Herbicidal composition containing drift retardant and preparation method thereof

Abstract

A herbicidal composition for reducing the ectopic movement or drift of a herbicide is described. The herbicidal composition may include an auxin herbicide, an oil or an ester of an oil, and a polymer emulsifier, such as glyceryl ethoxylate-polyricinoleate, glyceryl ethoxylate-poly-(12-hydroxystearate), polyethylene glycol (PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate) and combinations thereof. Methods for preparing such compositions and methods for preparing such polymer emulsifiers are also described.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of and priority to U.S. Provisional Application Serial No. 62 / 959,389, filed on January 10, 2020, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to a herbicidal composition concentrate comprising at least one herbicide (e.g., an auxin herbicide), an oil or an ester thereof, and a polymer emulsifier. The present disclosure also generally relates to a method for preparing such a herbicidal composition concentrate and a method for preparing the polymer emulsifier. Background Art

[0004] Auxinic herbicides, such as dicamba (3,6-dichloro-2-methoxybenzoic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid), are commonly used to control the growth of auxin-sensitive plants on agricultural and non-agricultural lands. Off-site movement of these herbicides has become a concern and may result in restrictions on the use of these herbicides. For example, migration of these herbicides from the application site to adjacent crop plants, such as soybeans and cotton, can occur, causing contact damage to sensitive plants. Off-site movement of auxinic herbicides can occur through three main mechanisms: physical movement or drift of small particles in the spray, contamination of the sprayer, and volatility of the herbicide after application. Monsanto has demonstrated this by using the trade name Vaporgrip TM Technology adds potassium acetate to auxin herbicide formulations to address volatility issues.

[0005] To address drift problems, drift retardants (DRAs) (also called drift reducers or drift control agents) can be included in the herbicidal composition. DRAs used in herbicidal sprays can work by changing the size distribution of particles formed by the nozzle, for example, by partially inhibiting the formation of the smallest particles (also called driftable fines), which settle the slowest and are most likely to drift with the wind. The definition of the size limit of "driftable fines" varies, but particles with a diameter of less than 150 μm are generally considered to be prone to drift. There are generally two types of DRAs. The first type of DRA is a polymer that can increase the extensional viscosity of the spray mixture. These polymers, which in commercial practice are limited to polyacrylamide, polyethylene oxide, and guar gum, can shift the spray particle size distribution to larger diameters. Although such polymers can be useful for some nozzles, for example, TeeJet's Turbo Induction(TTI TM ) Nozzle and Ultra Lo-Drift (ULD) nozzles are effective in reducing driftable fines, but they may be less popular because they can result in a significantly coarser spray, which can provide poorer coverage and, in turn, affect weed control. In addition, if such polymers are incorporated into herbicide formulations, they often result in unacceptably high viscosities.

[0006] The second type of DRA is called an "oil" or "emulsion" DRA. As the name implies, an oil-based DRA (mostly immiscible in water) is included in a can formulation as an emulsion or microemulsion. This type of drift retardant is available as an additive to a spray can under trade names such as Border EG (Precision Labs) and (Winfield). These oil or emulsion DRAs are effective in suppressing driftable fines, are suitable for a variety of nozzles, and have little effect on the average particle size of the spray; therefore, they provide better application coverage and herbicidal efficacy. Although the use of oil or emulsion DRAs as tank additives is common and straightforward, there are still technical challenges in adding them to auxin herbicide formulations, especially when producing auxin herbicide formulations with high auxin herbicide loadings. For example, auxin herbicides, such as dicamba and 2,4-D, are typically formulated in concentrated aqueous solution in salt form. A current commercial example is Dow's Enlist and Enlist One TM Product that incorporates a proprietary emulsion-type DRA into an aqueous solution of 2,4-D choline salt. Also included is the dimethylamine salt of glyphosate. Clariant has also published a report on a proprietary DRA that can be added to the diglycolamine (DGA) salt of dicamba.

[0007] However, it is well known that stabilizing emulsions in concentrated salt solutions is very difficult because emulsifiers do not perform well at high ionic strengths. Emulsions can be stabilized by two mechanisms, ionic repulsion and steric stabilization. At high ionic strengths, the electrostatic repulsion between oil droplets can be masked, preventing ionic stabilization. Typical nonionic surfactants (which can stabilize emulsions by steric repulsion) rely on polyethylene glycol (PEG) chains, but PEG chains can have poor solubility and less extended structures in media with high electrolyte content.

[0008] These considerations, as well as the need to achieve high auxin loadings, favor formulations with minimal oil-based DRAs. Thus, another challenge with utilizing oil-based DRAs is maintaining anti-drift efficacy with limited amounts of oil-based DRAs, particularly compared to the oil added to the spray tank when commercial spray adjuvants are used. Thus, auxin herbicide compositions having DRAs added thereto to reduce herbicide drift are desired, particularly reduced drift compositions that do not have a significant reduction in herbicidal efficacy relative to currently available compositions. Summary of the invention

[0009] New and useful herbicidal compositions comprising a drift retardant (DRA) and a polymeric emulsifier and methods of making the same are set forth in the appended claims. Illustrative embodiments are also provided to enable one skilled in the art to make and use the claimed subject matter.

[0010] On the one hand, a herbicidal composition concentrate is described. The herbicidal composition concentrate comprises at least one herbicide, an oil or an ester of an oil and a polymer emulsifier. The at least one herbicide may be present in an amount (acid equivalent weight) greater than or equal to about 5% by weight of the composition concentrate, and the at least one herbicide may include an auxin herbicide. The polymer emulsifier may be selected from glyceryl ethoxylate-polyricinoleate, glyceryl ethoxylate-poly-(12-hydroxystearate), polyethylene glycol (PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate) and combinations thereof. In some embodiments, the herbicidal composition concentrate further comprises a surfactant selected from phosphate, alkyl polysaccharide, alkoxylated castor oil and combinations thereof. In some embodiments, the herbicidal composition concentrate also comprises at least one monocarboxylic acid or its monocarboxylate.

[0011] On the other hand, a method for preparing a herbicidal composition concentrate is described. The method includes mixing at least one herbicide with an oil or an ester of an oil and a polymer emulsifier to form a herbicidal composition concentrate. The at least one herbicide can be mixed in an amount greater than or equal to about 5% by weight (acid equivalent weight) of the composition concentrate, and the at least one herbicide can include an auxin herbicide. The polymer emulsifier can be selected from glyceryl ethoxylate-polyricinoleate, glyceryl ethoxylate-poly-(12-hydroxystearate), polyethylene glycol (PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate) and combinations thereof. In some embodiments, the oil or an ester of an oil can be mixed with a polymer emulsifier to form a first mixture, and the at least one herbicide can be mixed with the first mixture to form a herbicidal composition concentrate. In some embodiments, the method also includes mixing at least one surfactant with at least one herbicide, an oil or an ester of an oil and a polymer emulsifier. The surfactant can be selected from phosphate esters, alkyl polysaccharides, alkoxylated castor oils and combinations thereof. In some embodiments, the method further comprises mixing at least one monocarboxylic acid or a monocarboxylate salt thereof with at least one herbicide, an oil or an ester of an oil, and a polymeric emulsifier.

[0012] In another aspect, a method for preparing a polymer surfactant selected from the group consisting of glycerol ethoxylate-polyricinoleate, glycerol ethoxylate-poly-(12-hydroxystearate), polyethylene glycol (PEG)-polyricinoleate, and PEG-poly-(12-hydroxystearate) is described. The method comprises contacting liquid or molten PEG or ethoxylated glycerol with C1-C4 alkyl ricinoleate or C1-C4 alkyl 12-hydroxystearate in the presence of a basic catalyst to form a reaction mixture at a reaction temperature sufficient to keep the reaction mixture in a liquid state.

[0013] Further benefits of the present invention will become clear to those skilled in the art by reading this patent application.The embodiments of the present invention described in the following paragraphs are intended to illustrate the present invention and should not be construed as narrowing the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1A and 1B Shown is the mass spectrum of glycerol ethoxylate-4-ricinoleate characterized by matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). DETAILED DESCRIPTION

[0015] The following description of exemplary embodiments provides information that enables those skilled in the art to make and use the subject matter set forth in the appended claims, but it may omit certain details that are already known in the art. Therefore, the following detailed description should be regarded as illustrative rather than limiting.

[0016] The present disclosure provides a herbicidal composition concentrate (e.g., comprising an auxin herbicide), wherein the composition exhibits reduced drift. Specifically, in addition to the auxin herbicide, the composition also comprises an oil or an ester of an oil and a polymer emulsifier. The polymer emulsifier may be selected from phosphate esters, alkyl polysaccharides, alkoxylated castor oils and combinations thereof. The composition may also comprise a surfactant and / or at least one monocarboxylic acid or its monocarboxylate to reduce the volatility of the herbicide when applied.

[0017] Typically, auxin herbicides, such as dicamba and 2,4-D, are formulated in concentrated aqueous solution in salt form. It is well known that stabilizing emulsions in concentrated salt solutions is very difficult because emulsifiers perform poorly at high ionic strengths. In addition, the inclusion of a monocarboxylic acid or its monocarboxylate salt for reducing volatility further increases the ionic strength of the composition, subsequently increasing the difficulty of stabilizing oil-based DRA emulsions and preventing undesirable creaming.

[0018] However, it has been surprisingly found that emulsions and microemulsions of oils can be stabilized with polymer emulsifiers including two or more polyethylene glycol (PEG) chains capped with oligomers of fatty acids in solutions with auxin herbicides, particularly highly loaded salt forms of auxin herbicides (e.g., monoethanolamine (MEA) salts of dicamba). In addition, the polymer emulsifiers described herein can be incorporated into herbicidal compositions including auxin herbicides at levels that improve spray particle size distribution. When many common nozzles are applied per label direction, the compositions provided herein can advantageously prevent auxins such as dicamba and 2,4-D from drifting. In addition, when DRA is needed, the composition can provide compliance assurance, thereby enhancing product management. Incorporating DRA into herbicidal composition concentrates also provides convenience and cost savings for growers and applicators compared to purchasing and adding herbicides and DRAs separately. In various aspects, the compositions described herein are applied by nozzles (e.g., but not limited to Greenleaf XL (TDXL), Lechler ID, Wilger DR, AIXR, ULD and TTI) provides significant suppression of fines without significantly increasing the average particle size of the spray. The compositions described herein with built-in DRA enable improved spray quality with better coverage and weed control.

[0019] A. Auxin Herbicide Components

[0020] The term "auxin herbicide" refers to a herbicide that acts as an analog of an auxin plant growth hormone, thereby affecting plant growth regulation. Examples of auxin herbicides suitable for use in the herbicidal composition of the present invention include, without limitation, benzoic acid herbicides, phenoxy herbicides, pyridinecarboxylic acid herbicides, pyridyloxy herbicides, pyrimidinecarboxyl herbicides, quinolinecarboxylic acid herbicides, and benzothiazole herbicides.

[0021] Examples of auxin herbicides include, but are not limited to: 3,6-dichloro-2-methoxybenzoic acid (dicamba); 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); dichloropropane; 2-methyl-4-chlorophenoxyacetic acid (MCPA); 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB); 4-chlorophenoxyacetic acid; 2,4,5-trichlorophenoxy Acetic acid (2,4,5-T); clopyralid; clopyralid; clopyralid; triclopyr; 2-methyl-4-chloropropionic acid; picloram; quinolinic acid; cyproconazole; chloranil; halauxifen; fluorpyrauxifen; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid -1H-indol-6-yl)pyridine-2-carboxylic acid; benzyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylic acid; methyl 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylic acid; methyl 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)-1H-indol-6-yl]pyridine-2-carboxylic acid; methyl 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylic acid; butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, including salts and esters thereof; racemic mixtures and resolved isomers thereof; and combinations thereof.

[0022] In any embodiment, the herbicidal composition concentrate may include dicamba, or an agriculturally acceptable salt or ester thereof. Examples of suitable dicamba salts include, but are not limited to, N,N-bis-[aminopropyl]methylamine salts, monoethanolamine (MEA) salts, dimethylamine salts (e.g., etc.), isopropylamine salts, triethanolamine salts, diglycolamine salts (e.g., etc.), potassium and sodium salts, and combinations thereof. Commercial sources of dicamba and its agriculturally acceptable salts include those sold under the trade names DISTINCT, and Those products that are sold.

[0023] In any embodiment, the herbicidal composition concentrate may include an agriculturally acceptable salt of dicamba, wherein the salt is selected from the group consisting of N,N-[aminopropyl]methylamine salts, monoethanolamine salts, dimethylamine salts, isopropylamine salts, diglycolamine salts, potassium salts, and sodium salts, and combinations thereof.

[0024] Throughout the remainder of the present specification, when reference is made to dicamba or an agriculturally acceptable salt or ester thereof, those skilled in the art will understand that the principles of the present invention are generally applicable to auxin herbicides, including those described above, and that the present invention is not limited to herbicidal compositions comprising dicamba or an agriculturally acceptable salt or ester thereof.

[0025] Additionally or alternatively, the herbicidal composition concentrate may include 2,4-D or an agriculturally acceptable salt or ester thereof. Examples of suitable salts of 2,4-D include, but are not limited to, choline salts, dimethylamine salts, triethanolamine salts, and isopropylamine salts, and combinations thereof. Examples of suitable esters of 2,4-D include, but are not limited to, methyl esters, ethyl esters, propyl esters, butyl esters (2,4-DB), and isooctyl esters, and combinations thereof. Commercial sources of 2,4-D and its agriculturally acceptable salts and esters include those sold under the trade names FORMULA OPT- and WEEDAR Those products that are sold.

[0026] Additionally or alternatively, the herbicidal composition concentrate may comprise an agriculturally acceptable salt of 2,4-D, wherein the salt is selected from the group consisting of choline salts, dimethylamine salts, triethanolamine salts and isopropylamine salts, and combinations thereof.

[0027] Additionally or alternatively, the herbicidal composition concentrate may comprise an agriculturally acceptable ester of 2,4-D, wherein the ester is selected from the group consisting of butyl ester (ie, 2,4-DB) and isooctyl ester, and combinations thereof.

[0028] Additionally or alternatively, the herbicidal composition concentrate may comprise at least two auxin herbicides, for example, dicamba or an agriculturally acceptable salt or ester thereof, and 2,4-D or an agriculturally acceptable salt or ester thereof.

[0029] Additionally or alternatively, the herbicidal composition concentrate may comprise an agriculturally acceptable auxin herbicide salt (e.g., dicamba salt, 2,4-D salt, and / or 2,4-DB salt) that is an ionic liquid as described in published application US 2013 / 0109572, i.e., a salt that is liquid at a temperature of about 150° C. or less. The entire text of US 2013 / 0109572 is incorporated herein by reference.

[0030] B. Oil component

[0031] In various aspects, the herbicidal composition concentrate comprises an oil or an ester thereof. The oil or the ester thereof can be used as a DRA.

[0032] The example of suitable oil includes but is not limited to vegetable oil, ester of vegetable oil, petroleum-based oil and combination thereof. Suitable vegetable oil includes but is not limited to soybean oil, ester of soybean oil, canola oil, ester of canola oil, palm oil, ester of palm oil, rapeseed oil, ester of rapeseed oil, sunflower oil, ester of sunflower oil, corn oil, ester of corn oil, peanut oil, ester of peanut oil, sesame oil, ester of sesame oil, olive oil, ester of olive oil and combination thereof. Suitable ester of vegetable oil includes but is not limited to methyl ester, such as canola acid methyl ester, soybean acid methyl ester etc., and ethyl ester, such as canola acid ethyl ester, soybean acid ethyl ester etc.

[0033] Suitable petroleum-based oils include, but are not limited to, alkanes (e.g., C6-C9 alkanes, normal alkanes, cycloalkanes, isoalkanes, etc.), distillates, naphthas (e.g., heavy naphthas, paraffinic naphthas, petroleum spirits, solvent naphthas, etc.), mineral oils, aliphatic oils, aromatic oils, crude oils, olefins, olefin mixtures, and combinations thereof. In any embodiment, the petroleum-based oil may have a suitable flash point, typically greater than 150°F, such as ISOPAR M TM (Available from ExxonMobil).

[0034] C. Polymer emulsifier component

[0035] 1. Structure of polymer emulsifier

[0036] It has been surprisingly found that polymeric emulsifiers comprising two or more polyethylene glycol (PEG) chains terminated with oligomers of fatty acids can stabilize emulsions and microemulsions of the oils and esters thereof described herein in solutions with auxinic herbicides, particularly highly loaded auxinic herbicides in salt form (e.g., the monoethanolamine (MEA) salt of dicamba). In addition, the polymeric emulsifiers described herein can be incorporated into herbicidal compositions comprising auxinic herbicides at levels that advantageously improve the spray particle size distribution.

[0037] In any embodiment, the polymer emulsifier may include two or more oligomers of ricinoleic acid or 12-hydroxystearic acid, which are commercially available from castor oil and hydrogenated castor oil, respectively. Without being bound by theory, it is believed that the polymer emulsifiers described herein can be more resistant to the collapse of PEG chains in high ionic strength media than conventional surfactants because the presence of two or more hydrophobes (e.g., ricinoleate blocks or 12-hydroxystearate blocks) embedded in the oil droplets can stretch the ethylene oxide (EO) chains of the polymer emulsifier. The fatty acid units can be separated by C 12 -Hydroxyl and C1-carboxylic acid are linked to each other by esterification. The structures of these oligomers are shown below:

[0038]

[0039] Where X 1 can be H or ricinoleate and X 2 It can be H or 12-hydroxystearate.

[0040] The oligomers can be esterified to PEG chains or ethoxylated glycerols, which can provide hydrophilicity to balance the hydrophobic effects of the fatty acid oligomers. In any embodiment, the polymer emulsifier can include a PEG chain of at least 500 molecular weight esterified at both ends, or the hydrophile can consist of multiple PEG chains. The unesterified terminal hydroxyl groups can be combined with an organic linker such as glycerol or polyglycerol. A glycerol with 26 ethylene oxide units, called "glycereth-26," can be used, for example, as G-26 is commercially available from Lonza. Cocoate esters of glycerol ethoxylates with varying degrees of ethoxylation are also commercially available, such as glycerol PEG-7 cocoate, CAS Reg. No. 68553-03-7, available from Spectrum Chemical or Kao Chemical. In particular, the polymeric emulsifier may include esterified ethoxylated glycerol, for example, glycerol ethoxylate esterified to poly-12-hydroxystearic acid, CAS Reg. No. 1939051-18-9.

[0041] In any embodiment, the polymer emulsifier can be selected from glycerol ethoxylate-polyricinoleate, glycerol ethoxylate-poly-(12-hydroxystearate), polyethylene glycol (PEG)-polyricinoleate, PEG-poly-(12-hydroxystearate) and combinations thereof. Glycerol ethoxylate-polyricinoleate can correspond in structure to Formula A:

[0042]

[0043] Wherein i+j+k=10-50 or 20-35 and r+s+t=3-12 or 4-8. In any embodiment, each of i, j and k can independently be an integer from 0-50, an integer from 0-35, an integer from 0-20, an integer from 0-10, an integer from 1-50, an integer from 1-35, an integer from 1-20, an integer from 1-10, an integer from 5-50, an integer from 5-35, an integer from 5-20 or an integer from 5-10. For example, i can be 1, j can be 5, and k can be 4; or, i can be 0, j can be 10, and k can be 12, etc. In any embodiment, each of r, s and t can independently be an integer from 0 to 12, an integer from 0 to 8, an integer from 0 to 4, an integer from 0 to 3, an integer from 1 to 12, an integer from 1 to 8, an integer from 1 to 4, an integer from 1 to 3, an integer from 2 to 12, an integer from 2 to 8, an integer from 2 to 4, or an integer from 2 to 3. For example, r can be 1, s can be 1 and t can be 1; or r can be 0, s can be 3 and t can be 5, etc.

[0044] Glycerol ethoxylate-poly-(12-hydroxystearate) may correspond in structure to Formula B:

[0045]

[0046] Wherein i+j+k=10-50 or 20-35 and r+s+t=3-12 or 4-8. In any embodiment, each of i, j and k can independently be an integer from 0-50, an integer from 0-35, an integer from 0-20, an integer from 0-10, an integer from 1-50, an integer from 1-35, an integer from 1-20, an integer from 1-10, an integer from 5-50, an integer from 5-35, an integer from 5-20 or an integer from 5-10. For example, i can be 1, j can be 5, and k can be 4; or, i can be 0, j can be 10, and k can be 12, etc. In any embodiment, each of r, s and t can independently be an integer from 0 to 12, an integer from 0 to 8, an integer from 0 to 4, an integer from 0 to 3, an integer from 1 to 12, an integer from 1 to 8, an integer from 1 to 4, an integer from 1 to 3, an integer from 2 to 12, an integer from 2 to 8, an integer from 2 to 4, or an integer from 2 to 3. For example, r can be 1, s can be 1 and t can be 1; or r can be 0, s can be 3 and t can be 5, etc.

[0047] Polyethylene glycol (PEG)-polyricinoleate may correspond in structure to Formula C:

[0048]

[0049] Wherein j=50-250 or 130-200 and s+r=2-10 or 3-6. In any embodiment, s and r can each independently be an integer from 0 to 10, an integer from 0 to 6, an integer from 0 to 3, an integer from 0 to 2, an integer from 1 to 10, an integer from 1 to 6, an integer from 1 to 3 or an integer from 1 to 2. For example, s can be 1 and r can be 3; or s can be 0 and r can be 7, etc.

[0050] PEG-poly-(12-hydroxystearate) may correspond in structure to Formula D:

[0051]

[0052] Wherein j=50-250 or 130-200 and s+r=2-10 or 3-6. In any embodiment, s and r can each independently be an integer from 0 to 10, an integer from 0 to 6, an integer from 0 to 3, an integer from 0 to 2, an integer from 1 to 10, an integer from 1 to 6, an integer from 1 to 3 or an integer from 1 to 2. For example, s can be 1 and r can be 3; or s can be 0 and r can be 7, etc.

[0053] Exemplary polymeric emulsifiers are shown below. Polymer (1) corresponds to PEG end-functionalized with a ricinoleate oligomer, and polymer (2) corresponds to glycerol ethoxylate end-functionalized with a 12-hydroxystearate oligomer:

[0054]

[0055] 2. Method for preparing polymer emulsifier

[0056] In various aspects, a method for preparing a polymer emulsifier as described herein is also provided. Oligomers of ricinoleic acid or 12-hydroxystearic acid esterified with glycerol and other polyols are known in the art and are prepared by first forming oligomers (usually using acid catalysis and solvents) and then acid-catalyzed esterification. Oligomerization generally requires high temperatures and / or extended time to drive off water. For example, Takeda et al. oligomerized 12-hydroxystearic acid in toluene at about 200° C. by p-toluenesulfonic acid catalysis for 6 hours (K.Takeda, Y.Kokeguchi, H.Sone, K.Kawai, "Oil Base and External Preparation Containing Same," 2008, US7,993,631, see Example 1). Similarly, Yamato et al. first oligomerized 12-hydroxystearic acid in xylene at 200° C. with a nitrogen stream for 15 hours. The oligomer was then esterified with dipentaerythritol at 210° C. (Y. Yamato, Y. Oi, M. Fujisawa, “Esterification Reaction Products and Cosmetic Products,” US 2008 / 0260663, see Production Example 1).

[0057] Similar polymerization reactions can also be performed enzymatically, but the process may be slow and require a water absorbent. For example, Zhang et al. polymerized ricinoleic acid on lipase PS at 60°C in the presence of molecular sieves for 7 days (Zhang, B.-X; Azuma, J.-I.; Takeno, S.; Suzuki, N.; Nakazawa, Y.; Uyama, H., "Improvement of the Rheological Properties of trans-1,4-polyisoprene from Eucommia ulmoides Oliver by Tri-branched Poly (ricinoleic acid), "Polymer Journal, 2016, 48, 821-7). The esterification of ethoxylated glycerol with fatty acids also requires extended reaction time under acidic conditions. For example, the esterification reaction between glycerol having 110-150 ethylene oxide (EO) units and tallow fatty acid requires 16 hours at 160° C. (AT Oliva, OP Biols, JBL Losas, EP Queralt, “Esters of Fatty Acids with Ethoxylated Polyols,” 1996, US 5,576,451, Henkel, Production Examples 1-3).

[0058] Advantageously, the method for preparing a polymer emulsifier as described herein can be achieved by performing all esterification in a single reactive step using esters of fatty acids rather than free fatty acids as starting materials. In any embodiment, C1-C4 alkyl esters can be starting materials. Suitable C1-C4 alkyl esters include, but are not limited to, methyl esters, such as methyl ricinoleate and methyl 12-hydroxystearate, and ethyl esters. Methanol (an exemplary byproduct or byproduct from the esterification reaction using a sodium methoxide catalyst described herein) is more volatile than water; therefore, it is easier to drive off, which advantageously allows the method described herein to be carried out at lower temperatures and with shorter reaction times. The conversion of castor oil to its methyl esters (mainly methyl ricinoleate) is known in the art (Knothe, G.; Cermak, SC; Evangelista, RL, "Methyl Esters from Vegetable Oils with Hydroxy Fatty Acids: Comparison of Lesquerella and Castor MethylEsters," Fuel, 2012, 96, 535-40). Methyl ricinoleate and methyl 12-hydroxystearate (derived from hydrogenated castor oil) are both commercially available.

[0059] The preparation of the polymer emulsifier described herein may include contacting PEG or ethoxylated glycerol with a suitable C1-C4 alkyl ester (e.g., methyl ricinoleate or methyl 12-hydroxystearate) in the presence of a basic catalyst at a suitable temperature and in a suitable reaction vessel for a suitable period of time to form a reaction mixture. Suitable temperatures include temperatures sufficient to keep the reaction mixture liquid. Examples of suitable temperatures include temperatures greater than or equal to about 70°C, greater than or equal to about 90°C, greater than or equal to about 110°C, greater than or equal to about 130°C, greater than or equal to about 150°C, greater than or equal to about 170°C, or about 180°C; or about 70°C to about 180°C, about 90°C to about 170°C, or about 110°C to about 150°C. Examples of suitable time periods include greater than or equal to about 60 minutes (1 hour), greater than or equal to about 120 minutes (2 hours), greater than or equal to about 180 minutes (3 hours), or about 240 minutes (4 hours); or about 60 minutes to about 240 minutes, about 120 minutes to about 240 minutes, or about 120 minutes to about 180 minutes. Examples of suitable alkaline catalysts include, but are not limited to, metal oxide catalysts, such as metal alkoxides or metal hydroxides. The metal alkoxide may be a metal C1-C4 alkoxide, such as, but not limited to, sodium methoxide and sodium ethoxide. The metal hydroxide may include, but is not limited to, sodium hydroxide and potassium hydroxide. In particular, the alkaline catalyst may be sodium methoxide. In any embodiment, the alkaline catalyst may be present in a concentration of greater than or equal to about 0.1%, greater than or equal to about 0.5%, greater than or equal to about 1%, greater than or equal to about 1.5%, greater than or equal to about 2%, greater than or equal to about 2.5%, or about 3% based on the total mass of the reaction mixture; or about 0.1% to about 3%, about 1% to about 3%, or about 2% to about 3%. As will be appreciated by those skilled in the art, the aforementioned time and temperature parameters may vary based on how the preparation is performed, such as the length of agitation, etc. For example, the reaction mixture may be stirred or agitated under suitable conditions to cause volatilization of the alcohol byproduct of the basic catalyst (e.g., C1-C4 alcohol byproduct such as methanol). These suitable conditions include, but are not limited to, maintaining a temperature above the boiling point of the alcohol, purging the headspace of the reactor with an inert gas, applying a vacuum, or a combination thereof.

[0060] A slow stream of nitrogen can be used to help remove alcohol byproducts (e.g., methanol) from the reaction mixture. In any embodiment, the reaction mixture can be a homogeneous liquid, for example, PEG and / or ethoxylated glycerol can each be in a liquid or molten state. In some embodiments, a C1-C4 alkyl ester, such as methyl ricinoleate or methyl 12-hydroxystearate, can be added dropwise to the PEG or ethoxylated glycerol under stirring, and the reaction can continue for at least 20 minutes after the addition is completed. In any embodiment, no solvent is required. The basic catalyst can be neutralized with a small amount of acid (e.g., acetic acid) at the end of the reaction, and the entire reaction mass is used in the formulation without further purification.

[0061] The exemplary reaction scheme below shows the reaction of PEG with methyl ricinoleate. Reactions involving ethoxylated glycerol or methyl 12-hydroxystearate follow the same reaction pathway.

[0062]

[0063] D. Surfactant

[0064] The herbicidal composition concentrate described herein may further comprise one or more surfactants. Examples of suitable surfactants include phosphate esters, alkyl polysaccharides, alkoxylated castor oils and combinations thereof. Such surfactants are particularly suitable due to their tolerance to high salt levels. In addition, when used at the level required for stabilizing the oil emulsion in the herbicide formulation containing the auxin herbicide, the surfactants described herein can not excessively increase the amount of fine droplets in the agricultural spray.

[0065] In any embodiment, the surfactant can be a phosphate ester. Examples of suitable phosphate esters include, but are not limited to, alkoxylated phosphate esters of fatty acids. Alkoxylation can include alkoxy chains of any length. For example, polyethylene oxide or polypropylene oxide. Examples of the ester include polyethylene glycol octyl phosphate, polyethylene glycol isotridecyl phosphate, polyethylene glycol cetearyl phosphate, polyethylene glycol decyl phosphate, polyethylene glycol oleyl phosphate, polyethylene glycol polypropylene glycol cetyl phosphate, polyethylene glycol tridecyl phosphate and polyethylene glycol isotridecyl phosphate. Additionally or alternatively, the phosphate ester can be an ethoxylated alkyl phosphate, for example, having less than 10 EO units. Commercially available ethoxylated alkyl phosphates include Crodafos TM O3A and Crodafos TM O5A, both available from Croda, Inc.

[0066] Additionally or alternatively, the surfactant may be an alkyl polysaccharide. Examples of suitable alkyl polysaccharides include, but are not limited to, compounds of formula (1):

[0067] R 11 -O-(sug) u Formula (1)

[0068] Where R 11It is a straight or branched substituted or unsubstituted hydrocarbon group selected from alkyl, alkenyl, alkylphenyl, alkenylphenyl having about 4 to about 22 carbon atoms or about 4 to 18 carbon atoms. The sug part is a sugar residue and can be an open or cyclic (i.e., pyranose) structure. Sugar can be a monosaccharide, disaccharide, oligosaccharide or polysaccharide with 5 or 6 carbon atoms. Examples of suitable sugar moieties (including their corresponding pyranose forms) include ribose, xylose, arabinose, glucose, galactose, mannose, talose (telose), gulose, allose, altrose, idose, lyxose, ribulose, sorbose (sorbitan), fructose and mixtures thereof. Examples of suitable disaccharides include maltose, lactose and sucrose. Disaccharides, oligosaccharides and polysaccharides can be a combination of two or more identical sugars, such as maltose (two glucoses), or a combination of two or more different sugars, such as sucrose (a combination of glucose and fructose). The degree of polymerization u is an average number from 1 to about 10, from 1 to about 8, from 1 to about 5, from 1 to about 3, and from 1 to about 2.

[0069] In various embodiments, the alkyl polysaccharide may be an alkyl polyglucoside (APG) surfactant of formula (1), wherein: R 11 is a branched or straight chain alkyl group preferably having 4 to 22 carbon atoms or 8 to 18 carbon atoms, or a mixture of alkyl groups with an average value within the given range; sug is a glucose residue (e.g., glucoside); and u is from 1 to about 5, and more preferably from 1 to about 3. In various embodiments, the surfactant component comprises an APG of formula (1), wherein R 11 is a branched or straight chain alkyl group having 8 to 10 carbon atoms or a mixture of alkyl groups having an average value within the given range, and u is from 1 to about 3.

[0070] Non-limiting examples of commercially available alkyl polyglucosides include, for example, or Surfactants such as Agnique PG 264, Agnique PG 8105 and Agnique 8107, all available from Dow, Inc., and TRITON TM BG and TRITON TM CG.

[0071] Additionally or alternatively, the surfactant may be an alkoxylated castor oil, such as an ethoxylated castor oil (e.g., having less than 30 EO units) or a propoxylated castor oil. Alkoxylated castor oils may be prepared by reaction of castor oil or hydrogenated castor oil with ethylene oxide, propylene oxide, ethylene glycol, or propylene glycol. Examples of suitable alkoxylated castor oils include, but are not limited to, CO-40(40EO), 8242, 8243, 8244, and Cirrasol from Croda Inc. TM G-1292 (25EO). Other suitable examples may include Emulpon from AkzoNobel Nouryon TM CO-550, CO-360, CO-200 and Surfom from Oxiteno 360 and R 540.

[0072] Additionally or alternatively, the surfactant may include various quaternary ammonium compounds. The quaternary ammonium compounds include various alkyl / aryl quaternary ammonium compounds and alkoxylated alkyl / aryl quaternary ammonium compounds, including but not limited to ethoxylated quaternary ammonium compounds.

[0073] In some embodiments, the quaternary ammonium compound has the structure of Formula (I):

[0074]

[0075] Where R 1 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene; each R 3 R is independently hydrogen, or a straight or branched chain alkyl group having 1 to about 4 carbon atoms; 4 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; x and y are independently a number from 0 to about 10; and X - It is an agriculturally acceptable anion.

[0076] Specific examples of quaternary ammonium compounds include tetrabutylammonium salts (e.g., tetrabutylammonium chloride and tetrabutylammonium chloride hydroxide) and trimethyl-tetradecylammonium salts (e.g., trimethyl-tetradecylammonium chloride). Other examples include the Tomamine series of quaternary ammonium compounds available from Evonik, especially the Tomamine Q series, which are represented by formula (II):

[0077]

[0078] Where R is an alkyl group (e.g. C1-C 20alkyl), n is the total number of moles of EO (CH2CH2O), and n+z is generally a number of 0 to 15. Specific examples of tommamines include Q-14-2 (isodecyloxypropyl dihydroxyethyl methyl ammonium chloride), Q-17-2 (isotridecyloxypropyl dihydroxyethyl methyl ammonium chloride), Q-17-5 (isotridecyloxypropyl poly (5) oxyethylene methyl ammonium chloride) and Q-18-2 (octadecyl dihydroxyethyl methyl ammonium chloride).

[0079] E. Monocarboxylic Acid / Monocarboxylate Component

[0080] "Monocarboxylic acid" refers to a hydrocarbon or substituted hydrocarbon containing only one carboxyl functional group (i.e., R 1 -C(O)OH). "Monocarboxylate" refers to a salt (i.e., R 1 -C(O)OM, wherein M is an agriculturally acceptable cation). In one embodiment, the composition comprises at least one monocarboxylate salt, which may be present in the aqueous composition in whole or in part in dissociated form as a monocarboxylate anion and a corresponding cation.

[0081] Typical monocarboxylic acids and monocarboxylates generally contain hydrocarbons or unsubstituted hydrocarbons selected from, for example, unsubstituted or substituted straight or branched chain alkyls (e.g., C1-C 20 alkyl, such as methyl, ethyl, n-propyl, isobutyl, etc.), unsubstituted or substituted straight-chain or branched alkenyl (e.g., C2-C 20 The monocarboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid and benzoic acid. In another embodiment, the monocarboxylic acid salt is selected from the group consisting of formate, acetate, propionate and benzoate.

[0082] In one embodiment, the herbicidal composition comprises a herbicidal composition having the formula R 1 -C(O)OM monocarboxylate, wherein R 1 is unsubstituted or substituted C1-C 10 In another embodiment, the herbicidal composition comprises a herbicidal composition having the formula R 1 -C(O)OM monocarboxylate, wherein R 1 is an unsubstituted C1-C6 alkyl group, and M is an alkali metal salt. In another embodiment, the herbicidal composition comprises a compound having the formula R 1 -C(O)OM monocarboxylate, wherein R 1is an unsubstituted C1-C3 alkyl group, and M is an alkali metal salt selected from sodium and potassium. In another embodiment, the monocarboxylate is potassium acetate. In another embodiment, the monocarboxylate is sodium acetate.

[0083] F. Alkali metal phosphate

[0084] The herbicidal composition concentrate may optionally further comprise an alkali metal phosphate, such as dipotassium hydrogen phosphate. For example, dipotassium hydrogen phosphate can provide additional buffering and / or water-conditioning for the aqueous herbicidal composition of the present invention. Dipotassium hydrogen phosphate is particularly effective as a substitute for ammonium sulfate in herbicidal composition application mixtures prepared using hard water.

[0085] G. Non-herbicide additives

[0086] The herbicidal composition concentrate may optionally further comprise conventional additives, such as other surfactants, safeners, solubilizers, thickeners, flow enhancers, foam regulators, cryoprotectants, UV protectants, preservatives, biocides and / or other additives which are necessary or desired to improve the performance, crop safety or handling of the composition.

[0087] In any embodiment, the herbicidal composition concentrate may contain less than about 10 ppm ammonium sulfate. In another embodiment, the herbicidal composition concentrate does not contain ammonium sulfate.

[0088] In any embodiment, the herbicidal composition concentrate contains no acids other than monocarboxylic acids.

[0089] H. Other herbicide components

[0090] The herbicidal composition concentrate may optionally contain at least one other herbicide. Representative examples of other herbicides include, but are not limited to, hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetyl-CoA carboxylase (ACCase) inhibitors, acetolactate synthase (ALS) inhibitors, acetohydroxyacid synthase (AHAS) inhibitors, photosystem II (PS II) inhibitors, photosystem I (PS I) inhibitors, protoporphyrinogen oxidase (PPO or Protox) inhibitors, carotenoid biosynthesis inhibitors, enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, glutamine synthetase inhibitors, dihydropteroate synthase inhibitors, mitosis inhibitors, nucleic acid inhibitors, cellulose inhibitors, oxidative phosphorylation uncouplers, dihydropteroate synthase inhibitors, fatty acid and lipid biosynthesis inhibitors, auxin transport inhibitors, salts and esters thereof, racemic mixtures and resolved isomers thereof, and mixtures thereof; salts and esters thereof; racemic mixtures and resolved isomers thereof; and combinations thereof.

[0091] Application mixtures can be prepared by diluting an aqueous herbicidal concentrate composition as described herein. Other herbicides can be "tank mixed" with an application mixture prepared from an aqueous herbicidal concentrate composition described herein.

[0092] Examples of herbicides in these classes of other herbicides are provided below. When a herbicide is referred to generically by name herein, unless otherwise limited, the herbicide includes all commercially available forms known in the art, such as salts, esters, free acids and free bases, and stereoisomers thereof.

[0093] Representative examples of HPPD inhibitors include, but are not limited to, fenpyroxil, fluazifop, pyraclostrobin, oxadiazine, fluazifop, flufenac, flucyclopent, fluazifop, flutolan, fluazifop, flutolan, fluazifop, flutolan, fluazifop, flutolan, pyraclostrobin, pyraclostrobin, pyrazoline, benzaclostrobin, sulfamethoxam, cypermethrin, tolpyralate, teflonone, their salts and esters, and mixtures thereof.

[0094] Representative examples of ACCase inhibitors include, but are not limited to, chlorazifop, clofos-butyl, clethodim, cypermethrin, pinoxaden, sethoxydim, pyraclostrobin and oxathiocarb, their salts and esters, and mixtures thereof. Another group of ACCase inhibitors includes chlorazifop, clofop-butyl, clofop, cyhalofop-butyl, diclofop, diclofop-methyl, oxadiazine, thiazolyl, fluazifop, fluazifop-butyl, isoxadiazine, oxadiazine, oxadiazine, quizalofop and trifop, their salts and esters, and mixtures thereof. ACCase inhibitors also include mixtures of one or more "dim" and one or more "fop", and their salts and esters.

[0095] Representative examples of ALS or AHAS inhibitors include, but are not limited to, amidosulfuron, azimsulfruon, benzamidinesulfuron, bispyribac-sodium, chlorimuron, chlorsulfuron, chlorsulfuron, chlorsulfuron, chlorsulfuron, chlorsulfuron, cyprosulfuron, bispyribac-sodium, ethametsulfuron, ethoxysulfuron, fluazifop-methyl, bispyribac-sodium, fluazifop-methyl ... Sulfur-methyl, imazapic, methazapic, methyl imazapic, imazapic, imazaquin, imazapic, imazapic, imazalsulfuron, iodosulfuron-methyl, metsulfuron-methyl, nicosulfuron, penoxsulam, primisulfuron-methyl, propansulfuron-methyl, prosulfuron, pyrazosulfuron-methyl, pyrimidinesulfuron-butyl, pyrimidinesulfuron-butyl, sulfamethoxam, sulfamethoxam, sulfamethoxam, thiocarb-methyl, thifensulfuron-methyl, ether bensulfuron-methyl, bensulfuron-methyl, trifloxysulfuron and flufenac, their salts and esters, and mixtures thereof.

[0096] Representative examples of photosystem I inhibitors include, but are not limited to, diquat and paraquat, their salts and esters, and mixtures thereof. Representative examples of photosystem II inhibitors include, but are not limited to, ametryn, amitriptyline, atrazine, bentazon, herbicide, bromoxynil, chlorotoluron, cyanazine, betamethrin, dichlorvos, oxazolidinone, diuron, fluuron, hexazinone, ioxynil, isoproturon, linuron, metamitron, methylbenzenesulfuron, methoxuron, metribuzin, chlorothiazin, betamethrin, promethazine, promethazine, propanil, cypermethrin, pyralid, cypermethrin, simazine, simethrin, thiocarb, terbuthion, terbuthion, and thiocarb, their salts and esters, and mixtures thereof.

[0097] Representative examples of PPO inhibitors include, but are not limited to, diphenyl ethers (acifluorfen, chlorfenapyr, fenpyroxil, fluazifop-butyl, fomesafen, lactofen, oxyfluorfen-butyl), N-phenylphthalimides (indolone, fumiclorac, fluazifop-butyl, fluazifop-butyl), oxadiazoles (oxadiazine, oxadiazine), oxazolidinones (oxadiazine-butyl), phenylpyrazoles (fluazolate, fluazifop-butyl), , pyrimidinedione (bispyribac-butyl, fluazifop-butyl, fluazifop-butyl, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate, thiadiazoles (methyl fluazifop-butyl, fluazifop-butyl), triazinones (trifluoxetine), triazolinones (trifluoxetine, mesotrione, sulfentrazone) and others (flupyridazine-butyl, fluazifop-butyl, bispyribac-butyl).

[0098] Representative examples of carotenoid biosynthesis inhibitors include, but are not limited to, aclonifen, difluanid, mesotrione, and sulcotrione.

[0099] Representative examples of EPSP inhibitors include, but are not limited to, N-phosphonomethylglycine (glyphosate).

[0100] Representative examples of glutamine synthetase inhibitors include, but are not limited to, glufosinate.

[0101] Representative examples of dihydropteroate synthase inhibitors include, but are not limited to, sulfamethoxazole.

[0102] Representative examples of mitotic inhibitors include, but are not limited to, acetochlor, alachlor, dithiopyr, S-metolachlor, and thiamethoxam.

[0103] Representative examples of nucleic acid inhibitors include, but are not limited to, diquat, chlorpyrifos, metamidine, and nonanoic acid.

[0104] In any embodiment, the herbicidal composition concentrate further comprises an additional herbicide selected from the group consisting of acetochlor, glyphosate, glufosinate, fluazifop-butyl, fomesulfuron, and agriculturally acceptable salts thereof.

[0105] In one embodiment, the herbicidal composition concentrate also comprises glyphosate or its agriculturally acceptable salt. Suitable glyphosate salts include, for example, ammonium salts, diammonium salts, dimethylammonium salts, monoethanolamine salts, isopropylamine salts and sylvite, and combinations thereof. In any embodiment, the glyphosate salt is selected from monoethanolamine salts, isopropylamine salts and sylvite, and combinations thereof.

[0106] In any embodiment, the herbicidal composition concentrate further comprises glufosinate-ammonium or an agriculturally acceptable salt thereof.

[0107] In any embodiment, the herbicidal composition concentrate comprises dicamba or an agriculturally acceptable salt or ester thereof, and glyphosate or an agriculturally acceptable salt thereof. Additionally or alternatively, the herbicidal composition concentrate comprises dicamba or an agriculturally acceptable salt thereof; glyphosate or an agriculturally acceptable salt thereof; and a non-ammoniacal agriculturally acceptable acetate. Commercial sources of glyphosate and its agriculturally acceptable salts include those sold under the trade names HONCHO ROUNDUP ROUNDUP and Those products that are sold.

[0108] Additionally or alternatively, the herbicidal composition concentrate comprises 2,4-D or an agriculturally acceptable salt or ester thereof, and glyphosate or an agriculturally acceptable salt thereof. Additionally or alternatively, the herbicidal composition concentrate comprises 2,4-D or an agriculturally acceptable salt or ester thereof; glyphosate or an agriculturally acceptable salt thereof; and a non-ammoniac agriculturally acceptable acetate.

[0109] In any embodiment, the herbicidal composition concentrate comprises dicamba or an agriculturally acceptable salt or ester thereof, and glufosinate or an agriculturally acceptable salt thereof. Additionally or alternatively, the herbicidal composition concentrate comprises 2,4-D or an agriculturally acceptable salt or ester thereof, and glufosinate or an agriculturally acceptable salt thereof.

[0110] In any embodiment, the herbicidal composition concentrate comprises an agriculturally acceptable non-auxin herbicide salt (such as a glyphosate salt) which is an ionic liquid described in published application US2013 / 0109572, i.e., a salt that is liquid at a temperature of about 150°C or less. I. Component Loading

[0111] 1. Herbicide load:

[0112] Herbicidal composition concentrate as herein described can be diluted with water before application.Concentrated herbicidal composition as herein described can comprise based on acid equivalent (ae or ae) usually, for example, from about 120 to about 600g ae / L, from about 300 to about 600g ae / L, from about 350 to about 600g ae / L, from about 400 to about 600g ae / L, from about 450 to about 600g ae.e. / L or from about 500 to about 600g ae / L total herbicide load.As used herein, term " total herbicide load " contains the herbicide load when only having a kind of herbicide in composition, for example, a kind of auxin herbicide or a kind of non-auxin herbicide, and when having one or more herbicides (for example, two kinds of auxin herbicides or auxin herbicide and non-auxin herbicide) total load. Other examples of representative total herbicide loadings include about 120, 150, 200, 250, 300, 350, 400, 450, 500, 550 and 600 g ae / L and ranges thereof (i.e., a total herbicide loading from about 120 to about 150 g ae / L, from about 150 to about 200 g ae / L, from about 200 to about 250 g ae / L, from about 250 to about 300 g ae / L, from about 300 to about 350 g ae / L, from about 350 to about 400 g ae / L, from about 400 to about 450 g ae / L, from about 450 to about 500 g ae. / L, from about 500 to about 550 g ae / L, and from about 550 to about 600 g ae / L).

[0113] In any embodiment, the herbicidal composition can be a liquid concentrate comprising, for example, a total amount of herbicide (acid equivalent weight) greater than or equal to about 5%, greater than or equal to about 10%, greater than or equal to about 15%, greater than or equal to about 20%, greater than or equal to about 30%, greater than or equal to about 40%, greater than or equal to about 50%, greater than or equal to about 60%, or about 70%, based on the weight of the composition concentrate. Additionally or alternatively, the herbicidal composition is a liquid concentrate comprising, for example, a total amount of herbicide (acid equivalent weight) from about 5% to about 70%, about 5% to about 60%, about 5% to about 50%, about 10% to about 40%, about 10% to about 30%, or about 10% to about 20%, based on the weight of the composition concentrate.

[0114] In the herbicidal composition concentrate comprising an auxin herbicide and a non-auxin herbicide, the weight ratio of the auxin herbicide to the non-auxin herbicide, based on acid equivalents, is typically no greater than about 50:1, for example, about 50:1, 25:1, 10:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, about 1:10 or a range thereof, such as from about 50:1 to about 1:10, from about 50:1 to about 1:5, from about 50:1 to about 1:1, from about 50:1 to about 3:1, from about 50:1 to about 5:1, from about 50:1 to about 10:1, from about 25:1 to about 1:1 or from about 25:1 to about 3:1.

[0115] In specific embodiments, the herbicidal composition concentrate can include an auxin herbicide in an amount from about 5% to about 70%, from about 5% to about 60%, from about 5% to about 50%, from about 10% to about 40%, from about 10% to about 30%, or from about 10% to about 20%, by weight of the composition concentrate (acid equivalent weight), and a non-auxin herbicide in an amount from about 10% to about 70%, from about 15% to about 60%, from about 15% to about 50%, or from about 20% to about 40%, by weight of the composition concentrate (acid equivalent weight).

[0116] For any given auxinic herbicide, one skilled in the art can readily determine using routine experimentation the minimum concentration of auxinic herbicide and the minimum ratio of auxinic herbicide to any other auxinic herbicides and / or non-auxinic herbicides contained in the herbicidal composition that is required for the intended application.

[0117] 2. Oil load

[0118] In any embodiment, oil or its ester as described herein can be present in the composition concentrate with a total oil load of greater than or equal to about 1%, greater than or equal to about 1.5%, greater than or equal to about 2%, greater than or equal to about 5%, greater than or equal to about 8%, greater than or equal to about 10%, greater than or equal to about 12%, greater than or equal to about 15% or about 20% by weight of the composition concentrate. As used herein, the term "total oil load" encompasses the oil load when only one oil or its ester is present in the composition and the total load when there are one or more oils and / or its esters. Additionally or alternatively, oil or its ester can be present in the composition concentrate with a total oil load of about 1% to about 20%, about 1% to about 15%, about 2% to about 12%, about 2% to about 10%, or about 5% to about 10% by weight of the composition concentrate.

[0119] Advantageously, the total oil loading in the composition concentrates described herein can provide at least 10 ml of oil spray / acre (0.404686 ha), preferably at least 30 ml of oil spray / acre (0.404686 ha), when the composition concentrate is sprayed at its agronomic rate (e.g., 560 g acid equivalent per hectare (ha) for dicamba).

[0120] 3. Polymer emulsifier loading

[0121] In any embodiment, the polymer emulsifier as described herein can be present in the composition concentrate at a total polymer emulsifier loading of greater than or equal to about 0.2 wt.%, greater than or equal to about 0.5 wt.%, greater than or equal to about 0.7 wt.%, greater than or equal to about 1 wt.%, greater than or equal to about 2 wt.%, greater than or equal to about 3 wt.%, greater than or equal to about 4 wt.%, greater than or equal to about 5 wt.%, greater than or equal to about 6 wt.%, greater than or equal to about 7 wt.%, greater than or equal to about 8 wt.%, greater than or equal to about 9 wt.%, greater than or equal to about 10 wt.%, or about 15 wt.%, based on the weight of the composition concentrate. As used herein, the term "total polymer emulsifier loading" encompasses the polymer emulsifier loading when only one polymer emulsifier is present in the composition as well as the total loading when one or more polymer emulsifiers are present. Additionally or alternatively, the polymeric emulsifier can be present in the composition concentrate at a total emulsifier loading of about 0.2 wt.% to about 15 wt.%, about 0.2 wt.% to about 15 wt.%, about 0.2 wt.% to about 10 wt.%, about 0.5 wt.% to about 10 wt.%, or about 1 wt.% to about 5 wt.%, based on the weight of the composition concentrate.

[0122] Additionally or alternatively, the polymer emulsifiers and oils or esters thereof described herein can be present in the composition concentrate at a total polymer emulsifier and oil loading of greater than or equal to about 0.5 wt.%, greater than or equal to about 0.7 wt.%, greater than or equal to about 1 wt.%, greater than or equal to about 2 wt.%, greater than or equal to about 3 wt.%, greater than or equal to about 4 wt.%, greater than or equal to about 5 wt.%, greater than or equal to about 6 wt.%, greater than or equal to about 7 wt.%, greater than or equal to about 8 wt.%, greater than or equal to about 9 wt.%, or greater than or equal to about 10 wt.%, based on the weight of the composition concentrate. As used herein, the term "total polymer emulsifier and oil loading" encompasses the polymer emulsifier loading when only one polymer emulsifier and oil and / or ester thereof is present in the composition as well as the total loading when one or more polymer emulsifiers and one or more oils and / or esters thereof are present. Additionally or alternatively, the polymeric emulsifier and the oil or ester thereof can be present in the composition concentrate at a total emulsifier and oil loading of about 0.5 wt.% to about 10 wt.%, about 0.5 wt.% to about 8 wt.%, or about 1 wt.% to about 7 wt.%, based on the weight of the composition concentrate.

[0123] 4. Surfactant loading

[0124] In any embodiment, the surfactants described herein can be present in the composition concentrate at a total surfactant loading of greater than or equal to about 1 wt.%, greater than or equal to about 2 wt.%, greater than or equal to about 3 wt.%, greater than or equal to about 4 wt.%, greater than or equal to about 5 wt.%, greater than or equal to about 6 wt.%, greater than or equal to about 7 wt.%, greater than or equal to about 8 wt.%, greater than or equal to about 9 wt.%, greater than or equal to about 10 wt.%, greater than or equal to about 12 wt.%, greater than or equal to about 15 wt.%, greater than or equal to about 20 wt.%, greater than or equal to about 25 wt.%, greater than or equal to about 25 wt.%, or about 30 wt.%, based on the weight of the composition concentrate. As used herein, the term "total surfactant loading" encompasses the surfactant loading when only surfactant is present in the composition as well as the total loading when one or more surfactants are present. Additionally or alternatively, the surfactant can be present in the composition concentrate at a surfactant loading of about 1 wt.% to about 30% wt.%, about 1 wt.% to about 25% wt.%, about 2 wt.% to about 25 wt.%, about 3 wt.% to about 25 wt.%, about 4 wt.% to about 25 wt.%, about 5 wt.% to about 25 wt.%, about 5 wt.% to about 20 wt.%, about 10 wt.% to about 20 wt.%, about 15 wt.% to about 20 wt.%, or about 10 wt.% to about 15 wt.%, based on the weight of the composition concentrate.

[0125] 5. Monocarboxylic acid / monocarboxylate loading:

[0126] In any embodiment, the herbicidal composition concentrate may contain a single monocarboxylic acid or a monocarboxylate salt thereof, or a mixture of two or more monocarboxylic acids or monocarboxylates thereof.

[0127] In various embodiments, the concentration of the volatile auxin herbicide in the vapor phase surrounding an herbicidal composition comprising an auxin herbicide and a monocarboxylic acid or a monocarboxylate thereof is less than about 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5% of the concentration of the volatile auxin herbicide in the vapor phase surrounding a reference composition not containing the monocarboxylate.

[0128] The monocarboxylic acid or monocarboxylate load of the herbicidal composition may generally depend on the auxin herbicide load of the herbicidal composition, the salt form of the auxin herbicide, and the properties of any other components of the herbicidal composition, and is an amount sufficient to reduce the volatility of the auxin herbicide (relative to a reference composition that does not contain the monocarboxylic acid or monocarboxylate but otherwise has the same composition). For example, the volatility of the monoethanolamine salt and diglycolamine salt of Mediben is lower than the dimethylamine salt and isopropylamine salt of Mediben, and the load required for the lower volatility salt may be less than the load required for the higher volatility salt. In addition, the load of the monocarboxylic acid or its monocarboxylate may vary with the specific combination of auxin herbicides, optional non-auxin herbicides, and monocarboxylic acids or their monocarboxylates.

[0129] In the herbicidal composition concentrate described herein, the molar ratio of the auxin herbicide to the monocarboxylic acid or its monocarboxylate is generally not less than about 1:10 and not more than about 10:1. Representative molar ratios of auxin herbicide acid equivalents (ae) to total monocarboxylic acids or their monocarboxylates are, for example, from 1:10 to about 10:1, from about 3:10 to about 10:1, from about 1:5 to about 5:1, and from about 3:1 to about 1:3. In any embodiment, the molar ratio of the auxin herbicide to the monocarboxylic acid or its monocarboxylate is from about 2:1 to about 1:2. In any embodiment, the molar ratio of the auxin herbicide to the monocarboxylic acid or its monocarboxylate is about 1:1.

[0130] In any embodiment, the herbicidal composition concentrate may contain a monocarboxylic acid or a monocarboxylate salt thereof in an amount from about 0.25% to about 35%, about 5% to about 30%, or about 5% to about 20% by weight of the concentrate (acid equivalent weight).

[0131] 6. Alkali metal phosphate / alkali metal carbonate loading

[0132] When the herbicidal composition concentrate contains an alkali metal phosphate such as dipotassium hydrogen phosphate, the molar ratio of the alkali metal phosphate to the monocarboxylic acid or its monocarboxylate salt may be, for example, from about 1:5 to about 5:1, from about 3:1 to about 1:3, or from about 2:1 to about 1:2. In any embodiment, the molar ratio of the alkali metal phosphate to the monocarboxylic acid or its monocarboxylate salt is about 1:1.

[0133] When the herbicidal composition concentrate contains an alkali metal carbonate such as potassium carbonate, the molar ratio of the alkali metal carbonate to the monocarboxylic acid or its monocarboxylate salt may be, for example, from about 1:5 to about 5:1, from about 3:1 to about 1:3, or from about 2:1 to about 1:2. In any embodiment, the molar ratio of the alkali metal carbonate to the monocarboxylic acid or its monocarboxylate salt is about 1:1.

[0134] J. Method for preparing herbicidal composition concentrate

[0135] Also provided is a method for preparing a herbicidal composition concentrate as described herein. The formed herbicidal composition concentrate can be an emulsion or a microemulsion. The method may include mixing at least one herbicide as described herein, such as an auxin herbicide, with an oil or an ester of an oil as described herein and a polymer emulsifier as described herein to form a herbicidal composition concentrate. In any embodiment, the oil or the ester of the oil can be mixed with the polymer emulsifier to form a first mixture, and at least one herbicide can be mixed with the first mixture to form a herbicidal composition concentrate. The oil or the ester of the oil can be a vegetable oil, an ester of a vegetable oil, or a petroleum-based oil, all as described herein. For example, the oil or the ester of the oil can be selected from soybean oil, an ester of soybean oil, canola oil, an ester of canola oil, palm oil, an ester of palm oil, rapeseed oil, an ester of rapeseed oil, sunflower seed oil, an ester of sunflower seed oil, corn oil, an ester of corn oil, peanut oil, an ester of peanut oil, sesame oil, an ester of sesame oil, olive oil, an ester of olive oil, and a combination thereof.

[0136] The polymer emulsifier can be selected from glyceryl ethoxylate-polyricinoleate (e.g., corresponding to formula (A) as described herein), glyceryl ethoxylate-poly-(12-hydroxystearate) (e.g., corresponding to formula (B) as described herein), polyethylene glycol (PEG)-polyricinoleate (e.g., corresponding to formula (C) as described herein), PEG-poly-(12-hydroxystearate) (e.g., corresponding to formula (D) as described herein) and combinations thereof. The at least one auxin herbicide can be selected from dicamba, agriculturally acceptable salts of dicamba (e.g., N,N-[aminopropyl]methylamine salts, monoethanolamine salts, dimethylamine salts, isopropylamine salts, diglycolamine salts, potassium salts and sodium salts, and combinations thereof), agriculturally acceptable esters of dicamba, 2,4-D, agriculturally acceptable salts of 2,4-D, agriculturally acceptable esters of 2,4-D and combinations thereof.

[0137] The total herbicide loading of the composition concentrate can be as described herein, for example, in an amount of at least about 5% to about 50% by weight of the composition concentrate (acid equivalent weight). The total oil loading of the composition concentrate can be as described herein, for example, in an amount of at least about 1.5% by weight of the composition concentrate. The total polymer emulsifier loading of the composition concentrate can be as described herein, for example, in an amount of at least about 0.2% by weight of the composition concentrate.

[0138] In any embodiment, the method may further include mixing at least one herbicide with water to form an aqueous solution prior to mixing with the oil or ester of the oil and the polymer emulsifier. Additionally or alternatively, the method may further include mixing at least one surfactant as described herein (e.g., a phosphate ester, an alkyl polysaccharide, an alkoxylated castor oil, or a combination thereof) with at least one herbicide, the oil or ester of the oil and the polymer emulsifier.

[0139] Additionally or alternatively, the method may further comprise mixing at least one monocarboxylic acid (e.g., acetic acid) or a monocarboxylate thereof (e.g., potassium acetate) with at least one herbicide, an oil or an ester of an oil, and a polymer emulsifier. In any embodiment, the herbicidal composition concentrate may contain, by weight of the concentrate, for example, an amount of a monocarboxylic acid or a monocarboxylate thereof as described herein (acid equivalent weight) of about 5% to about 30% and / or a molar ratio of at least one monocarboxylic acid or a monocarboxylate thereof as described herein to an auxin herbicide of, for example, about 1:10 to about 10:1.

[0140] Additionally or alternatively, the method may also include mixing at least one other herbicide (e.g., glyphosate, agriculturally acceptable salts of glyphosate, glufosinate, agriculturally acceptable salts of glufosinate and combinations thereof) with at least one auxin herbicide, oil or oil ester and a polymer emulsifier. Optionally, a defoamer may be added to inhibit the formation of foam during mixing. Suitable defoamers include, but are not limited to, polysiloxane defoamers, such as SAG 1572 purchased from Momentive. Other herbicides may be present in the herbicidal composition concentrate in an amount (acid equivalent weight) as described herein, such as, by weight of the composition, from about 15% to about 60%.

[0141] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims.

[0142] Example

[0143] The following non-limiting examples are provided to further illustrate the present invention. It should be noted that the composition examples below are presented based on the components initially combined to form the reported tank mix or concentrate. The various embodiments of the present invention are intended to encompass such initial compositions as well as any corresponding compositions resulting from the interaction between the components when combined, such as the case where a monocarboxylate salt is formed in situ by combining a monocarboxylic acid with a neutralizing base.

[0144] Example 1 - Preparation of glycerol ethoxylate-4-ricinoleate

[0145] 100g (about 0.1mol) of glycerol ethoxylate (Mn~1000) (product 441864, obtained from MilliporeSigma) is placed in a 3-necked, vacuum-dried 500-ml flask equipped with a stirring rod and preheated in an 80°C oven under flowing nitrogen. The flask is transferred to a 110°C oil bath, and the septum pierced by a needle, a pressure-balancing funnel, and a right-angle hose connection adapter (serving as an outlet for nitrogen purge gas) open to the atmosphere are connected to the neck of the flask. A gentle nitrogen stream is started by a needle and kept stirring for 10 minutes. 2g of 25% sodium methoxide in methanol is added, and 125g of ricinoleic acid methyl ester (4 equivalents) (product R0029, obtained from TCI Chemicals) is started to be added dropwise. After the addition is completed (1 hour), stirring is continued for another 30 minutes, then 1g of acetic acid is added and the product is collected. The product is a light yellow translucent liquid with low viscosity.

[0146] The glycerol ethoxylate-4-ricinoleate product was characterized by matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). 10 microliters of each glycerol ethoxylate-4-ricinoleate product and matrix solution from Example 1 were combined in a microcentrifuge tube, and 1 microliter was spotted into a well of a MALDI-MS sample plate. The matrix solution consisted of 10 g / L α-cyano-4-hydroxycinnamic acid (CHCA), 10 mM NaCl, and 0.1% trifluoroacetic acid in 50% acetonitrile. The samples and standard peptides used for mass calibration were analyzed on an AB SCIEX TOF / TOF5800 MALDI-MS / MS mass spectrometer. The resulting mass spectrum is shown in Figure 1A and 1BIn. The spectrum of the glycerol ethoxylate starting material with NaCl matrix is ​​composed of a series of peaks separated by 44 mass units (mass of ethylene oxide monomer). The maximum peak is observed at mass 995.5 daltons, corresponding to the sodium adduct of glycerol with 20 EO units. As expected, the mass of glycerol ethoxylate-4-ricinoleate is larger, and also has most of the peaks separated by 44 mass units. The maximum peak observed corresponds to the glycerol ethoxylate with 18,19 and 20 EO functionalized with a ricinoleate unit, but the cluster with two ricinoleate units (20,21 and 22EO) and three ricinoleate (22,23 and 24EO) is also significant.

[0147] Example 2 - Preparation of Glyceryl Ethoxylate-7-Ricinoleate

[0148] The procedure of Example 1 was repeated to add the first four ricinoleic acid ester units. Then another 3 equivalents (94 g) were added over 30 minutes and then stirred for another 30 minutes. The product was a low viscosity liquid similar to 4-ricinoleic acid ester condensate.

[0149] Example 3 - Condensation of PEG 6000 with 6 equivalents of methyl ricinoleate

[0150] 180g of PEG, 6000mol wt. (0.03mol) (commercially available from Millipore Sigma) is added to a 500ml 3-necked vacuum-dried round-bottom flask equipped with a stirring bar and placed in a 90°C oven to melt the PEG. The flask is transferred to a 110°C oil bath, and a septum pierced by a needle, a pressure-equalizing funnel, and a right-angle hose connection adapter (serving as an outlet for nitrogen purge gas) open to the atmosphere are connected to the neck of the flask. A gentle nitrogen flow is started through the needle, and stirring is maintained for 10 minutes while the PEG reaches temperature. At this point, 2g of 25% sodium methoxide in methanol (available from MilliporeSigma) is added.

[0151] In 30 minutes, 56 g of ricinoleic acid methyl ester (6 equivalents) (product R0029, available from TCI Chemicals) was added dropwise and stirring continued for another 70 minutes. The product was a clear liquid with some suspended white waxy pieces. After standing overnight at room temperature, the product solidified into a white waxy substance.

[0152] Example 4 - Condensation of PEG 8000 with 6 equivalents of methyl ricinoleate

[0153] Follow the same procedure as in Example 3, except that the oil bath temperature is increased to 150°C due to the higher melting point of PEG 8000 (commercially available from Millipore Sigma). 160g of PEG 8000 (0.02mol) is kept overnight in a round-bottomed flask at 100°C baking ovens under nitrogen to melt PEG. The flask is then transferred to an oil bath. According to the procedure in Example 3, methyl ricinoleate was added to be reduced to 37.5g (6 equivalents) in 70 minutes, and 25% of the sodium methoxide was reduced to 1g due to the increase in PEG molecular weight. Before collecting the product, 1g of acetic acid was added to quench the methoxide catalyst. The product is a clear liquid that solidifies into a hard white solid after cooling.

[0154] Example 5 - MEA Dicamba Formulation with Soybean Oil, PEG-Ricinoleate Emulsifier, and High Levels of Potassium Acetate ("Vaporgrip TM ”)

[0155] The PEG-6000-6-ricinoleate obtained in Example 3 was dissolved in soybean oil, and a stock solution of dicamba monoethanolamine (MEA) salt having an acid equivalent dicamba concentration of 55% was prepared. The formulation was 26% dicamba on an acid equivalent basis, containing 1.89 moles of potassium acetate / mole dicamba to control volatility.

[0156] The following formulations having the compositions shown in Table 1 were prepared by combining the components and mixing for about 10 minutes followed by agitation with an Ika-Turrax T25 high shear rotor-stator mixer operated at a minimum of 15,000 rpm.

[0157] Table 1

[0158] MEA dicamba, 55% ae solution 47.3％ Acetic acid 14.1％ Potassium hydroxide, 45% wt / wt 27.8％ Crodafos O3A 0.5％ PEG-6000-6-Ricinoleate from Soybean Oil 5.5％ Toximul 8243 1.0％ Deionized water 3.8％

[0159] Variants of the formulation were prepared with 1%, 2% and 4% PEG-6000-6-ricinoleate in soybean oil, as well as a comparative formulation with soybean oil alone. These formulations were used for the spray particle size studies in Example 6.

[0160] Example 6 - Spray Particle Size of Tank Mix with Roundup Powermax

[0161] Tank mixes 1, 2, and 3 shown in Table 2 were prepared from the dicamba formulation of Example 5 and Roundup Powermax in tap water to provide a spray rate of 560 / 1260 g acid equivalent / hectare of dicamba / glyphosate, assuming a spray rate of 15 gallons (56.7812 liters) per acre (0.404686 ha). A tank mix of Roundup Xtendimax (a diglycolamine dicamba formulation without a built-in drift retarder) and Powermax was used as a control (control tank mix).

[0162] The mixture was sprayed with two nozzles (Wilger UR11004 at 50 psi and Wilger DR11005 at 40 psi) in a spray particle size measurement system that recirculated the tank mixture. Spray particle size was measured using a Malvern Spraytec laser diffraction spray particle sizer. The volume percentage of the spray consisting of "driftable fines" defined as droplets with a diameter below 150 μm is a widely accepted measure of the drift tendency of agricultural sprays.

[0163] Table 2 below shows the fines percentage for these spray mixtures. Inclusion of soybean oil in the formulation greatly reduced drift, and increasing the level of PEG-6000-6-ricinoleate improved the performance of the soybean oil drift retarder using both nozzles.

[0164] Table 2 Volume % <150 μm of 26% ae dicamba formulation with soybean oil containing PEG-6000-6-ricinoleate (tank mixes 1-3) tank mixed with Roundup Powermax I at 560 g / ha ae, 15 gal / acre spray

[0165]

[0166] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system and performing any incorporated method. The patentable scope of the invention is defined by the claims, and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements that are insubstantially different from the literal language of the claims.

Claims

1. A herbicidal composition concentrate comprising: (a) at least one herbicide present in an amount greater than or equal to 5% by weight of the composition concentrate, acid equivalent weight, wherein the at least one herbicide comprises an auxinic herbicide, wherein the auxinic herbicide is selected from the group consisting of dicamba, agriculturally acceptable salts of dicamba, agriculturally acceptable esters of dicamba, 2,4-D, agriculturally acceptable salts of 2,4-D, agriculturally acceptable esters of 2,4-D, and combinations thereof; (b) oil or an ester of such oil; and (c) a polymer emulsifier polyethylene glycol (PEG)-polyricinoleate, wherein the polyethylene glycol (PEG)-polyricinoleate corresponds in structure to Formula C: Where j=50-250 and s+r=2-10.

2. The herbicidal composition concentrate according to claim 1, wherein the at least one herbicide is present in an amount of 5% to 50% by weight of the composition concentrate, acid equivalent weight.

3. The herbicidal composition concentrate according to claim 1 or 2, wherein the auxin herbicide is an agriculturally acceptable salt of dicamba, wherein the salt is selected from N,N-[aminopropyl]methylamine salt, monoethanolamine salt, dimethylamine salt, isopropylamine salt, diglycolamine salt, potassium salt, sodium salt, and combinations thereof.

4. The herbicidal composition concentrate according to claim 1 or 2, wherein the oil or the ester of the oil is present in an amount greater than or equal to 1.5% by weight of the composition concentrate.

5. The herbicidal composition concentrate according to claim 1 or 2, wherein the oil or the ester of the oil is a vegetable oil, an ester of a vegetable oil or a petroleum-based oil.

6. The herbicidal composition concentrate according to claim 1 or 2, wherein the oil or the ester of the oil is selected from the group consisting of soybean oil, esters of soybean oil, canola oil, esters of canola oil, palm oil, esters of palm oil, rapeseed oil, esters of rapeseed oil, sunflower oil, esters of sunflower oil, corn oil, esters of corn oil, peanut oil, esters of peanut oil, sesame oil, esters of sesame oil, olive oil, esters of olive oil, and combinations thereof.

7. The herbicidal composition concentrate according to claim 1 or 2, wherein the polymer emulsifier is present in an amount greater than or equal to 0.2% by weight of the composition concentrate.

8. The herbicidal composition concentrate according to claim 1 or 2, further comprising a surfactant selected from the group consisting of phosphoric acid esters, alkyl polysaccharides, alkoxylated castor oils and combinations thereof.

9. The herbicidal composition concentrate according to claim 1 or 2, further comprising at least one monocarboxylic acid or a monocarboxylate thereof.

10. The herbicidal composition concentrate according to claim 9, wherein the at least one monocarboxylic acid or monocarboxylate salt thereof is present in an amount of 5% to 30% by weight of the composition concentrate, acid equivalent weight.

11. The herbicidal composition concentrate according to claim 9 or claim 10, wherein the molar ratio of the at least one monocarboxylic acid or its monocarboxylate to the auxin herbicide is from 3:10 to 10:

1.

12. The herbicidal composition concentrate according to claim 9 or 10, wherein the monocarboxylic acid is acetic acid or the monocarboxylate is potassium acetate.

13. The herbicidal composition concentrate according to claim 1 or 2, wherein the at least one herbicide further comprises a herbicide selected from the group consisting of glyphosate, agriculturally acceptable salts of glyphosate, glufosinate, agriculturally acceptable salts of glufosinate, and combinations thereof.

14. The herbicidal composition concentrate according to claim 1 or 2, wherein the composition concentrate is an emulsion or a microemulsion.

15. A method for preparing a herbicidal composition concentrate, the method comprising: mixing at least one herbicide with an oil or an ester of said oil and a polymer emulsifier to form a herbicidal composition concentrate, wherein the at least one herbicide is mixed in an amount greater than or equal to 5% by weight of the composition concentrate, acid equivalent weight, and the at least one herbicide comprises an auxinic herbicide, wherein the auxinic herbicide is selected from the group consisting of dicamba, agriculturally acceptable salts of dicamba, agriculturally acceptable esters of dicamba, 2,4-D, agriculturally acceptable salts of 2,4-D, agriculturally acceptable esters of 2,4-D, and combinations thereof; The polymer emulsifier is polyethylene glycol (PEG)-polyricinoleate, wherein The polyethylene glycol (PEG)-polyricinoleate corresponds in structure to Formula C: Where j=50-250 and s+r=2-10.

16. The method of claim 15, wherein the oil or ester of the oil is mixed with the polymeric emulsifier to form a first mixture, and the at least one herbicide is mixed with the first mixture to form the herbicidal composition concentrate.

17. The method according to claim 15 or 16, wherein the composition concentrate comprises the at least one herbicide in an amount of 5% to 50% by weight, acid equivalent weight.

18. The method of claim 15 or 16, wherein the auxin herbicide is an agriculturally acceptable salt of dicamba, wherein the salt is selected from N,N-[aminopropyl]methylamine salts, monoethanolamine salts, dimethylamine salts, isopropylamine salts, diglycolamine salts, potassium salts, sodium salts, and combinations thereof.

19. The method of claim 15 or 16, further comprising mixing the at least one herbicide with water to form an aqueous solution prior to mixing with the oil or ester of the oil and the polymer emulsifier.

20. The method of claim 15 or 16, wherein the composition concentrate comprises the oil or the ester of the oil in an amount greater than or equal to 1.5% by weight of the composition concentrate.

21. The method of claim 15 or 16, wherein the oil or the ester of the oil is a vegetable oil, an ester of a vegetable oil, or a petroleum-based oil.

22. The method of claim 15 or 16, wherein the oil or the ester of the oil is selected from the group consisting of soybean oil, esters of soybean oil, canola oil, esters of canola oil, palm oil, esters of palm oil, rapeseed oil, esters of rapeseed oil, sunflower oil, esters of sunflower oil, corn oil, esters of corn oil, peanut oil, esters of peanut oil, sesame oil, esters of sesame oil, olive oil, esters of olive oil, and combinations thereof.

23. The method of claim 15 or 16, wherein the composition concentrate comprises the polymeric emulsifier in an amount greater than or equal to 0.2% by weight of the composition concentrate.

24. The method of claim 15 or 16, further comprising mixing at least one surfactant with the at least one herbicide, the oil or ester of the oil, and the polymeric emulsifier, wherein the surfactant is selected from the group consisting of phosphate esters, alkyl polysaccharides, alkoxylated castor oils, and combinations thereof.

25. The method of claim 15 or 16, further comprising mixing at least one monocarboxylic acid or a monocarboxylate salt thereof with the at least one herbicide, the oil or an ester of the oil, and the polymeric emulsifier.

26. The method of claim 25, wherein the composition concentrate comprises the at least one monocarboxylic acid or monocarboxylate salt thereof in an amount of 5% to 30% by weight of the composition concentrate, acid equivalent weight.

27. The method of claim 25 or claim 26, wherein the molar ratio of the at least one monocarboxylic acid or monocarboxylate thereof to the auxin herbicide is from 3:10 to 10:

1.

28. The method of claim 26 or 27, wherein the monocarboxylic acid is acetic acid or the monocarboxylate salt is potassium acetate.

29. The method of claim 15 or 16, wherein the at least one herbicide further comprises a herbicide selected from the group consisting of glyphosate, agriculturally acceptable salts of glyphosate, glufosinate, agriculturally acceptable salts of glufosinate, and combinations thereof.

30. The method of claim 15 or 16, wherein the composition concentrate formed is an emulsion or a microemulsion.

31. A herbicidal composition concentrate comprising: (a) at least one herbicide present in an amount greater than or equal to 5% by weight of the composition concentrate, acid equivalent weight, wherein the at least one herbicide comprises an auxinic herbicide, wherein the auxinic herbicide is selected from the group consisting of dicamba, agriculturally acceptable salts of dicamba, agriculturally acceptable esters of dicamba, 2,4-D, agriculturally acceptable salts of 2,4-D, agriculturally acceptable esters of 2,4-D, and combinations thereof; (b) oil or an ester of such oil; and (c) a polymeric emulsifier comprising glycerol ethoxylate-polyricinoleate corresponding in structure to Formula A: Where i+j+k=10-50 and r+s+t=3-12.

32. A herbicidal composition concentrate comprising: (a) at least one herbicide present in an amount greater than or equal to 5% by weight of the composition concentrate, acid equivalent weight, wherein the at least one herbicide comprises an auxinic herbicide, wherein the auxinic herbicide is selected from the group consisting of dicamba, agriculturally acceptable salts of dicamba, agriculturally acceptable esters of dicamba, 2,4-D, agriculturally acceptable salts of 2,4-D, agriculturally acceptable esters of 2,4-D, and combinations thereof; (b) oil or an ester of such oil; and (c) a polymeric emulsifier comprising glycerol ethoxylate-poly-(12-hydroxystearate) corresponding in structure to Formula B: Where i+j+k=10-50 and r+s+t=3-12.

33. A herbicidal composition concentrate comprising: (a) at least one herbicide present in an amount greater than or equal to 5% by weight of the composition concentrate, acid equivalent weight, wherein the at least one herbicide comprises an auxinic herbicide, wherein the auxinic herbicide is selected from the group consisting of dicamba, agriculturally acceptable salts of dicamba, agriculturally acceptable esters of dicamba, 2,4-D, agriculturally acceptable salts of 2,4-D, agriculturally acceptable esters of 2,4-D, and combinations thereof; (b) oil or an ester of such oil; and (c) a polymeric emulsifier comprising polyethylene glycol (PEG)-polyricinoleate corresponding in structure to Formula C: Where j=50-250 and s+r=2-10.

34. A herbicidal composition concentrate comprising: (a) at least one herbicide present in an amount greater than or equal to 5% by weight of the composition concentrate, acid equivalent weight, wherein the at least one herbicide comprises an auxinic herbicide, wherein the auxinic herbicide is selected from the group consisting of dicamba, agriculturally acceptable salts of dicamba, agriculturally acceptable esters of dicamba, 2,4-D, agriculturally acceptable salts of 2,4-D, agriculturally acceptable esters of 2,4-D, and combinations thereof; (b) oil or an ester of such oil; and (c) a polymeric emulsifier comprising PEG-poly-(12-hydroxystearate) corresponding in structure to Formula D: Where j=50-250 and s+r=2-10.

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