit into existing production systems. Moreover, for many farmers, herbicide reduction may seem more feasible in terms of profitability and productivity than organic farming.

[0031] An effective strategy to reduce herbicide use is to use synergistic combinations of herbicides, which optimize the function of the chemical and allow it to be more effective at lower application rates.

[0032] The present invention relates to bio-based herbicide synergists comprising polymers and methods of their use to enhance the activity of herbicides or reduce the effective amount of herbicide active ingredient, thereby reducing the harmful effects of herbicides on crops, humans and the environment.

[0033] The inventors have surprisingly found that polyferulate can be successfully used to enhance herbicidal activity and can be considered as a synergist. Polyferulate is a bio-based polymer that has no insecticidal properties by itself, but enhances the effect of herbicides or other chemicals. The addition of polyferulate increases the activity of herbicides (at low doses), thereby reducing the harmful effects on crops, humans and the environment. The present invention further relates to a composition for reducing the dose of herbicides on weeds. The composition comprises polyferulate and is applied to the weeds or to the soil in contact with the weeds.

[0034] Unless otherwise defined, all terms used in disclosing the present invention, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. As a further guide, definitions of terms are included to better understand the teachings of the present invention.

[0035] As used herein, the following terms have the following meanings:

[0036] As used herein, "a," "an," and "the" refer to singular and plural references unless the context clearly indicates otherwise. By way of example, "a section" refers to one or more sections.

[0037] As used herein, "comprise," "comprising," and "comprises" and "comprising of" are synonymous with "include," "including," "includes," or "contain," "containing," "contains," and are inclusive or open-ended terms that specify the presence of subsequent components, e.g., and do not exclude or preclude the presence of additional, unrecited components, features, elements, materials, steps that are known in the art or disclosed therein.

[0038] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range, as well as the recited endpoints.

[0039] The terms "weight percent," "weight percent," "% wt," or "wt%," unless otherwise defined, herein and throughout this specification refer to the relative weight of each component in relation to the weight of the entire formulation.

[0040] The term "one or more" or "at least one", e.g., one or more or at least one member of a group of members, is in itself clear, but by way of further illustration, the term specifically encompasses reference to any one of said members, or any two or more of said members, e.g., any >3, >4, >5, >6 or >7 of said members, etc., and up to all of said members.

[0041] An agent that enhances the efficiency of a herbicide, as used herein, refers to an agent that synergistically enhances the herbicidal effect (as defined by Colby in Calculating Synergistic and Antagonistic Responses of Herbicide Combinations. Weeds, Vol. 15, No. 1 (Jan., 1967), pp. 20-22) when combined with a herbicide. Furthermore, when combined with the agent, the amount of the herbicide required to achieve the same herbicidal effect can be reduced.

[0042] Ferulic acid, also known as (2E)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoic acid, is a hydroxycinnamic acid. Other hydroxycinnamic acids are caffeic acid, coumaric acid, etc. "Polyferulate" is a polymer of ferulic acid, containing at least two ferulic acid monomers. After polymerization, a wide variety of chemical structures can be obtained, since ferulic acid contains several active groups. Therefore, the degree of polymerization can be determined based on the molecular weight. There are no free ferulic acid monomers in polyferulate.

[0043] In a first aspect, the present invention relates to a herbicide enhancer for increasing the efficiency of a herbicide comprising polyferulate having an average molecular weight of more than 400 g / mol.

[0044] In a second aspect, the present invention relates to a herbicide formulation comprising a herbicide and polyferulic acid. Some literature on pest control discloses the use of ferulic acid or dimers. However, the inventors have unexpectedly observed that polyferulic acid can improve the efficacy of herbicides without phytotoxicity. The application rate of the same effective herbicide can be reduced when mixed with polyferol, where the weight ratio of herbicide to polymer is 1:10-1000:1, preferably 1:10-500:1, more preferably 1:8-400:1, even more preferably 1:5-250:1, and most preferably 1:4-200:1.

[0045] In one embodiment of the present invention, the average molecular weight of the polyferulate in the formulation is greater than 400 g / mol, more preferably greater than 700 g / mol. In a more preferred embodiment, the polyferulate has an average molecular weight of 700-100000 g / mol, preferably 700-50000 g / mol, even more preferably 800-40000 g / mol, even more preferably 900-35000 g / mol, and most preferably 1000-30000 g / mol.

[0046] In one embodiment, the weight ratio of the herbicide to polyfurate is 1:8 to 300:1, more preferably 1:5 to 100:1, even more preferably 1:3 to 50:1, and most preferably 1:2 to 40:1.

[0047] In another embodiment, the weight ratio of the herbicide to polyfurate is 1:3 to 20:1, more preferably 1:2 to 10:1. In another embodiment, the weight ratio of the herbicide to polyfurate is 1:5 to 40:1, more preferably 1:2 to 25:1.

[0048] In a preferred embodiment, the weight ratio of components (A: herbicide) to (B: polyferulate) is in the range of up to 1000:1, more preferably up to 900:1, more preferably up to 800:1, more preferably up to 700:1, more preferably up to 600:1, more preferably up to 500:1: even more preferably up to 400:1, even more preferably up to 300:1, even more preferably up to 200:1, even more preferably up to 180:1, even more preferably up to 160:1, even more preferably up to 140:1, even more preferably up to 120:1.

[0049] In a preferred embodiment, said weight ratio of components (A) and (B) ranges from at most 100:1, more preferably at most 80:1, even more preferably at most 60:1, and even more preferably at most 40:1.

[0050] In a preferred embodiment, the weight ratio of components (A) and (B) is in the range of 0.1: to 50:1, more preferably 0.2:1 to 46:1, even more preferably 0.3:1 to 43:1, even more preferably 0.4:1 to 40:1, and most preferably 0.6:1 to 30:1.

[0051] In a preferred embodiment, the weight ratio of components (A) and (B) is in the range of 1:1 to 32:1, more preferably 1.2:1 to 30:1, even more preferably 1.4:1 to 28:1, even more preferably 1.6:1 to 26:1, even more preferably 1.8:1 to 24:1, and even more preferably 2:1 to 20:1.

[0052] In another preferred embodiment, the herbicide is capable of inhibiting photosynthesis in photosystem I or causing inhibition of protoporphyrinogen oxidase (PPO). In a further embodiment, the herbicide is from the chemical family of phenylpyrazoles or triazolinones.

[0053] In another preferred embodiment, the herbicide is capable of inhibiting the production of acetyl-CoA carboxylase (ACCase), acetohydroxyacid synthase (AHAS), photosynthesis or lipid synthesis in photosystem II. The herbicide may be from the chemical families of cyclohexanedione, sulfonylurea, carbamate or benzofuran.

[0054] In another preferred embodiment, the herbicide may be a carboxylic acid or alkanoic acid, such as acetic acid, pelargonic acid, other fatty acids, etc. The weight ratio of said herbicide to polyferulate is 1:1 to 1000:1, preferably 1:1 to 800:1, more preferably 1:1 to 200:1, more preferably 4:1 to 200:1, and most preferably 8:1 to 200:1. In an embodiment where the herbicide is pelargonic acid, less polyferulate is required per dose of herbicide.

[0055] In some embodiments, the herbicide has the following mechanism of action, as indicated and designated by the Herbicide Resistance Action Committee (HRAC) in the HRAC code: Inhibition of 2-acetolactate synthase ALS (acetohydroxyacid synthase AHAS) 3-Microtubule polymerization inhibition 4-Auxin Mimics 5-Photosynthesis inhibition in photosystem II Inhibition of 9-EPSP synthase 10-Glutamine synthetase inhibitor 12-Phytoene desaturase inhibitor 14-PPO inhibitor herbicide 15-VLCFA Inhibition 22-Electron conversion in photosystem I 31-Serine-Threonine Protein Phosphatase Inhibitor

[0056] In some embodiments, the herbicide is selected from the chemical families: phenylpyrazole, triazolinone, fatty acid, nonanoic acid, glycine, triazolopyrimidine, cyclohexanedione, pyridinium, sulfonylurea, carbamate, benzofuran, benzoic acid, bipyridylium, dinitroaniline, diphenyl ether, oxyacetamide, phenoxycarboxylic acid, phosphinic acid, pyridine carboxylic acid, pyridine carboxamide, uracil, dicarboxylic acid, inorganic compound, phenylurea, phosphate ester, or carboxylic acid.

[0057] In some embodiments, the herbicide is selected from the following list: 2,4-D, acetic acid, aminopyralid, capric acid, caprylic acid, carfentrazone ethyl, cyclanilide, dicamba, dichlorprop P, diflufenican, diquat, endothal, fatty acids C7-C20 (pelargonic acid), fatty acids C7-C18 and C18 unsaturated potassium salts, fatty acids C8-C10 methyl esters, flazasulfuron, flufenacet, fluroxypyr, glufosinate, glyphosate, iodosulfuron, MCPA, oleic acid, oryzalin, oxyflufen, paraquat, pelargonic acid, penoxsulam, picloram, pyraflufen-ethyl, saflufenacil, sodium chlorate, thidiazuron, tribufos, or triclopyr. In other embodiments, the salts of the above herbicides are selected in combination with the polymer.

[0058] The composition preferably contains 10-90% of the recommended dosage of a chemical herbicide, more preferably 25-75% and 1-250 g ai / ha, more preferably 5-100 g ai / ha, most preferably 10-25 g ai / ha of polyferulate.

[0059] However, it is clear that the invention is not limited to this use or to field applications: the method according to the invention can be applied to any kind of setup, such as hydroponics, vertical farming, etc.

[0060] The important advantage of the composition comprising polyferulate is that the use of the composition reduces the dosage of herbicide, allowing herbicide to be used more efficiently in target plants.Thus, the use of the composition described herein allows herbicide to be used at a lower dosage, reducing the possible adverse effects on crop seed germination, plant growth and / or yield, while effectively combating unwanted weeds.In contrast to known herbicide enhancers, the composition has biological properties, is not risky to the environment, and has a lower risk of inducing resistance to herbicides in weeds.

[0061] The compositions compensate for or reduce the environmental pollution and human and animal health effects of herbicides without substantially reducing their herbicidal action on unwanted vegetation.

[0062] In some embodiments, the compositions may be in a more concentrated form, which is preferable for transport and storage of the composition, while in some embodiments, the compositions may be in a more diluted form, which is preferable for direct application to plants.

[0063] According to a further or alternative embodiment, the composition comprises a hydrophilic and / or lipophilic surfactant, the hydrophilic and / or lipophilic surfactant having a concentration of 0.01-30.00 wt% relative to the total weight of the composition. As used herein, the term "surfactant" refers to an amphiphilic organic compound, which indicates that it contains both hydrophobic and hydrophilic groups. Thus, surfactants contain both water-insoluble (or oil-soluble) and water-soluble components. As a result of their unique structure, surfactants diffuse in water and adsorb to the interface between the oil and water phases.

[0064] According to further or alternative embodiments, the composition has a pH of from 1 to 12. Preferably, the composition has a pH of from 5 to 8.

[0065] According to further or alternative embodiments, the composition is applied to the target plants before, simultaneously with, or after application of a herbicide.

[0066] According to some embodiments, applying the formulation to the weeds comprises foliar application by spraying the composition onto the leaves of the weeds. Spraying the composition is a particularly preferred application method, as it allows for homogeneous distribution of the composition onto the weeds. Moreover, spraying is a very fast method of distributing the composition, allowing for the treatment of large surface areas of the plant.

[0067] The present invention includes a method of applying 5-95% of the recommended dose of the herbicide when applied alone and applying 1-500 g of polyferulate simultaneously with the herbicide or within 10 days before or after application of the herbicide, more preferably applying only 20-75% of the recommended dose of the herbicide when applied alone in combination with 10-25 g / ha of polyferulate.

[0068] In another embodiment, the herbicide is mixed with 5-30 g / ha of polyferulate, or 20-50 g / ha of polyferulate. In another embodiment, the herbicide is mixed with 2-20 g / ha of polyferulate, or 20-40 g / ha of polyferulate. In another embodiment, the herbicide is mixed with 1-250 g / ha of polyferulate, or 10-300 g / ha of polyferulate. In a preferred embodiment, the herbicide is mixed with 1-100 g / ha of polyferulate, more preferably 1-50 g / ha of polyferulate, even more preferably 1-25 g / ha of polyferulate, and most preferably 5-25 g / ha of polyferulate.

[0069] In another embodiment, the herbicide is applied at 20-85% of the recommended dosage if applied alone, and 1-250 g / ha of polyferulate is applied simultaneously with the herbicide or within 10 days before or after application of the herbicide, preferably 10-25 g / ha of polyferulate.

[0070] Herbicide formulations containing a herbicide and a polyerulate in the appropriate ratios of the present invention can be formulated with conventional formulation adjuvants known in the art, such as, for example, one or more carriers.

[0071] In a preferred embodiment, the herbicide composition of the present invention further comprises one or more additional components selected from the group including other pesticides such as herbicides, insecticides, fungicides, or other pesticide active ingredients, safety agents, antioxidants, chemical stabilizers, adhesives, fertilizers, fragrances, colorants, liquid carriers, solid carriers, surfactants, crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet conditioners, pigments, foaming agents, light-blocking agents, compatibilizers, defoamers, sequestering agents, neutralizing agents and buffers, wetting agents and dispersants, preservatives, thickeners, corrosion inhibitors, freezing point depressants, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, tackifiers, and humectants such as propylene glycol. According to a preferred embodiment, the herbicide composition can also comprise various pesticide active compounds, such as compounds from the group of acaricides, nematicides, bird repellents, and soil structure improvers.

[0072] The herbicide formulation comprising herbicide and polyferulate can be used to control weeds in a can or tank mix. In another embodiment, both components of the formulation are not applied together, but are applied separately during a period of up to 10 days. More preferably, the period between the application of the two components is less than 5 days. Application can be carried out by spraying on foliage, application to soil, and direct application to water systems.

[0073] Said synergistic effect of herbicides and polyferulates can be observed, for example, in the case of ready-mix application, such as ready-to-use formulations, emulsifiable concentrate formulations, microemulsifiable concentrate formulations, suspension concentrate formulations, oil-dispersible formulations, soluble liquid formulations, wettable powder formulations, water-dispersible granules, water-soluble granules, and in the case of tank mixes; but also when the active compounds are applied (split) at different times (packed as combi-packs or monodoses, for example). It is also possible to apply the herbicides or herbicidal compositions in several portions (sequential application), for example, post-emergence or early post-emergence followed by mid-emergence or late post-emergence application. For some herbicides, when applied as tank mixes, the spray obtained must be applied relatively soon after preparation.

[0074] The herbicide formulation according to the first aspect of the present invention has very good herbicidal properties and can be used to control unwanted vegetation.In some embodiments, the herbicide formulation according to the first aspect of the present invention can be used as a general herbicide to control unwanted vegetation, especially in non-agricultural areas, such as footpaths, amenity areas such as squares, and also under trees and shrubs, railway tracks, etc.The herbicide formulation according to the first aspect of the present invention is characterized by a particularly fast-acting and long-lasting action.

[0075] In another embodiment of the use according to the third aspect of the invention, the herbicide formulation is applied to one or more unwanted vegetation just before, during or after emergence of one or more crops adjacent to said unwanted vegetation, and the herbicide composition may be reapplied at predetermined time intervals of 1 to 20 days, more preferably 4 to 10 days, most preferably 5 to 7 days until harvest of said one or more crops.

[0076] In a third aspect, the present invention relates to a method for controlling pests or aiding the harvest (desiccant), said method comprising: applying a herbicide from the chemical families phenylpyrazole, triazolinone, glycine, triazolopyrimidine, cyclohexanedione, pyridinium, sulfonylurea, carbamate, benzofuran or carboxylic acid at 2-98% of the recommended dose when applied alone, and applying 1-500 g / ha of polyferulate simultaneously with the herbicide or during a period of 10 days before or after application of the herbicide.

[0077] In a further embodiment, the herbicide is applied in a mixture of 20-85% of the recommended dose when applied alone with 1-250 g / ha of polyferulate, and in a further embodiment, the herbicide is applied in a mixture of 20-75% of the recommended dose when applied alone with 10-25 g / ha of polyferulate.

[0078] In one embodiment, polyferulate is used for crop drying. Crop drying refers to the application of chemicals to crops just before harvest to kill leaves and / or plants, so that the crop dries out more quickly and uniformly from environmental conditions. Chemicals used in agriculture are herbicides and / or defoliants used to artificially promote the drying of plant tissues. Crop drying by the use of herbicides is practiced worldwide for various edible and non-edible crops. The main purpose is to improve the efficiency and reduce the cost of mechanical harvesting. When polyferulate is used in combination with said herbicides and / or defoliants, it is expected to improve efficiency.

[0079] In one embodiment, polyferulate is used in a method for controlling or drought weeds. The method includes applying a herbicide at about 40-60% of the recommended dose when used alone, and applying about 12-20 g of polyferulate simultaneously with a pesticide or 10 days before or after application of the pesticide. Preferably, the time difference between application of the herbicide and polyferulate is less than 72 hours.

[0080] In another aspect, the present invention relates to the use of the herbicide formulation according to the embodiment of the first aspect in a premix concentrate (applied before, in combination - co-formulation - or after a herbicide / desiccant / defoliant) or in a tank mix with a herbicide / desiccant / defoliant to control weeds or to aid in the harvest (desiccant).

[0081] In some embodiments, the formulations described herein can be used to increase plant uptake of the herbicide by 40-75% compared to plant uptake using only the herbicide without the polymer.

[0082] The present invention relates to the use of formulations, either by premix concentrates or in tank mixes with herbicides, where polyferulate is applied before, at the same time (co-formulation) or after herbicides, to control weeds or to aid in harvest (desiccant).The present invention relates to the use of herbicide augmentants, either by premix concentrates or in tank mixes with herbicides, where polyferulate is applied before, at the same time (co-formulation) or after herbicides, to control weeds or to aid in harvest (desiccant).

[0083] The present invention relates to the use of a herbicide enhancer to increase the efficiency of a herbicide, wherein the herbicide enhancer comprises a polyferulate having an average molecular weight of more than 400 g / mol.

[0084] The present invention is further described by the following non-limiting examples which further illustrate the present invention but are not intended to, and should not be construed as, limiting the scope of the invention.

[0085] The invention will now be explained in more detail with reference to non-limiting examples. EXAMPLES

[0086] Example 1. Preparation of polyferulate Polyferulate is prepared by an environmentally friendly procedure. The oxidation of biobased ferulic acid and subsequent polymerization are enzymatically promoted. 3 L of 50 mM potassium phosphate buffer (pH 6.0), 2 L of methanol, 20 mL of 1% horseradish peroxidase (HRP) solution (activity 150 units / mg), 1 L of a methanolic solution of ferulic acid (10 g / L) and 0.6% hydrogen peroxide (400 ml) are added dropwise at 0.5 mL / min to the reaction mixture. The reaction is monitored simultaneously by FPLC-SEC and LC-MS using a Sephacryl S-200 column. The reaction is carried out at 30 °C until neither monomeric ferulic acid nor small oligomers are detectable in the reaction mixture (approximately 48 h). Polyferulate is isolated by precipitation at low pH, purified by washing with cold water and lyophilized.

[0087] Example 2: Compositions containing polyferulate and a chemical herbicidal active ingredient (AI) The following tables (1-5) include exemplary compositions that contain both polyferulate and herbicide according to the present invention. The compositions exemplified below are particularly suitable as desiccants to combat weed growth in target crops or as harvesting aids. Polyferulate herein functions synergistically, i.e. as an adjuvant that enhances herbicidal activity in target plants.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] Example 3. Synergistic effect of polyferulate and herbicides on potato desiccation Preparation for harvest is an important step in potato production, since intensive fertilization leads to lush growth of the aboveground parts. The tubers of such crops mature very slowly and are prone to mechanical damage (pain). Drying potatoes before harvesting improves the tuber appearance, promotes periderm development, and improves storability.

[0094] The potato experiment was conducted in a randomized block with four replications. The field area was approximately 40.0 m 2 (4.0 m wide and 10.0 m long). The desiccant was applied by spraying. 15 days after treatment, the desiccant efficiency was visually assessed and the condition of potato leaves and stems was compared between desiccant-treated and untreated plots. The efficacy of the desiccant was expressed as a percentage, with 100% being total leaf and stem damage and 0% being the absence of desiccant effect.

[0095] [Table 6]

[0096] Expected responses of herbicide combinations according to Colby (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations. Weeds, Vol. 15, No. 1 (Jan., 1967), pp. 20-22). If the observed response is greater than expected, the combination is synergistic; if it is less than expected, it is antagonistic. If the observed and expected responses are equal, the combination is additive. The difference between the observed and expected values ​​indicates synergy with a plus sign and antagonism with a minus sign.

[0097] Surprisingly, polyferulate showed synergistic effects with all three herbicides tested, nevertheless, the low molecular weight oligomer (diferulate) and monomer (ferulic acid) showed opposite effects (antagonists).

[0098] Example 4. Herbicide synergy of polyferulate depends on molecular weight. Polyferulates of different molecular weights were prepared by varying the reaction time of the enzymatic procedure described in Example 1. The molecular weight of each polyferulate batch was determined by SEC using a sephacryl S-200 column. Herbicide synergy was evaluated in potato plants with carfentrazone-ethyl (desiccant) as described in Example 3.

[0099] [Table 7]

[0100] Expected responses of herbicide combinations according to Colby (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations. Weeds, Vol. 15, No. 1 (Jan., 1967), pp. 20-22). If the observed response is greater than expected, the combination is synergistic; if it is less than expected, it is antagonistic. If the observed and expected responses are equal, the combination is additive. The difference between the observed and expected values ​​indicates synergy with a plus sign and antagonism with a minus sign.

[0101] Surprisingly, the synergistic effect on the herbicidal activity of polyferulate increases with increasing molecular weight: the average MV2408 polyferulate shows a higher (>2-fold) difference between observed and predicted responses (according to Colby) than the MV1251 polyferulate, which shows a >3-fold difference between observed and predicted responses compared to the 930 molecular weight polyferulate.

[0102] Example 5. Polyferulate enhances the herbicidal activity of various chemically active ingredients (AIs). The experiments were carried out on Lemna minor growing under in vitro conditions. Lemna minor (Duckweed) was purchased from a local market. Stock cultures were maintained on modified Hoagland's medium under controlled environment. The pH of the medium was adjusted to 6.0 and plants were grown under static conditions in a plant growth chamber at 25 ± 2°C and a 16h / 8h light / dark regime.

[0103] For the experiments, leaves without visible chlorosis were removed from the stock cultures and exposed to the appropriate treatments. Each treatment was replicated six times with an initial leaf count of three leaves per replicate. Individual leaves were transferred to 12-well multiplates containing Hoagland medium (control), Hoagland medium containing polyferulate, herbicides or the combinations shown in Table 8. All chemicals were evaluated at the same concentration (10 mg / L). Multiplates were covered with transparent covers to prevent evaporation. Herbicidal activity was evaluated as the reduction in fresh weight compared to untreated plants after one week of incubation under the conditions described.

[0104] [Table 8]

[0105] *-Predicted responses of herbicide combinations according to Colby (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations. Weeds, Vol. 15, No. 1 (Jan., 1967), pp. 20-22). If the observed response is greater than expected, the combination is synergistic; if it is less than expected, it is antagonistic. If the observed and expected responses are equal, the combination is additive. The difference between the observed and expected values ​​indicates synergy with a plus sign and antagonism with a minus sign.

[0106] Since the experiments were performed "in vitro", all herbicidal molecules were used at low concentrations (10 mg / L). Under these conditions, not all molecules show herbicidal activity alone. However, when these herbicidal molecules were combined with polyferulate, synergistic effects were observed in all cases.

[0107] Example 6. Polyferulate enhances herbicidal activity in weed control. Echinochloa gracilis is a generalist weed commonly found in crops (mainly rice, maize and vegetables), gardens, roadsides, disturbed areas, waste disposal sites and pastures. It also grows along waterways, edges of lakes and ponds, marshes and wetlands and other moist habitats. It can invade natural areas and completely displace native vegetation. This weed poses a major threat to rice productivity worldwide and is commonly reported as a noxious weed in economically important crops worldwide. Echinochloa gracilis is a vigorous grower and a high seed producer, with each Echinochloa gracilis plant producing up to 42,000 seeds.

[0108] The experiment with barnyard millet was carried out in four replicates in independent pots. The area of ​​the field plots was approximately 40.0 m. 2 (width 4.0 m, length 10.0 m). Herbicides were applied by spraying. Herbicidal activity was evaluated visually 20 days after treatment.

[0109] [Table 9]

[0110] *-Predicted responses of herbicide combinations according to Colby (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations. Weeds, Vol. 15, No. 1 (Jan., 1967), pp. 20-22). If the observed response is greater than expected, the combination is synergistic; if it is less than expected, it is antagonistic. If the observed and expected responses are equal, the combination is additive. The difference between the observed and expected values ​​indicates synergy with a plus sign and antagonism with a minus sign.

[0111] Surprisingly, polyferulate showed synergistic effects with all three herbicides tested, and similar effects were observed when the polyferulate concentration was increased up to 25 g / ha.

[0112] Example 7. Dose-effect of polyferulate and desiccant herbicides combinations on potato The test was carried out on potato plants in a greenhouse. The desiccant (pyraflufen-ethyl, a protoporphyrinogen oxidase (PPO) inhibitor) was applied alone or in combination with polyferulate at different rates of the recommended dose. The herbicide's efficacy was first evaluated 3 days after foliar application by measuring the photosynthetic capacity of treated leaves using QY (quantum yield) and the final desiccation efficiency was evaluated 14 days after treatment. The herbicidal activity (desiccation efficiency) was evaluated as the reduction in fresh weight relative to untreated plants (control) and expressed as a percentage.

[0113] [Table 10]

[0114] The results indicate that polyferulate stimulates the mechanism of action of PPO-type herbicides (reduction of photosynthesis) and therefore indicates that a lower dose of the active herbicide can be used with similar effectiveness in terms of drying potato leaves.

[0115] Example 8. Herbicide synergy of polyferulate depending on application time Herbicide synergy was evaluated in potato with pyraflufen-ethyl (desiccant). Polyferulate was applied the day before desiccant spraying (D-1), tank-mixed with desiccant (D-0), or the day after desiccant spraying (D+1). Potato experiments were performed in randomized blocks with 4 replications. Desiccant was applied by spraying. Desiccant efficiency was visually evaluated 15 days after treatment and potato leaf and stem condition was compared between desiccant-treated and untreated plots. Desiccant efficacy was expressed as a percentage, with 100% being total leaf and stem damage and 0% being the absence of desiccant effect.

[0116] [Table 11]

[0117] Expected responses of herbicide combinations according to Colby (Calculating Synergistic and Antagonistic Responses of Herbicide Combinations. Weeds, Vol. 15, No. 1 (Jan., 1967), pp. 20-22). If the observed response is greater than expected, the combination is synergistic; if it is less than expected, it is antagonistic. If the observed and expected responses are equal, the combination is additive. The difference between the observed and expected values ​​indicates synergy with a plus sign and antagonism with a minus sign.

[0118] Surprisingly, there is an increased synergistic effect on the herbicidal activity of polyferulate when applied to the target plants prior to, simultaneously with, or even after application of the herbicide.

[0119] The invention is in no way limited to the embodiments described in the examples, on the contrary, the method according to the invention can be realized in many different ways without departing from the scope of the invention.

[0120] Example 9. Polyferulate enhances herbicide uptake into plant leaves Tomato plants (Solanum lycopersicum) were sprayed with dilutions of pyraflufen-ethyl herbicide or pyraflufen-ethyl herbicide combined with polyferulate. Samples of treated leaves were taken 2 and 24 hours after treatment. To describe the distribution of pyraflufen-ethyl residues on and in the leaves of the plants, an extraction procedure following successive steps was used. Four fractions of pesticide residues were collected: (i) the pesticide fraction that is easily washed off by rain, presumed to correspond to the water-washable fraction, (ii) the pesticide fraction adsorbed on the leaf surface, presumed to correspond to the ethanol-extractable fraction, (iii) the pesticide fraction that has penetrated the cuticle, presumed to correspond to the hexane-extractable fraction, and (iv) the pesticide fraction that has penetrated the leaf tissue, presumed to correspond to the bound residue fraction. The table shows the overall balance of the distribution of the herbicide between the different extractable fractions from the leaves.

[0121] [Table 12]

[0122] These results indicate that application of the herbicide in combination with polyferulate enhanced the penetration of the active molecules into different leaf fractions. The presence of polyferulate not only increased the amount of active molecules detected in the different layers of the vegetable leaves, but also accelerated the kinetics of absorption over time.

[0123] Example 10. Polyferrates applied alone to plants disrupt plant physiology without killing the plants. Three-week-old tomato plants (Solanum lycopersicum) were sprayed with polyferulate solutions of different concentrations. 24 hours after treatment, the photosynthetic activity (QY) and peroxidase activity of the plants were quantified. QY measures the maximum photochemical yield of PSII, i.e., the efficiency of photosynthesis at the beginning of the photosynthetic chain. Peroxidases are ubiquitous enzymes and have been reported to be present in all genera of organisms. These enzymes are catalyzing the oxidation of substrates using hydrogen peroxide as an electron acceptor. Numerous biotic and abiotic stress factors have been implicated in the induction of peroxidase in plants. The results are shown in the table.

[0124] [Table 13]

[0125] These results indicate that polyferulate slightly reduces plant photosynthetic activity and induces plant stress responses, such as peroxidase activity.

[0126] Example 11: Effect of foliar application of polyferulate on Arabidopsis thaliana Arabidopsis seeds were sown in soil and pots were vernalized (4°C, dark) for 4 days for uniform seed germination. Afterwards, pots were placed in a growth chamber and maintained under a 12-h light (21°C, 60% relative humidity) and 12-h dark (16°C, 70% relative humidity) cycle. At least 50 30-day-old developed seedlings were used for the experiment. Half of the plants were sprayed with a solution containing polyferulate and the other half were sprayed with water (control-C). All plant leaves from three biological replicates were flash frozen in liquid nitrogen. Samples were taken 24 h after foliar spray treatment and transcriptome sequencing was performed.

[0127] The table below shows the number of genes that were differentially expressed after treatment with the composition. Only genes with expression dysregulated >2-fold relative to the control were considered.

[0128] [Table 14]

[0129] These results indicate that foliar application of compositions containing polyferulate to plants has a significant effect on the plant transcriptome. To gain insight into the molecular mechanisms involved in the bioactivity of polyferulate, we performed gene ontology (GO) enrichment analysis of differentially expressed genes (DEGs), some of which are summarized in the table below.

[0130] [Table 15]

[0131] These results indicated that a significant number of the differentially regulated genes were related to biological processes related to plant responses to stress conditions, indicating that treatment of Arabidopsis with compositions containing polyferulate had a significant effect on plant metabolism.

Claims

1. 1. Use of a herbicide enhancer to increase the efficiency of a herbicide, wherein the herbicide enhancer comprises polyferulate having an average molecular weight greater than 400 g / mol.

2. herbicides from the chemical families of phenylpyrazoles, triazolinones, glycines, triazolopyrimidines, cyclohexanediones, pyridiniums, sulfonylureas, carbamates, benzofurans, benzoic acids, fatty acids, nonanoic acids, bipyridyliums, dinitroanilines, diphenyl ethers, oxyacetamides, phenoxycarboxylic acids, phosphinic acids, pyridinecarboxylic acids, pyridinecarboxamides, uracildicarboxylic acids, inorganic compounds, phenylureas, phosphate esters or carboxylic acids; and a polymer, The herbicide formulation wherein the polymer is a polyferulate having an average molecular weight greater than 400 g / mol, and the weight ratio of the herbicide to the polymer is from 1:10 to 1000:

1.

3. 3. The formulation of claim 2, wherein the polyferulate has an average molecular weight of 700 to 50,000 g / mol.

4. A formulation according to any one of claims 2 to 3, wherein the polyferulate has an average molecular weight of 1000 to 30000 g / mol.

5. 4. The formulation of any of claims 2-3, wherein the weight ratio of said herbicide to said polymer is from 1:5 to 500:

1.

6. 4. The formulation of any of claims 2 to 3, wherein the herbicide is from the sulfonylurea, pyridinium, carbamate or benzofuran chemical family and the weight ratio of the herbicide to the polyferulate is from 1:5 to 100:

1.

7. 4. The formulation of any of claims 2 to 3, wherein the herbicide is from the chemical family of phenylpyrazoles, glycines, triazolopyrimidines, triazolinones and cyclohexanediones, and the weight ratio of the herbicide to the polyferulate is from 1:5 to 100:

1.

8. 4. The formulation of any of claims 2-3, wherein the herbicide is from the chemical family of benzoic acid, bipyridylium, dinitroaniline, diphenyl ether, oxyacetamide, phenoxycarboxylic acid, phosphinic acid, pyridinecarboxylic acid, pyridinecarboxamide or uracil, and the weight ratio of the herbicide to the polyferulate is from 1:5 to 100:

1.

9. 7. The formulation of claim 6, wherein the weight ratio of said herbicide to said polyferulate is from 1:2 to 40:

1.

10. 4. The formulation of claim 2, wherein the herbicide is a carboxylic acid and the weight ratio of the herbicide to the polyferulate is from 1:1 to 200:

1.

11. 11. The formulation of claim 10, wherein the weight ratio of said herbicide to said polyferulate is from 8:1 to 100:

1.

12. 11. The formulation of claim 10, wherein the herbicide is pelargonic acid.

13. 1. A method for controlling pests or aiding in harvest (desiccation) comprising: applying 2 to 98% of the recommended rate of a herbicide from the phenylpyrazole, triazolinone, glycine, triazolopyrimidine, cyclohexanedione, pyridinium, sulfonylurea, carbamate, benzofuran, or carboxylic acid chemical family when applied alone; applying 1 to 500 g / ha of polyferulate simultaneously with the herbicide or within 10 days before or after application of the herbicide.

14. The method according to claim 13, wherein the herbicide is applied in a mixture of 20-85% of the recommended dosage when applied alone with 1-250 g / ha of polyferulate, preferably 10-25 g / ha of polyferulate.

15. Use of the herbicide formulations according to claims 2-3 as premix concentrates (applied before, in combination with - co-formulation - or after said herbicide / desiccant / defoliant) or tank mixes with said herbicide / desiccant / defoliant to control weeds or to aid the harvest (desiccant).

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