US20120142532A1 - Low volatility auxin herbicide formulations - Google Patents

Low volatility auxin herbicide formulations Download PDF

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US20120142532A1
US20120142532A1 US13/389,864 US201013389864A US2012142532A1 US 20120142532 A1 US20120142532 A1 US 20120142532A1 US 201013389864 A US201013389864 A US 201013389864A US 2012142532 A1 US2012142532 A1 US 2012142532A1
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dicamba
formulation
auxin
herbicide
salt
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Daniel R. Wright
Eric J. Roskamp
Ronald J. Brinker
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Monsanto Technology LLC
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Monsanto Technology LLC
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the present invention generally relates to low volatility auxin herbicide formulations.
  • Auxin herbicides have proven to be effective and highly beneficial for control of unwanted plants.
  • Auxin herbicides include 2,4-D (2,4-dichlorophenoxyacetic acid), 2,4-DB (4-(2,4-dichlorophenoxy)butanoic acid), dichloroprop (2-(2,4-dichlorophenoxy)propanoic acid), MCPA ((4-chloro-2-methylphenoxy)acetic acid), MCPB (4-(4-chloro-2-methylphenoxy)butanoic acid), aminopyralid (4-amino-3,6-dichloro-2-pyridinecarboxylic acid), clopyralid (3,6-dichloro-2-pyridinecarboxylic acid), fluoroxypyr ([(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid), triclopyr ([(3,5,6-trichloro-2-pyridinyl)oxy]acetic acid), di
  • Volatility and drift problems are commonly associated with auxin herbicides. Volatile auxin herbicides can, under certain conditions of application, vaporize into the surrounding atmosphere and thereby migrate from the application site to adjacent crop plants, such as soybeans and cotton, where contact damage to sensitive plants can occur. Spray drift can be attributed to volatility as well as to the physical movement of small particles, such as spray droplet particles, from the target site to adjacent crop plants.
  • dicamba is absorbed into solid phase natural or synthetic polymers.
  • the resulting particle sizes are typically not suitable for spray application therefore limiting use to granular drop application.
  • Microencapsulation in a polymer shell is also known in the art, but the relatively high solubility of dicamba and its salts precludes successful use of that technology in aqueous suspensions and commercial dicamba microencapsulation products have not been developed.
  • auxin herbicide formulations that are efficacious, yet non-phytotoxic to sensitive crops located in areas adjacent to the target site, and for auxin formulations that are less prone to volatility and physical drift.
  • auxin herbicide formulations exhibiting low volatility and/or drift and methods for their use.
  • the present invention is directed to an aqueous herbicidal solution concentrate formulation useful for killing or controlling the growth of unwanted plants, the formulation comprising a solution comprising an auxin herbicide component consisting essentially of auxin herbicide salts and comprising at least 50 grams acid equivalent per liter of dicamba monoethanolamine salt.
  • the present invention is further directed to an aqueous herbicidal solution concentrate formulation useful for killing or controlling the growth of unwanted plants, the formulation comprising a solution comprising an auxin herbicide component consisting essentially of auxin herbicide salts and comprising at least 550 grams acid equivalent per liter of dicamba potassium salt.
  • the present invention is further directed to an aqueous herbicidal solution concentrate formulation useful for killing or controlling the growth of unwanted plants, the formulation comprising an auxin herbicide component consisting essentially of auxin herbicide salts and comprising at least 50 grams acid equivalent per liter of dicamba diethanolamine salt.
  • the present invention is further directed to low volatility auxin herbicide formulations comprising an auxin herbicide component consisting essentially of an auxin herbicide salt or a mixture of auxin herbicide salts and a polybasic polymer or mixture of polybasic polymers, wherein the formulation is an aqueous solution.
  • the polymer has a molecular weight of from 600 to 3,000,000 Daltons and has a nitrogen content of from 13 to 50 percent by weight
  • the present invention is further directed to a method of using an auxin herbicide to control auxin-susceptible plants growing in and/or adjacent to a field of crop plants.
  • the method comprises diluting a formulation comprising a solution of (i) at least 50 grams acid equivalent per liter of dicamba monoethanolamine salt or dicamba diethanolamine salt or at least 550 grams acid equivalent per liter of dicamba potassium salt with water to provide an aqueous herbicidal application mixture or (ii) forming an aqueous application mixture from a low volatility auxin herbicide formulation comprising an auxin herbicide component consisting essentially of an auxin herbicide salt or a mixture of auxin herbicide salts and a polybasic polymer or mixture of polybasic polymers.
  • the aqueous herbicidal application mixture is applied to the foliage of the auxin-susceptible plants.
  • the present invention is further directed to a method of reducing the volatility of auxin herbicides.
  • the method comprises providing a nitrogen containing polybasic polymer source for use in preparation of an aqueous herbicidal application mixture comprising an auxin herbicide for application to auxin susceptible plants.
  • the auxin herbicide content of said auxin herbicide consists essentially of the salts of one or more auxin herbicide species.
  • the polybasic polymer has a molecular weight from 600 to 3,000,000 Daltons and has a nitrogen content from 10 to 50 percent by weight.
  • the present invention is still further directed to a method for controlling auxin susceptible plants.
  • the method comprises obtaining a nitrogen containing polybasic polymer source comprising at least one polybasic polymer species, wherein the polybasic polymer has an average molecular weight of from 600 to 3,000,000 Daltons and has an average nitrogen content of from 13 to 50 percent by weight and obtaining an auxin herbicide source having a herbicide content consisting essentially of one or more auxin herbicide salt species.
  • the nitrogen containing polybasic polymer source and auxin herbicide source are mixed with water to produce an aqueous auxin application mixture that is applied to the auxin susceptible plants.
  • the present invention is yet further directed to a method of counseling a person responsible for control of auxin susceptible plants.
  • the method comprises (i) identifying an auxin herbicide source to be used in the preparation of an aqueous auxin application mixture, the auxin herbicides contained in said auxin herbicide source consisting essentially of one or more auxin herbicide salt species, (ii) identifying a nitrogen containing polybasic polymer source comprising at least one polybasic polymer species, wherein the polybasic polymer has an average molecular weight of from 600 to 3,000,000 Daltons and has an average nitrogen content of from 13 to 50 percent by weight and (iii) enabling said person to prepare said aqueous auxin application mixture from materials comprising said auxin herbicide source and said nitrogen containing polybasic polymer source for application to said auxin susceptible plants.
  • FIG. 1 is a graph depicting the percent of spray volume for prior art compositions and compositions of the present invention having droplet particle sizes of less than 150 microns and less than 100 microns wherein the prior art and inventive composition solutions contained about 0.56 weight percent acid equivalent dicamba and were sprayed at 165 kPa pressure by means of a flatfan 9501E nozzle.
  • auxin herbicide formulations exhibiting low volatility, controlled droplet particle size, reduced physical and reduced vapor drift are provided.
  • the formulations of the present invention provide enhanced protection from crop injury to auxin tolerant or resistant crops while maintaining comparably effective herbicidal efficacy on unwanted plants located in the target area.
  • auxin herbicide dicamba is made, one skilled in the art will understand that the principles of the present invention apply generally to auxin herbicides, including those described above, and the invention is not limited to dicamba herbicidal formulations.
  • formulations and methods are provided that effectively control auxin herbicide release to give both commercially acceptable weed control and a commercially acceptable rate of crop injury.
  • the formulations provide enhanced crop protection in over the top application to plants.
  • a “commercially acceptable rate of weed control” varies with the weed species, degree of infestation, environmental conditions, and the associated crop plant.
  • commercially effective weed control is defined as least about 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or even greater than 95%.
  • “Weed control,” as used herein, refers to any observable measure of control of plant growth, which can include one or more of the actions of (1) killing, (2) inhibiting growth, reproduction or proliferation, and (3) removing, destroying, or otherwise diminishing the occurrence and activity of plants.
  • Weed control can be measured by any of the various methods known in the art. For example, weed control can be determined as a percentage as compared to untreated plants following a standard procedure wherein a visual assessment of plant mortality and growth reduction is made by one skilled in the art specially trained to make such assessments. In another control measurement method, control is defined as an average plant weight reduction percentage between treated and untreated plants. Preferably, commercial weed control is achieved at no greater than 30 days after treatment (DAT), such as from 18 to 30 DAT.
  • DAT days after treatment
  • a “commercially acceptable rate of crop injury” for the present invention likewise varies with the crop plant species. Typically, a commercially acceptable rate of crop injury is defined less than about 20%, 15%, 10% or even less than about 5%.
  • Crop damage can be measured by any means known in the art, such as those describe above for weed control determination. Preferably, crop damage appears no more than from 10% to 20% at no greater than 30 DAT, such as from 3 to 21 or from 3 to 30 DAT.
  • the auxin-susceptible plants can be weeds or crop plants.
  • Crop plants include, for example, vegetable crops, grain crops, flowers, root crops and sod.
  • Crop plants of the present invention include hybrids, inbreds, and transgenic or genetically modified plants.
  • the crop plants are auxin tolerant species that are not susceptible to auxin herbicides or are a transgenic species that contain an auxin (e.g., dicamba) resistant trait.
  • auxin e.g., dicamba resistant corn, cotton or soybean.
  • Dicamba resistant crops can further comprise one or more additional traits including, without limitation: herbicide resistance (e.g., resistance to other auxin herbicides (e.g., 2,4-D or fluoroxypyr), glyphosate, glufosinate, acetolactate synthase inhibitor herbicides (e.g., imazamox, imazethapyr, imazaquin and imazapic), acetyl CoA carboxylase inhibitors (e.g., sethoxydim and clethodim), etc.); insect resistance such as Bacillus thuringiensis (Bt); high oil; high lysine; high starch; nutritional density; and/or drought resistance.
  • Bt Bacillus thuringiens
  • the weeds and/or crop plants are glyphosate tolerant or contain a glyphosate resistant trait. Examples include glyphosate resistant corn, cotton or soybean.
  • the crop plants comprise stacked traits such as dicamba and glyphosate resistance; dicamba and glufosinate resistance; dicamba and acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) resistance; dicamba, glyphosate and glufosinate resistance; dicamba, glyphosate and ALS or AHAS resistance; dicamba, glufosinate and ALS or AHAS resistance; or dicamba, glyphosate, glufosinate and ALS or AHAS resistance.
  • the plants can additionally include other herbicide, insect and disease resistance traits, as well as combinations of those traits. For instance, the plants can have dicamba, 2,4-D or fluoroxypyr resistant traits.
  • low volatility commercially acceptable formulations of auxin herbicides are achieved by combining 2,4-D, 2,4-DB, dichloroprop, MCPA, MCPB, aminopyralid, clopyralid, fluoroxypyr, triclopyr, diclopyr, mecoprop, mecoprop-P, dicamba, picloram, quinclorac, aminocyclopyrachlor, agriculturally acceptable salts of any of these herbicides, racemic mixtures or resolved isomers thereof, or mixtures thereof (i) in aqueous solution with one or more soluble polybasic polymers such as, for example, a polymeric polyamine and/or (ii) by raising the pH of aqueous solutions thereof.
  • soluble polybasic polymers such as, for example, a polymeric polyamine and/or
  • auxin herbicide salts include, without limitation, sodium, potassium, ammonium, lithium, diammonium, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, dimethylamine, diethylamine, triethylamine, methylamine, ethylamine, diglycolamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine and dodecylamine, and mixtures thereof.
  • the concentration of volatilized auxin herbicide in the vapor phase surrounding a low volatility auxin herbicide formulation comprising an auxin herbicide salt and one or more polybasic polymers is less than the concentration of volatilized auxin herbicide in the vapor phase surrounding a reference formulation formulated in the absence of the polybasic polymer(s), but otherwise having the same formulation as the low volatility auxin herbicide formulation.
  • the concentration of volatilized dicamba herbicide in the vapor phase surrounding the low volatility dicamba herbicide formulations of the present invention comprising a polybasic polymer has been discovered to be less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2 or 0.1 that of the concentration of volatilized dicamba herbicide in the vapor phase surrounding a similarly formulated reference formulation but not containing the polybasic polymer.
  • Volatilization can be measured by means known to those skilled in the art such as by distilling auxin herbicide compositions and analyzing the distillation condensate and/or distilled composition for auxin content.
  • a gas stream can be passed over auxin formulations into which the auxin herbicide volatilizes from the formulation. The gas stream can then be quantitatively analyzed for dicamba content by methods known in the art.
  • polybasic polymers reduce auxin salt volatility because dissociated auxin salt forms ionic bonds with the polybasic polymer and binds the auxin in solution. Any residue from a herbicidal application of the auxin, is therefore inhibited from dissociating to the free acid.
  • the free acid is about 100 times more volatile than bound dicamba acid or salt.
  • additional localization of an auxin in or around the polymer matrix may be achieved through cation-pi complexation. It is known that ammonium salts form stable cation-pi complexes with the pi systems of aromatic rings.
  • the ammonium ions of the polymer can form cation-pi or pi-cation-pi complexes with the auxin. This additional complex interaction may further contribute to reduction in volatilization of the auxin.
  • reduced dicamba volatility in combination with relatively fast dicamba release from the polymer can be achieved by formulating dicamba salts with a polybasic polymer having a relatively weak ion exchange capability. It is believed that low ion exchange capacity polymers retard dicamba salt disassociation to the free acid form thereby reducing volatility, but those polymers do not bind the dicamba strongly enough to retard release rate to an extent that efficacy is reduced. It is further believed that dicamba bound to polymers having relatively strong ion exchange capability would likewise have a reduced volatilization rate as compared to a similarly formulated formulation, but not containing the polymer.
  • polybasic polymers are effective auxin herbicide drift control agents because these polymers, when utilized in aqueous auxin formulations, can reduce the number of spray drops having a diameter of less than about 200 microns, 150 microns, or even 100 microns. It is believed, without being bound to any particular theory, that in addition to reducing auxin volatility, polybasic polymers also function as thickeners or rheological property modifying agents that increase solution viscosity resulting in a greater number of large spray droplet particles in the size distribution and restricting the generation of small droplet particles. For a given velocity, wind will move large droplet particles a shorter distance as compared to smaller droplet particles.
  • an increase in average spray drop size from about 10 microns to about 150 microns can decrease the lateral distance a droplet particle travels in a light wind after normal spraying by about 300 to 500 meters.
  • Spray droplet particle size can be measured by methods known to those skilled in the art such as phase doppler droplet particle analysis (PDPA).
  • PDPA phase doppler droplet particle analysis
  • polybasic polymers having from 4 to about 100,000 nitrogen atoms per molecule, from about 15 to about 100,000 nitrogen atoms per molecule, from about 25 to about 100,000 nitrogen atoms per molecule, from about 50 to about 100,000 nitrogen atoms per molecule, or even from about 100 to about 100,000 nitrogen atoms per molecule, or mixtures of polybasic polymers having an average number of nitrogen atoms within the above ranges, are preferred.
  • an average nitrogen content of from 10% to about 50% by weight, from 13% to about 50%, from 15% to about 50%, from about 20% to about 50%, from about 30% to about 45% by weight, or even about 30% to about 40% by weight is preferred.
  • Examples of typical polymer molecular weights, or average molecular weight for polymer mixtures, (in Daltons) for the practice of the present invention include 600, 800, 1,300, 1,500, 2,000, 2,500, 5,000, 10,000, 20,000, 50,000, 75,000, 100,000, 250,000, 500,000, 750,000, 1,000,000, 1,250,000, 1,500,000, 1,750,000, 2,000,000, 2,250,000, 1,500,000, 1,750,000, 2,000,000, 2,250,000, 2,500,000, 2,500,000 or even 3,000,000, and ranges thereof.
  • Polybasic polymers suitable for the practice of the present invention are preferably hydrophilic and have an aqueous solubility of at least 5% v/v, more preferably at least 10% v/v.
  • Formulations comprising an auxin herbicide salt are generally compatible with polybasic polymers in tank mixes as well as in concentrate formulations.
  • the polybasic polymers of the present invention do not require separate addition into a spray tank.
  • the polybasic polymers of the present invention can be combined with auxin herbicide formulations before use on plants such as by addition to auxin herbicide concentrate compositions or auxin herbicide tank mixes, or by introducing an auxin herbicide composition and a polybasic polymer or polymer combination as separate feed streams to a spraying or application system so that the feed streams are co-mixed immediately prior to use.
  • a weight ratio of dicamba acid equivalent (a.e.) to polybasic polymer or combination of polymers of from 1:100 to about 100:1, from about 1:50 to about 50:1, from about 1:1 to about 100:1, from about 1:1 to about 50:1, from about 1:1 to about 25:1, from about 1:1 to about 10:1, from about 3:1 to about 10:1 or from about 5:1 to about 10:1 is preferred.
  • formulations contain from about 1% to about 10% v/v total polybasic polyamine and from about 360 to about 750, from about 400 to about 750, from about 450 to about 750, from about 460 to about 750, from about 470 to about 750, from about 480 to about 750, from about 490 to about 750, or from about 500 to about 750 grams a.e. per liter (g a.e./L) dicamba.
  • auxin herbicide salts are generally preferred as compared to the acid form for combination with polybasic polymers. Suitable cations for auxin herbicide salts include, for example and without restriction, DMA, MEA, DEA, triethanolamine (TEA), potassium, sodium, IPA and DGA. In some embodiments of the present invention, the auxin herbicide component of the formulation consists essentially of auxin herbicide salts.
  • MEA, DEA and potassium dicamba are preferred because they are believed to be compatible with polybasic polymers such as polymeric polyamines, such that high concentrations in aqueous solution can be achieved while volatility is low as compared to other dicamba salt formulations that do not contain the polymer and without requiring the pH of the formulation to be 9 or greater.
  • dicamba low volatility can be achieved by formulating dicamba as the monoethanolamine or diethanolamine salt.
  • MEA and diethanolamine (DEA) salts of dicamba are less volatile than other dicamba salts, such as the DMA and IPA salts, known in the art.
  • the concentration of volatilized dicamba in the vapor phase surrounding the aqueous dicamba MEA or DEA concentrate formulation is less than the concentration of volatilized dicamba in the vapor phase surrounding a reference formulation formulated from dicamba salts known in the art such as dimethylamine dicamba, isopropylamine dicamba, or mixtures thereof, but otherwise having the same composition as the dicamba MEA concentrate formulation.
  • dicamba salts having relatively volatile cations such as or IPA
  • concentration of volatilized dicamba herbicide in the vapor phase surrounding an MEA dicamba formulation has been discovered to be from 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or ranges thereof, that of the concentration of volatilized dicamba herbicide in the vapor phase surrounding similarly formulated IPA dicamba.
  • the amount of dicamba volatilizing from an aqueous solution of the sodium, potassium, MEA or DEA salt can also be a function of pH, with volatilization varying inversely with pH.
  • dicamba volatility decreases with increasing pH.
  • HA pKa+log [HA/A ⁇ ]
  • MEA salt of dicamba provides higher aqueous solubility and lower viscosity as compared to dicamba acid and other dicamba salts known in the art, such as the dimethylamine (DMA) and isopropylamine (IPA) salts.
  • DMA dimethylamine
  • IPA isopropylamine
  • MEA salt aqueous solubility at 20° C. is about 66.1 weight percent a.e. (wt % a.e.), or about 885 grams acid equivalent per liter (g a.e./L) as compared to 54.6 wt % a.e.
  • DMA salt of dicamba is believed to have a solubility at 20° C. of about 45 wt % a.e. (600 g a.e./L).
  • MEA, potassium and DEA dicamba tank mix formulations are provided.
  • the tank mix formulations preferably comprise from about 0.1 to about 50 g a.e./L, such as 0.1, 0.5, 1, 5, 10, 25 or 50 g a.e./L, and ranges thereof.
  • MEA dicamba concentrate formulations are provided.
  • the concentrate formulations preferably comprise at least 50 g a.e./L, such as from about 50 to about 885, from about 100 to about 885, from about 200 to about 885, from about 300 to about 885, from about 400 to about 885, from about 500 to about 885, from about 550 to about 885, or from about 600 to about 885 g a.e./L MEA dicamba.
  • 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850 or 885 g a.e./L and ranges thereof.
  • potassium dicamba concentrate formulations are provided.
  • the concentrate formulations preferably comprise at least 550 g a.e./L, such as from about 550 to about 720, or from about 600 to about 720 g a.e./L potassium dicamba.
  • DEA dicamba concentrate formulations are provided.
  • the concentrate formulations preferably comprise at least 50 g a.e./L, from about 50 to about 720, from about 100 to about 720, from about 200 to about 720, from about 300 to about 720, from about 400 to about 720, from about 500 to about 720, from about 550 to about 720, or from about 600 to about 720 g a.e./L DEA dicamba.
  • mixed dicamba salt compositions comprising at least one of the MEA, DEA or potassium salt are provided.
  • suitable salts include the sodium, ammonium, lithium, diammonium, triethanolamine, triisopropanolamine, DMA, diethylamine, triethylamine, methylamine, ethylamine, DGA, propylamine (such as IPA or n-propyl), butylamine, pentylamine, hexylamine, heptylamine, octylamine, dodecylamine and decylamine dicamba salts.
  • the mixed salts include two or more dicamba salts selected from the MEA, DEA, sodium, potassium, IPA, DGA and DMA salts, wherein at least one salt is the MEA, DEA or potassium salt of dicamba.
  • the total dicamba concentration for the mixed salt compositions on an acid equivalent basis is at least about 52.5, 100, 150, 200, 250, 300, 350, 400, 450, 480, 500, 520, 540, 560, 575, 580, 600, 620, 640, 660, 680 or 700 grams per liter, and ranges thereof.
  • a minimum ratio of the dicamba salts i.e. a lower limit from the upper limit of 20:1 that is necessary to achieve the objects of the invention in view of the other components of the formulation, such as a co-herbicide component, polybasic polymer component and/or surfactant component and their respective concentrations.
  • MEA dicamba concentrate formulations are only moderately irritating to eyes at a pH of about 8. Eye irritation measurement can be done according to the methods provided in U.S. Environmental Protection Agency Office of Prevention, Pesticides and Toxic Substances, Health Effects Test Guidelines (for example, OPPTS 870.2400 Acute Eye Irritation, August 1998).
  • MEA dicamba formulations are generally classified in the eye irritation (rabbit) FIFRA (Federal Insecticide, Fungicide and Rodenticide Act) category III (moderate irritation).
  • the polybasic polymer is a polymeric polyamine, polymeric polyimine, nitrogen-substituted vinyl polymer, polyoxazoline, polymeric polypeptide, polymeric polyamide, polypropyleneimine dendrimer, polyethyleneimine dendrimer or a polyamidoamine dendrimer. Combinations thereof are also within the scope of the present invention.
  • the polybasic polymer is a polymeric polyamine.
  • Polymeric polyamines include, for instance, polyethyleneimines, polyalkoxylated polyamines, and combinations thereof.
  • Particular polymeric polyamines include benzylated polyamines, ethoxylated polyamines, propoxylated polyamines, alkylated polyamines, esterified polyamines and combinations thereof.
  • the polymeric polyamines have structure (1):
  • R 1 is preferably independently hydrogen or an alkyl having from 1 to 12 carbon atoms
  • R 2 is preferably independently ethylene or C 6 arylene
  • R 3 is preferably independently hydrogen or an alkyl having from 1 to 4 carbon atoms
  • x is preferably selected to give a linear polyimine having a molecular weight of from 600 to 3,000,000 Daltons.
  • polymeric polyamines include polyaniline wherein R 2 is C 6 arylene and R 3 is hydrogen and polyethylene imine) wherein R 2 is ethylene and R 3 is hydrogen
  • the polymeric polyamine is a polymeric polyimine compound (hereafter referred to as “polyimines”) selected from linear polyimines and branched polyimines having a molecular weight of from about 800 to about 3,000,000 Daltons.
  • polyimines a polymeric polyimine compound selected from linear polyimines and branched polyimines having a molecular weight of from about 800 to about 3,000,000 Daltons.
  • Linear polyimines typically have structure (2):
  • each R 10 is independently hydrogen, a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms or an aryl group; each R 20 is independently an alkylene having from 1 to 4 carbon atoms; each R 30 is independently hydrogen or a hydrocarbyl having from 1 to 4 carbon atoms wherein R 30 substitution occurs at any of the R 20 carbon atoms; and x is a degree of polymerization of from about 1 to about 70,000.
  • R 10 is preferably independently hydrogen or an alkyl having from 1 to 12 carbon atoms
  • R 20 is preferably ethylene
  • R 30 is preferably independently hydrogen or an alkyl having from 1 to 4 carbon atoms
  • x is preferably selected to give a linear polyimine having a molecular weight of from 800 to 3,000,000 Daltons.
  • Branched polyimines typically have structure (3):
  • each R 10 is independently hydrogen, a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms or an aryl group; each R 20 is independently an alkylene having from 1 to 4 carbon atoms; and y is a degree of polymerization of from about 1 to about 70,000.
  • Each R 30 is independently hydrogen or an amine of formula (4):
  • R 30 is of formula (4) and wherein R 40 is an alkylene having from 1 to 4 carbon atoms, and R 41 and R 42 are independently selected from hydrogen, a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms, and an amine of formula (5):
  • R 50 is an alkylene having from 1 to 4 carbon atoms
  • R 51 and R 52 are independently selected from hydrogen and a hydrocarbyl or substituted hydrocarbyl having from 1 to 20 carbon atoms, and each z is independently from 0 to 5.
  • R 50 is preferably ethylene
  • R 51 and R 52 are preferably independently hydrogen or a hydrocarbyl having from 1 to 12 carbon atoms.
  • the sum of y and z are preferably selected to give a branched polyimine having a molecular weight of from 800 to 3,000,000 Daltons.
  • polymeric polyimines are also included within the scope of polymeric polyimines. Also included within the scope of polymeric polyimines:
  • each R 60 is independently hydrogen, a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms or an aryl group; each R 61 is independently hydrogen or a hydrocarbyl having from 1 to 6 carbon atoms; and x is a degree of polymerization of from about 1 to about 70,000 selected to yield a molecular weight of from 600 to 3,000,000 Daltons.
  • polyimines and polymeric polyimines include, but are not limited to, compounds of structures (7) and (8):
  • Formula (8) is generally representative of Lupasol® polyimine polymers available from BASF.
  • Epomin® is commercially available from Aceto Corp.
  • MW refers to the average molecular weight in Daltons
  • Viscosity refers to viscosity in mPa at 20° C.
  • Pour Pt refers to the pour point in ° C.
  • Density refers to the density in grams per mL measured at 20° C.
  • Rao refers to the ratio of primary:secondary:tertiary amine nitrogens:
  • polyalkylenimines can be functionalized by reaction with one or more alkylene oxides to form the hydroxyalkylated derivative.
  • a hydroxyalkylated derivative may be prepared by heating an aqueous solution of polyalkylenimine with the desired amount of alkylene oxide at a temperature of about 80° C. to about 135° C., optionally in the presence of an alkali metal catalyst such as sodium methoxide, potassium tert-butoxide, potassium or sodium hydroxide.
  • the polyalkylenimine is functionalized by reaction with ethylene oxide and/or optionally propylene oxide.
  • the polyalkylenimine is functionalized by reaction with about 1 to about 100 molar equivalents of ethylene oxide per ethylene unit in the polyalkylenimine. In still other embodiments, the polyalkylenimine is functionalized by reaction with about 1 to about 100 molar equivalents of ethylene oxide and about 1 to about 100 molar equivalents of propylene oxide per ethylene unit in the polyalkylenimine. In yet other embodiments, the polyalkylenimine is reacted first with the propylene oxide and subsequently with the ethylene oxide. For example, in some embodiments, the polyalkylenimine is functionalized by reaction with about 5 to about 25 molar equivalents of ethylene oxide and about 85 to about 98 molar equivalents of propylene oxide per ethylene unit in the polyalkylenimine.
  • Examples of commercial oxyalkylated polyalkylenimines include Lupasol SC-61B and Lupasol SK (available from BASF), and Kernelex 3550X, 3423X, 3546X, D600 and 3582X (available from Uniquema, New Castle, Del., USA).
  • Lupasol SC-61B is believed to be a hydroxylated (ethoxylated) polyethylenimine of formula (9):
  • R 90 is hydrogen or a continuation of the polymer chain and x is a value required to yield a molecular weight of about 110,000 Daltons.
  • the polybasic polymers are dendritic polymers (for example, starburst polymers), characterized as repeatedly branched molecules having attached functional groups distributed on the periphery of the branches thereby providing a highly functionalized surface.
  • dendritic polymers are polypropyleneimine dendrimers, polyethyleneimine dendrimers, and polyamidoamine dendrimers.
  • a molecular weight of from about 1000 to about 1,000,000 is preferred, representing from 1 to about 10 generation growth steps.
  • the polybasic polymer is a nitrogen-substituted vinyl polymer.
  • Vinyl polymers include polyvinyl acrylamides of formula (10):
  • each R 100 is independently hydrogen, a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms or an aryl group;
  • R 101 is a nitrogen-containing moiety; and
  • x is a degree of polymerization of from about 1 to about 70,000.
  • R 101 is acrylamide (—C(O)NH 2 ), allylamine (—CH 2 NH 2 ), pyridine, pyrazine, pyrazole or pyrazoline.
  • the polyacrylamides can comprise cationic monomers such as, for example, dimethyl aminoethyl acrylate methyl chloride, dimethyl aminoethyl methacrylate methyl chloride, acrylamidopropyl trimethyl ammonium chloride, methacryl amodopropyl trimethyl ammonium chloride, and diallyl dimethyl ammonium chloride.
  • cationic monomers such as, for example, dimethyl aminoethyl acrylate methyl chloride, dimethyl aminoethyl methacrylate methyl chloride, acrylamidopropyl trimethyl ammonium chloride, methacryl amodopropyl trimethyl ammonium chloride, and diallyl dimethyl ammonium chloride.
  • vinyl polymers include poly(vinyl pyridine), depicted in formula (12) comprising the monomer poly(2-vinyl pyridine):
  • the polybasic polymer is a polyamide.
  • Polyamide polymers include polymeric acrylamides comprising the repeating unit of general formula (14):
  • each R 140 is independently hydrogen or a hydrocarbyl having from 1 to 6 carbon atoms
  • each R 141 is independently alkylene having from 1 to 8 carbon atoms or arylene
  • each r is independently 0 or 1
  • x is a degree of polymerization of from about 1 to about 70,000.
  • polyamide polymers examples include polyisocyanates comprising the repeating unit of formula (15):
  • m is from 1 to 6.
  • the polybasic polymer material is a polyoxazoline comprising the repeating unit of formula (17):
  • R 170 is a substituted or unsubstituted alkylene group containing 1 to about 4 carbon atoms; R 171 is a hydrocarbyl or substituted hydrocarbyl that does not significantly decrease the water-solubility of the polymer; and n is an integer which provides the polymer with a molecular weight of from 600 to 3,000,000 Daltons.
  • R 170 may be substituted with hydroxy, amide or polyether.
  • R 170 is preferably methylene, ethylene, propylene, isopropylene or butylene.
  • R 170 is most preferably ethylene.
  • R 171 is preferably alkyl or aryl; R 171 may be substituted with hydroxy, amide or polyether.
  • R 171 is methyl, ethyl, propyl, isopropyl, butyl, or isobutyl.
  • R 170 is ethylene and R 171 is ethyl.
  • the polybasic polymer is a polymeric polypeptide (poly ⁇ -amino acid) comprising the repeating unit of formula (18):
  • each R 180 is independently selected from a side chain specific to amino acids, indicated in parentheses below.
  • R 180 may be hydrogen (glycine), —CH 3 (alanine), —CH(CH 3 ) 2 (valine), —CH 2 CH(CH 3 ) 2 (leucine), —CH(CH 3 )(CH 2 CH 3 ) (isoleucine), —(CH 2 ) 4 NH 2 (lysine), —CH 2 OH (serine), —CH(OH)(CH 3 ) (threonine), etc.
  • x is selected to provide a molecular weight between 600 and 3,000,000 Daltons.
  • polar R 180 groups are preferred to provide greater water solubility.
  • Polar amino acids include arginine, aspargine, aspartic acid, cysteine (slightly polar), glutamic acid, glutamine, histidine, lysine, serine, threonine, tryptophan (slightly polar) and tyrosine.
  • Any of the polymers described above for formulae (7) through (18) can be terminated with a head group independently selected from hydrogen, a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms or an aryl group.
  • surfactants can optionally be used in auxin herbicide formulations to effectively enhance herbicidal effectiveness.
  • solubilizers can be optionally be used to enhance polybasic polymer aqueous solubility.
  • a compound can function as both an efficacy enhancer and a solubilizer.
  • auxin herbicide component i.e., a high weight ratio of auxin a.e. to surfactant, for example in excess of about 20:1
  • such compounds may enhance polybasic polymer solubility but not effectively provide herbicidal efficacy enhancement.
  • at higher concentrations relative to the auxin herbicide component such compound may both enhance herbicidal efficacy and polyamine polymer solubility.
  • dicamba auxin
  • Surfactants are optionally included in auxin (dicamba) formulations to facilitate dicamba retention, uptake and translocation into the plant foliage and thereby enhance herbicidal effectiveness. It has been discovered that the polymeric polyamines of the present invention are at least as effective as surfactants for foliar retention, uptake and translocation of dicamba. Efficacious dicamba formulations containing polymeric polyamines or other polybasic polymers, with or without a surfactant, are therefore within the scope of the present invention.
  • one or more herbicidal efficacy enhancing surfactants known in the art can optionally be formulated with dicamba. It has been discovered that MEA dicamba formulations are compatible with most water soluble surfactants. A weight ratio of dicamba a.e. to surfactant of from 1:1 to 20:1. from 2:1 to 10:1 or from 3:1 to 8:1 is preferred.
  • Alkoxylated tertiary etheramine surfactants for use in the herbicidal formulations of the present invention have the general structure (19):
  • R 191 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms; each R 192 is a hydrocarbylene independently having 2, 3, or 4 carbon atoms; m is an average number from about 1 to about 10; R 193 and R 194 are each independently hydrocarbylene having 2, 3, or 4 carbon atoms; and the sum of x and y is an average value ranging from about 2 to about 60.
  • R 191 is preferably an alkyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 18 carbon atoms, from about 10 to about 16 carbon atoms, or from about 12 to about 18 carbons atoms, or from about 10 to about 14 carbon atoms.
  • Sources of the R 191 group include, for example, coco or tallow, or R 191 may be derived from synthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, or octadecyl groups.
  • Each R 192 may independently be propylene, isopropylene, or ethylene, and m is preferably from about 1 to 5, such as 2 to 3.
  • R 193 and R 194 may be ethylene, propylene, isopropylene, and are preferably ethylene.
  • the sum of x and y is preferably an average value ranging from about 2 to about 22, such as from about 2 to 10, or about 2 to 5. In some embodiments, the sum of x and y is preferably between about 10 and about 20, for example, about 15.
  • Specific alkoxylated tertiary etheramine surfactants for use in the herbicidal formulation of the present invention include, for example, any of the TOMAH E-Series surfactants, such as TOMAH E-14-2 (bis-(2-hydroxyethyl) isodecyloxypropylamine), TOMAH E-14-5 (poly (5)oxyethylene isodecyloxypropylamine), TOMAH E-17-2, TOMAH E-17-5 (poly (5) oxyethylene isotridecyloxypropyl amine), TOMAH E-19-2, TOMAH E-18-2, TOMAH E-18-5 (poly (5)oxyethylene octadecylamine), TOMAH E-18-15, TOMAH E-19-2 (bis-(2-hydroxyethyl) linear alkyloxypropylamine), TOMAH E-S-2, TOMAH E-S-15, TOMAH E-T-2 (bis-(2-hydroxyethyl) tallow amine), TOMA
  • Surfonic AGM 550 available from Huntsman Petrochemical Corporation wherein, for formula (9), R 191 is C 12-14 , R 192 is isopropyl, m is 2, R 193 and R 194 are each ethylene, and x+y is 5.
  • Alkoxylated quaternary etheramine surfactants for use in the herbicidal formulations of the present invention have the general structure (20):
  • R 201 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms;
  • Each R 202 is independently a hydrocarbylene having 2, 3, or 4 carbon atoms;
  • m is an average number from about 1 to about 10;
  • R 203 and R 204 are each independently hydrocarbylene having 2, 3, or 4 carbon atoms; and the sum of x and y is an average value ranging from about 2 to about 60.
  • R 205 is preferably a hydrocarbyl or substituted hydrocarbyl having from 1 to about 4 carbon atoms, more preferably methyl.
  • A is a charge balancing counter-anion, such as sulfate, chloride, bromide, nitrate, among others.
  • R 201 is preferably an alkyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 18 carbon atoms, from about 10 to about 16 carbon atoms, or from about 12 to about 18 carbons atoms, or from about 12 to about 14 carbon atoms.
  • Sources of the R 201 group include, for example, coco or tallow, or R 201 may be derived from synthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, or octadecyl groups.
  • Each R 202 may independently be propylene, isopropylene, or ethylene, and m is preferably from about 1 to 5, such as 2 to 3.
  • R 203 and R 204 may be ethylene, propylene, isopropylene, and are preferably ethylene.
  • the sum of x and y is preferably an average value ranging from about 2 to about 22, such as from about 2 to 10, or about 2 to 5. In some embodiments, the sum of x and y is preferably between about 10 and about 20, for example, about 15.
  • alkoxylated quaternary etheramine surfactants for use in the herbicidal formulation of the present invention include, for example, TOMAH Q-14-2, TOMAH Q-17-2, TOMAH Q-17-5, TOMAH Q-18-2, TOMAH Q-S, TOMAH Q-S-80, TOMAH Q-D-I, TOMAH Q-DT-HG, TOMAH Q-C-15, and TOMAH Q-ST-50.
  • Alkoxylated etheramine oxide surfactants for use in the herbicidal formulations of the present invention have the general structure (21):
  • R 211 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms;
  • Each R 212 is independently a hydrocarbylene having 2, 3, or 4 carbon atoms;
  • m is an average number from about 1 to about 10;
  • R 213 and R 214 are each independently hydrocarbylene having 2, 3, or 4 carbon atoms; and the sum of x and y is an average value ranging from about 2 to about 60.
  • R 211 is preferably an alkyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 18 carbon atoms, from about 10 to about 16 carbon atoms, or from about 12 to about 18 carbons atoms, or from about 12 to about 14 carbon atoms.
  • Sources of the R 211 group include, for example, coco or tallow, or R 211 may be derived from synthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, or octadecyl groups.
  • R 212 may be propylene, isopropylene, or ethylene, and m is preferably from about 1 to 5, such as 2 to 3.
  • Each R 213 and R 214 is independently ethylene, propylene, isopropylene, and are preferably ethylene.
  • the sum of x and y is preferably an average value ranging from about 2 to about 22, such as from about 2 to 10, or about 2 to 5. In some embodiments, the sum of x and y is preferably between about 10 and about 20, for example, about 15.
  • Specific alkoxylated etheramine oxide surfactants for use in the herbicidal formulation of the present invention include, for example, any of the TOMAH AO-series of surfactants, such as TOMAH AO-14-2, TOMAH AO-728, TOMAH AO-17-7, TOMAH AO-405, and TOMAH AO-455.
  • Alkoxylated tertiary amine oxide surfactants for use in the herbicidal formulations of the present invention have the general structure (22):
  • R 221 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms
  • R 222 and R 223 are each independently hydrocarbylene having 2, 3, or 4 carbon atoms
  • the sum of x and y is an average value ranging from about 2 to about 50.
  • R 221 is preferably an alkyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 18 carbon atoms, and still more preferably from about 12 to about 18 carbons atoms, for example coco or tallow.
  • R 221 is most preferably tallow.
  • R 222 and R 223 are preferably ethylene.
  • the sum of x and y is preferably an average value ranging from about 2 to about 22, more preferably between about 10 and about 20, for example, about 15.
  • Specific alkoxylated tertiary amine oxide surfactants for use in the herbicidal formulations of the present invention include, for example, any of the AROMOX series of surfactants, including AROMOX C/12, AROMOX C/12W, AROMOX DMC, AROMOX DM16, AROMOX DMHT, and AROMOX T/12 DEG.
  • Alkoxylated tertiary amine surfactants for use in the herbicidal formulations of the present invention have the general structure (23):
  • R 231 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms
  • R 232 and R 233 are each independently hydrocarbylene having 2, 3, or 4 carbon atoms
  • the sum of x and y is an average value ranging from about 2 to about 50.
  • R 231 is preferably an alkyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 18 carbon atoms, and still more preferably from about 12 to about 18 carbons atoms, for example coco or tallow.
  • R 1 is most preferably tallow.
  • R 232 and R 233 are preferably ethylene.
  • the sum of x and y is preferably an average value ranging from about 2 to about 22, more preferably between about 10 and about 20, for example, about 15.
  • alkoxylated tertiary amine surfactants for use in the herbicidal formulations of the present invention include, for example, Ethomeen T/12, Ethomeen T/20, Ethomeen T/25, Ethomeen T/30, Ethomeen T/60, Ethomeen C/12, Ethomeen C/15, and Ethomeen C/25, each of which are available from Akzo Nobel.
  • Alkoxylated quaternary amine surfactants for use in the herbicidal formulations of the present invention have the general structure (24):
  • R 241 , R 242 , R 243 , x and y are as described above for the alkoxylated tertiary amine surfactants of structure (II), i.e., R 241 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms, R 242 and R 243 are each independently hydrocarbylene having 2, 3, or 4 carbon atoms, and the sum of x and y is an average value ranging from about 2 to about 50.
  • R 244 is preferably a hydrocarbyl or substituted hydrocarbyl having from 1 to about 4 carbon atoms, more preferably methyl.
  • X is a charge balancing counter-anion, such as sulfate, chloride, bromide, nitrate, among others.
  • R 241 is preferably an alkyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 18 carbon atoms, and still more preferably from about 12 to about 18 carbons atoms, for example coco or tallow.
  • R 241 is most preferably tallow.
  • R 242 and R 243 are preferably ethylene.
  • the sum of x and y is preferably an average value ranging from about 2 to about 22, more preferably between about 10 and about 20, for example, about 15.
  • alkoxylated quaternary amine surfactants for use in the herbicidal formulation of the present invention include, for example, Ethoquad T/12, Ethoquad T/20, Ethoquad T/25, Ethoquad C/12, Ethoquad C/15, and Ethoquad C/25, each of which are available from Akzo Nobel.
  • an alkoxylated polyamine surfactant for use in the herbicidal formulations of the present invention is a surfactant having the general structure (25):
  • R 251 is an alkyl or alkenyl radical containing 6 to 25 carbon atoms and from 0 to 3 carbon-carbon double bonds;
  • R 252 is —OCH 2 CH 2 CH 2 —, —C( ⁇ O)OCH 2 CH 2 —, —C( ⁇ O)NHCH 2 CH 2 CH 2 —, or —CH 2 —;
  • each occurrence of R 254 is independently —H, —OC( ⁇ O)R 1 , —SO 3 ⁇ A + or —CH 2 C( ⁇ O)O ⁇ A + wherein A + is an alkali metal cation, ammonium or H ⁇ ;
  • each occurrence of a is from 3 to 8;
  • each R 253 is independently ethyl, isopropyl or n-propyl;
  • d, e, f and g are each independently from 1 to 20, b is from 0 to 10, c is 0 or 1, the sum of (c+d+e+f) is
  • the surfactants of formula (25) can optionally be in the form of a cation where one or more nitrogen atoms is additionally substituted with hydrogen, methyl, ethyl, hydroxyethyl or benzyl and one or more anions, equal in number to the number of said additionally substituted nitrogen atoms and being selected from chloride, methylsulfate and ethylsulfate.
  • the surfactants of formula (25) can further optionally be in the form of amine oxides.
  • Alkoxylated polyamine surfactants include, for example, ethoxylates of Adogen 560 (N-coco propylene diamine) containing an average of from 2EO to 20EO, for example, 4.8, 10 or 13.4EO; ethoxylates of Adogen 570 (N-tallow propylene diamine) containing an average of form 2EO to 20EO, for example, 13EO; and ethoxylates of Adogen 670 (N-tallow propylene triamine) containing an average of from 3EO to 20EO, for example, 14.9EO all of which are available from Witco Corp.
  • Adogen 560 N-coco propylene diamine
  • Adogen 570 N-tallow propylene diamine
  • Adogen 670 N-tallow propylene triamine
  • polyamine surfactants for use in the herbicidal formulations of the present invention have the general structure (26):
  • R 261 is C 8-20 , R 262 is C 14 and n is 2 or 3.
  • polyamines for use in the formulations and methods of the present invention include Triamine C(R 261 is coco (C 10-14 )), R 262 is C 3 , n is 2 and amine number (total mg KOH/g) is 500-525), Triamine OV (R 261 is oleyl (vegetable oil), R 262 is C 3 , n is 2 and amine number (total mg KOH/g) is 400-420), Triamine T (R 261 is tallow (C 16-18 ), R 262 is C 3 , n is 2 and amine number (total mg KOH/g) is 415-440), Triamine YT (R 261 is tallow (C 16-18 ), R 262 is C 3 , n is 2 and amine number (total mg KOH/g) is 390-415), Triameen Y12D (R 261 is dodecyl (C
  • Sulfate surfactants for use in the herbicidal formulations of the present invention have the general structure (27a-c):
  • R 271 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms, each R 272 is independently ethyl, isopropyl or n-propyl and n is from 1 to about 20.
  • M is selected from an alkali metal cation, ammonium, an ammonium compound or H + .
  • alkyl sulfates examples include sodium C 8-10 sulfate, sodium C 10-16 sulfate, sodium lauryl sulfate, sodium C 14-16 sulfate, diethanolamine lauryl sulfate, triethanolamine lauryl sulfate and ammonium lauryl sulfate.
  • alkyl ether sulfates examples include sodium C 12-15 pareth sulfate (1 EO), ammonium C 6-10 alcohol ether sulfate (3 EO), sodium C 6-10 alcohol ether sulfate (3 EO), isopropylammonium C 6-10 alcohol ether sulfate (3 EO), ammonium C 10-12 alcohol ether sulfate (3 EO), sodium lauryl ether sulfate (3 EO).
  • alkyl aryl ether sulfates include sodium nonylphenol ethoxylate sulfate (4 EO), sodium nonylphenol ethoxylate sulfate (10 EO), WitcolateTM 1247H(C 6-10 , 3EO, ammonium sulfate), WITCOLATE 7093 (C 6-10 , 3EO, sodium sulfate), WITCOLATE 7259 (C 8-10 sodium sulfate), WITCOLATE 1276 (C 10-12 , 5EO, ammonium sulfate), WITCOLATE LES-60A (C 12-14 , 3EO, ammonium sulfate), WITCOLATE LES-60C(C 12-14 , 3EO, sodium sulfate), WITCOLATE 1050 (C 12-15 , 10EO, sodium sulfate), WITCOLATE WAQ (C 12-16 sodium sulfate), WITCOLATE D-51-51 (nonylphenol 4EO, sodium sulfate
  • Sulfonate surfactants for use in the herbicidal formulations of the present invention correspond to sulfate structures (27a) through (27c) above except the R-substituted moiety is attached directly to the sulfur atom, for instance R 271 SO 3 ⁇ .
  • sulfonate surfactants include, for example, WitconateTM 93S (isopropylamine of dodecylbenzene sulfonate), WITCONATE NAS-8 (octyl sulfonic acid, sodium salt), WITCONATE AOS (tetradecyl/hexadecyl sulfonic acid, sodium salt), WITCONATE 60T (linear dodecylbenzene sulfonic acid, triethanolamine salt) and WITCONATE 605a (branched dodecylbenzene sulfonic acid, N-butylamine salt).
  • WitconateTM 93S isopropylamine of dodecylbenzene sulfonate
  • WITCONATE NAS-8 octyl sulfonic acid, sodium salt
  • WITCONATE AOS tetradecyl/hexadecyl sulfonic acid, sodium salt
  • Phosphate esters of alkoxylated alcohol surfactants for use in the herbicidal formulations of the present invention have the general monoester structure (28a) and the general diester structure (28b):
  • R 281 is a hydrocarbyl or substituted hydrocarbyl having from about 4 to about 22 carbon atoms
  • R 282 is a hydrocarbylene having 2, 3, or 4 carbon atoms
  • m is an average number from about 1 to about 60
  • R 283 and R 284 are each independently hydrogen or a linear or branched chain alkyl having from 1 to about 6 carbon atoms.
  • R 281 is preferably an alkyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 20 carbon atoms, or an alkylphenyl having from about 4 to about 22 carbon atoms, more preferably from about 8 to about 20 carbon atoms.
  • Sources of the R 281 group include, for example, coco or tallow, or R 281 may be derived from synthetic hydrocarbyls, such as decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, or octadecyl groups.
  • R 282 may be propylene, isopropylene, or ethylene, and is preferably ethylene.
  • m is preferably from about 9 to about 15.
  • R 283 and R 284 are preferably hydrogen.
  • Specific phosphate esters of alkoxylated alcohol surfactants for use in the herbicidal formulation of the present invention include, for example, EMPHOS CS-121, EMPHOS PS-400, and WITCONATE D-51-29, available from Witco Corp. Other examples are indicated in table C below for the Phospholan produces (available from Akzo Nobel) wherein the surfactants may comprise a mixture of the monoester and diester forms and wherein R 284 is not present in the diester as indicated and “prop.” refers to proprietary and “NR” refers to not reported.
  • the phosphate esters of the general monoester structure (28a) and the general diester structure (28b) are not alkoxylated, i.e., m is 0.
  • Examples of commercial products include Phospholan PS-900 and Phospholan 3EA.
  • R 281 R 282 R 283 /R 284 m di forms Phospholan nonyl phenol C 2 H 6 mono & di CS-131 Phospholan nonyl phenol C 2 H 6 high mono CS-1361 & di Phospholan nonyl phenol C 2 H 10 mono & di CS-141 Phospholan nonyl phenol C 2 H 8 mono & di CS-147 Phospholan prop. prop. prop. prop.
  • Alkyl polysaccharide surfactants for use in the herbicidal formulations of the present invention have the general structure (29):
  • R 291 is a straight or branched chain substituted or unsubstituted hydrocarbyl selected from alkyl, alkenyl, alkylphenyl, alkenylphenyl having from about 4 to about 22 carbon atoms, wherein sug and u are as defined above.
  • the polysaccharide surfactant may be an alkyl polyglucoside of formula (29) wherein: R 291 is a branched or straight chain alkyl group preferably having from 4 to 22 carbon atoms, more preferably from 8 to 18 carbon atoms, or a mixture of alkyl groups having an average value within the given range; sug is a glucose residue; and u is between 1 and about 5, and more preferably between 1 and about 3.
  • surfactants of formula (29) are known in the art. Representative surfactants are presented in Table D below wherein for each surfactant sug is a glucose residue.
  • Alkoxylated alcohol surfactants for use in the herbicidal formulations of the present invention have the general structure (30):
  • R 301 is hydrocarbyl or substituted hydrocarbyl having from 1 to about 30 carbon atoms
  • R 302 in each of the (R 302 O) x groups is independently C 2 -C 4 alkylene
  • R 303 is hydrogen, or a linear or branched alkyl group having from 1 to about 4 carbon atoms
  • x is an average number from 1 to about 60.
  • preferred R 301 hydrocarbyl groups are linear or branched alkyl, linear or branched alkenyl, linear or branched alkynyl, aryl, or aralkyl groups.
  • R 301 is a linear or branched alkyl or linear or branched alkenyl group having from about 8 to about 30 carbon atoms
  • R 302 in each of the (R 302 O) x groups is independently C 2 -C 4 alkylene
  • R 303 is hydrogen, methyl or ethyl
  • x is an average number from about 5 to about 50.
  • R 301 is a linear or branched alkyl group having from about 8 to about 25 carbon atoms
  • R 302 in each of the (R 302 O) x groups is independently ethylene or propylene
  • R 303 is hydrogen or methyl
  • x is an average number from about 8 to about 40.
  • R 301 is a linear or branched alkyl group having from about 12 to about 22 carbon atoms
  • R 302 in each of the (R 302 O) x groups is independently ethylene or propylene
  • R 303 is hydrogen or methyl
  • x is an average number from about 8 to about 30.
  • Preferred commercially available alkoxylated alcohols include: EmulginTM L, ProcolTM LA-15 (from Protameen); Brij TTM 35, Brij 56, Brij TTM 76, Brij TTM 78, Brij TTM 97, Brij TTM 98 and TergitolTM XD (from Sigma Chemical Co.); NeodolTM 25-12 and NeodolTM 45-13 (from Shell); HetoxolTM CA-10, HetoxolTM CA-20, HetoxolTM CS-9, HetoxolTM CS-15, HetoxolTM CS-20, HetoxolTM CS-25, HetoxolTM CS-30, Plurafac A38 and PlurafacTM LF700 (from BASF); ST-8303 (from Cognis); ArosurfTM 66 E10 and ArosurfTM 66 E20 (from Witco/Crompton); ethoxylated (9.4 EO) tallow, propoxylated
  • SURFONICTM NP95 of Huntsman a polyoxyethylene (9.5) nonylphenol
  • TERGITOL series from Dow and commercially available from Sigma-Aldrich Co. (Saint Louis, Mo.), including TERGITOL-15-S-5, TERGITOL-15-S-9, TERGITOL-15-S-12 and TERGITOL-15-S-15 (made from secondary, linear C 11 to C 15 alcohols with an average of 5 moles, 9 moles, 12.3 moles and 15.5 moles of ethoxylation, respectively); the SURFONIC LF-X series from Huntsman Chemical Co.
  • L12-7 and L12-8 made from linear C 10 to C 12 alcohols with an average of 7 moles and 8 moles, respectively, of ethoxylation
  • L24-7, L24-9 and L24-12 made from linear C 12 to C 14 alcohols with an average of 7 moles, 9 moles and 12 moles of ethoxylation, respectively
  • L68-20 made from primary, linear C 16-18 alcohols with an average of 20 moles of ethoxylation
  • L26-6.5 made from linear C 12 to C 16 alcohols with an average of 6.5 moles of ethoxylation
  • Ethylan 68-30 C 16-18 with an average of 20 moles of ethoxylation
  • the surfactant is selected from alkoxylated tertiary etheramines, alkoxylated quaternary etheramines, alkoxylated etheramine oxides, alkoxylated tertiary amines, alkoxylated quaternary amines, alkoxylated polyamines, sulfates, sulfonates, phosphate esters, alkyl polysaccharides, alkoxylated alcohols, and combinations thereof.
  • amidoalkylamine surfactants can optionally be formulated in compositions of the present invention comprising glyphosate co-herbicide.
  • Amidoalkylamine surfactants for use in such herbicidal formulations of the present invention have the general structure (31):
  • R 311 is a hydrocarbyl or substituted hydrocarbyl having from 1 to about 22 carbon atoms
  • R 312 and R 313 are each independently hydrocarbyl or substituted hydrocarbyl having from 1 to about 6 carbon atoms
  • R 314 is hydrocarbylene or substituted hydrocarbylene having from 1 to about 6 carbon atoms.
  • R 311 is preferably an alkyl or substituted alkyl having an average value of carbon atoms between about 4 to about 20 carbon atoms, preferably an average value between about 4 and about 18 carbon atoms, more preferably an average value from about 4 to about 12 carbon atoms, more preferably an average value from about 5 to about 12 carbon atoms, even more preferably an average value from about 6 to about 12 carbon atoms, and still more preferably an average value from about 6 to about 10 carbon atoms.
  • the R 311 alkyl group may be derived from a variety of sources that provide alkyl groups having from about 4 to about 18 carbon atoms, for example, the source may be butyric acid, valeric acid, caprylic acid, capric acid, coco (comprising mainly lauric acid), myristic acid (from, e.g., palm oil), soy (comprising mainly linoleic acid, oleic acid, and palmitic acid), or tallow (comprising mainly palmitic acid, oleic acid, and stearic acid).
  • the source may be butyric acid, valeric acid, caprylic acid, capric acid, coco (comprising mainly lauric acid), myristic acid (from, e.g., palm oil), soy (comprising mainly linoleic acid, oleic acid, and palmitic acid), or tallow (comprising mainly palmitic acid, oleic acid,
  • the amidoalkylamine surfactant component may comprise a blend of amidoalkylamines having alkyl chains of various lengths from about 5 carbon atoms to about 12 carbon atoms.
  • an amidoalkylamine surfactant component may comprise a blend of surfactants having R 311 groups that are 5 carbon atoms in length, 6 carbon atoms in length, 7 carbon atoms in length, 8 carbon atoms in length, 9 carbon atoms in length, 10 carbon atoms in length, 11 carbon atoms in length, and 12 carbon atoms in length, longer carbon chains, and combinations thereof.
  • the amidoalkylamine surfactant component may comprise a blend of surfactants having R 311 groups that are 5 carbon atoms in length, 6 carbon atoms in length, 7 carbon atoms in length, and 8 carbon atoms in length.
  • the amidoalkylamine surfactant component may comprise a blend of surfactants having R 1 groups that are 6 carbon atoms in length, 7 carbon atoms in length, 8 carbon atoms in length, 9 carbon atoms in length, and 10 carbon atoms in length.
  • the amidoalkylamine surfactant component may comprise a blend of surfactants having R 311 groups that are 8 carbon atoms in length, 9 carbon atoms in length, 10 carbon atoms in length, 11 carbon atoms in length, and 12 carbon atoms in length.
  • R 312 and R 313 are independently preferably an alkyl or substituted alkyl having from 1 to about 4 carbon atoms.
  • R 312 and R 313 are most preferably independently an alkyl having from 1 to about 4 carbon atoms, and most preferably methyl.
  • R 314 is preferably an alkylene or substituted alkylene having from 1 to about 4 carbon atoms.
  • R 314 is most preferably an alkylene having from 1 to about 4 carbon atoms, and most preferably n-propylene.
  • the amidoalkylamine surfactants are termed amidopropylamine (APA) surfactants.
  • R 311 is C 6-10 , i.e., an alkyl group having 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, or a blend of any of these, i.e., from about 6 carbon atoms to about 10 carbon atoms; R 312 and R 313 are each methyl; and R 314 is n-propylene (i.e., C 6-10 amidopropyl dimethylamine).
  • APA surfactants include Armeen APA 2 (where R 311 is C 2 and R 312 and R 313 are each hydrogen), Armeen APA 6 (where R 311 is C 6 and R 312 and R 313 are each methyl), Armeen APA 8, 10 (where R 311 is C 8-10 and R 312 and R 313 are each methyl), Armeen APA 12 (where R 311 is C 12 and R 312 and R 313 are each methyl), ACAR 7051 (where R 311 is C 5-9 and R 312 and R 313 are each methyl), ACAR 7059 (where R 311 is 2-ethyl hexyl and R 312 and R 313 are each methyl) and Adsee C80W (where R 311 is Coco and R 312 and R 313 are each methyl).
  • certain polybasic amine polymers may precipitate from solution in acidic aqueous formulations. It has been discovered that certain solubilizers improve amine polymer solubility in such formulations and function to prevent or inhibit precipitation. Under one theory, and without being bound to any particular theory, it is believed that the solubilizers help to maintain amine site hydration thereby inhibiting collapse of the polymer three-dimensional structure and associated precipitation from solution. It has been discovered that amine surfactants can function as both herbicidal efficacy enhancers and solubilizers.
  • solubilizers include, for example, amine surfactants such as alkoxylated tertiary etheramines, alkoxylated quaternary etheramines, alkoxylated etheramine oxides, alkoxylated tertiary amine oxides, alkoxylated tertiary amines, alkoxylated quaternary amines, polyamines, alkoxylated polyamines and betaines.
  • Solubilizers may also include primary, secondary or tertiary C 4 to C 16 alkyl or aryl amine compounds, or the corresponding quaternary ammonium compounds.
  • a weight ratio of polymer to solubilizer of from about 1:1 to about 50:1 is preferred, more preferably from about 2:1 to about 25:1.
  • compounds which enhance polymer solubility include amines or quaternary ammonium salt compounds having the general structures (32) and (33)
  • R 320 is linear or branched alkyl or aryl having from about 4 to about 16 carbon atoms
  • R 321 is hydrogen, methyl or ethyl
  • R 322 is hydrogen, methyl or ethyl
  • R 323 is hydrogen or methyl
  • a ⁇ is an agriculturally acceptable anion.
  • Non-limiting examples include, mixed C 8-16 alkyl amine (Armeen C), dimethylcocoamine (Arquad DMCD), cocoammonium chloride (Arquad C), of which are manufactured by Akzo Nobel, hexylamine, dimethylhexylamine, octylamine, dimethyloctylamine, dodecyltrimethyl amide and C 4-8 trialkyl amines.
  • amidoalkylamine surfactants as described above, can optionally be formulated as a solubilizer in compositions of the present invention comprising glyphosate co-herbicide.
  • Alkoxylated tertiary etheramines, alkoxylated quaternary etheramines, alkoxylated tertiary amines, alkoxylated quaternary amines, and octylamines are generally preferred stabilizers and, based on experimental evidence to date, provide greater polymer solubility and stability on a weight ratio basis than do amidoalkylamines.
  • the formulations of the invention may further comprise other additives such as conventional drift control agents, safeners, thickeners, flow enhancers, antifoaming agents, freeze protectants and/or UV protectants.
  • Suitable drift control agents are known to those skilled in the art and include the commercial products Gardian®, Gardian Plus®, Dri-Gard®, Pro-One XLTM, ArrayTM, CompadreTM, In-Place®, Bronc® Max EDT, EDT ConcentrateTM, Coverage® and Bronc® Plus Dry EDT.
  • Safeners are likewise known to those skilled in the art and include isoxadifen, benoxacor and dichlormid.
  • the dicamba formulations of the present invention are used in the preparation of concentrate, tank mix or ready to use (RTU) formulations further comprising one or more additional co-herbicides.
  • Co-herbicides include auxin herbicide salts other than dicamba salts (as previously described).
  • Co-herbicides also include acetyl CoA carboxylase (ACCase) inhibitors, acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors, photosystem II inhibitors, photosystem I inhibitors, protoporphyrinogen oxidase (PPO or Protox) inhibitors, carotenoid biosynthesis inhibitors, enolpyruvyl shikimate-3-phosphate (EPSP) synthase inhibitor, glutamine synthetase inhibitor, dihydropteroate synthetase inhibitor, mitosis inhibitors, synthetic auxins, auxin transport inhibitors and nucleic acid inhibitors, salts and esters thereof, and combinations thereof.
  • ACCase acetolactate synthase
  • AHAS acetohydroxy acid synthase
  • PPO protoporphyrinogen oxidase
  • EBP enolpyruvyl shikimate-3-phosphate
  • co-herbicides include racemic mixtures and resolved isomers.
  • Typical cations for the co-herbicide salts of the present invention include potassium, MEA, DMA, IPA, trimethylsulfonium (TMS) diethylammonium (DEA), lithium, and ammonium.
  • Typical anions for the formation of co-herbicide salts include chlorine, bromine, fluorine and acetate.
  • Typical esters include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isooctyl, ethylhexyl, ethoxyethyl, butoxyethyl, butoxypropyl and octanoate.
  • Examples of ACCase inhibitors include clethodim, clodinafop, fenoxaprop-P, fluazifop-P, quizalofop-P and sethoxydim.
  • Examples of ALS or AHAS inhibitors include flumetsulam, imazamethabenz-m, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, metsulfuron, prosulfuron and sulfosulfuron.
  • Examples of photosystem I inhibitors include diquat and paraquat.
  • Examples of photosystem II inhibitors include atrazine, cyanazine and diuron.
  • PPO inhibitors examples include acifluorofen, butafenacil, carfentrazone-ethyl, flufenpyr-ethyl, fluthiacet, flumiclorac, flumioxazin, fomesafen, lactofen, oxadiazon, oxyfluorofen and sulfentrazone.
  • carotenoid biosynthesis inhibitors include aclonifen, amitrole, diflufenican and sulcotrione.
  • Glyphosate is an EPSP inhibitor
  • glufosinate is a glutamine synthetase inhibitor
  • asulam is a dihydropteroate synthetase inhibitor.
  • mitosis inhibitors examples include acetochlor, alachlor, dithiopyr, S-metolachlor and thiazopyr.
  • Naptalam is an example of a auxin transport inhibitor.
  • nucleic acid inhibitors include difenzoquat, fosamine, metham and pelargonic acid.
  • water-soluble herbicides include, without restriction, 2,4-D, aminopyralid, clopyralid, fluoroxypyr, MCPA, and salts thereof; 2,4-DB salts, dichlorprop salts, MCPB salts, mecoprop salts, picloram salts, quinclorac salts, and triclopyr salts; and water soluble acids, salts and esters of acifluorfen, alloxydim, aminocarbazone, amidosulfuron, amitrole, asulam, azafenidin, azimsulfuron, beflubutamid, benazolin, bentazon, bensulfuron-methyl, bispyribac, bromacil, carbetamide, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, clomazone, dalapon, dazomet, dicamba, dichlormid, diclofop, diclopyr, dif
  • Suitable water-insoluble herbicides include, without restriction, acetochlor, acifluorfen, aclonifen, alachlor, ametryn, anilofos, atrazine, azafenidin, benfluralin, bensulfuron-methyl, bensulide, benzofenap, bifenox, bromoxynil, butachlor, butroxydim, butylate, cafenstrole, chlomethoxyfen, chlorbromuron, chloridazon, chlornitrofen, chlorotoluron, chlorthal-dimethyl, chlorthiamid, cinmethylin, clethodim, clodinafop-propargyl, cloransulam-methyl, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, desmedipham, desmetryn, dichlobenil, diclos
  • Some preferred water-soluble herbicides include 2,4-D and salts thereof, acifluorfen salts, carfentrazone-ethyl, fomesafen salts, glyphosate and salts thereof, glufosinate and salts thereof, imazamethabenz and salts and esters thereof, imazamox and salts and esters thereof, imazapic and salts and esters thereof, imazapyr and salts and esters thereof, imazaquin and salts and esters thereof, imazethapyr and salts and esters thereof, mecoprop salts, triclopyr salts, racemic mixtures and resolved isomers thereof, and combinations thereof.
  • Some preferred water-insoluble herbicides include acetochlor, alachlor, atrazine, azafenidin, bifenox, butachlor, butafenacil, diuron, dithiopyr, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluthiacet-methyl, lactofen, metazochlor, metolachlor (and S-metolachlor), oxadiargyl, oxadiazon, oxyfluorfen, pretilachlor, propachlor, propisochlor, pyraflufen-ethyl, sulfentrazone and thenylchlor, racemic mixtures and resolved isomers thereof, and combinations thereof.
  • Tank mix and RTU co-herbicide formulations of the present invention typically comprise from about 0.1 g a.e./L to about 50 g a.e./L total herbicide loading while co-herbicide concentrate formulations of the present invention typically comprise from about 50 to about 750 g a.e./L, from about 300 to about 750 g a.e./L, from about 350 to about g a.e./L, from about 400 to about 750 g a.e./L, from about 450 to about 750 g a.e./L, or even from about 500 to about 750 g a.e./L.
  • a weight ratio on an acid equivalent basis of the auxin herbicide to the total co-herbicide of 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 or even about 1:10 and ranges thereof, for example, 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, are preferred.
  • auxin herbicide and concentration thereof For any given auxin herbicide and concentration thereof, one skilled in the art can readily determine using routine experimentation a minimum ratio of that auxin herbicide to any co-herbicide or combination of co-herbicides that is necessary to achieve the objects of the invention in view of the other components of the formulation, such as a polybasic polymer component and/or surfactant component and their respective concentrations.
  • an auxin herbicide e.g., dicamba
  • a co-herbicide selected from glyphosate, glufosinate (or glufosinate-P), an ALS inhibitor, salts and esters thereof, or combinations thereof, for application to transgenic plants comprising an auxin (e.g., dicamba, 2,4-D or fluoroxypyr) resistant trait, a glyphosate resistant trait, a glufosinate resistant trait, an ALS resistant trait, or combinations thereof.
  • Crop tolerance to specific herbicides can be conferred by engineering genes into crops which encode appropriate herbicide metabolizing enzymes and/or insensitive herbicide targets.
  • Technology for introduction of a DNA molecule (genes) into cells is well known to those of skill in the art.
  • Methods and materials for transforming plant cells by introducing a DNA construct into a plant genome in the practice of this invention can include any of the well-known and demonstrated methods including, but not limited to:
  • Transformations of monocotyledon plants using electroporation, particle bombardment, and Agrobacterium have also been reported. Transformation and plant regeneration have been achieved in asparagus (Bytebier, et al., Proc. Natl. Acad. Sci .
  • Transformed cells are generally cultured in the presence of a selective media, which selects for the successfully transformed cells and induces the regeneration of plant shoots and roots into intact plants (Fraley, et al., Proc. Natl. Acad. Sci. U.S.A., 80: 4803 (1983)). Transformed plants are typically obtained within two to four months.
  • the regenerated transgenic plants are self-pollinated to provide homozygous transgenic plants.
  • pollen obtained from the regenerated transgenic plants may be crossed with non-transgenic plants, preferably inbred lines of agronomically important species.
  • Descriptions of breeding methods that are commonly used for different traits and crops can be found in one of several reference books, see, for example, Allard, Principles of Plant Breeding , John Wiley & Sons, NY, U.
  • the transformed plants may be analyzed for the presence of the genes of interest and the expression level and/or profile conferred by the regulatory elements of the present invention.
  • methods for plant analysis include, but are not limited to Southern blots or northern blots, PCR-based approaches, biochemical analyses, phenotypic screening methods, field evaluations, and immunodiagnostic assays.
  • the expression of a transcribable polynucleotide molecule can be measured using TaqMan® (Applied Biosystems, Foster City, Calif.) reagents and methods as described by the manufacturer and PCR cycle times determined using the TaqMan® Testing Matrix.
  • the Invader® (Third Wave Technologies, Madison, Wis.) reagents and methods as described by the manufacturer can be used transgene expression.
  • the seeds of the plants of this invention can be harvested from fertile transgenic plants and be used to grow progeny generations of transformed plants of this invention including hybrid plant lines comprising the construct of this invention and expressing a gene of agronomic interest.
  • Genetically engineered crop plants of the present include, for example, cotton, soybeans, sugar beet, sugar cane, plantation crops, tobacco, rape, maize and rice.
  • crops having herbicidal resistance given by a genetic engineering technique include corn, soybean and cotton having resistance to glyphosate (Roundup Ready®) and glufosinate (Liberty Link®).
  • Other examples of herbicide resistant crop plants include dicamba, 2,4-D, dicamba or sethoxydim resistant corn, cotton and soybean; imidazolinone (imazethapyr and imazapyr) resistant corn (Imi-Corn®) and soybeans; and glyphosate and glufosinate resistant corn (SmartStax®).
  • dicamba (or a salt thereof) is combined with glyphosate co-herbicide (or a salt or ester thereof), the crop plant comprises a glyphosate-resistant trait and the crop plant is further either (i) a plant species not susceptible to auxin herbicides or (ii) comprises a dicamba resistant trait.
  • Such compositions are useful to control (i) glyphosate susceptible plants and (ii) glyphosate resistant, but auxin susceptible, volunteer crop plants and/or weeds growing in a field of (iii) glyphosate and auxin resistant or tolerant crop plants.
  • the auxin co-herbicide is an ALS-inhibitor herbicide (or a salt or ester thereof), the crop plant comprises an ALS-resistant trait and the crop plant is further either (i) a plant species not susceptible to auxin herbicides or (ii) comprises a dicamba resistant trait.
  • Such compositions are useful to control (i) ALS susceptible plants and (ii) ALS resistant, but auxin susceptible, volunteer crop plants and/or weeds growing in a field of (iii) ALS and auxin resistant or tolerant crop plants.
  • Some preferred ALS herbicides include amidosulfuron, azimsulfuron, florasulam, halosulfuron (-methyl), imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, metsulfuron (-methyl), nicosulfuron, primisulfuron (-methyl), prosulfuron, rimsulfuron, sulfosulfuron, thifensulfuron (-methyl), triasulfuron, tribenuron (-methyl), trifloxysulfuron and triflusulfuron (-methyl), salts and esters thereof, and racemic mixtures and resolved isomers thereof.
  • the auxin co-herbicide is glufosinate (or glufosinate-P) (or a salt or ester thereof), the crop plant comprises a glufosinate-resistant trait and the crop plant is further either (i) a plant species not susceptible to auxin herbicides or (ii) comprises a dicamba resistant trait.
  • Such compositions are useful to control (i) glufosinate susceptible plants and (ii) glufosinate resistant, but auxin susceptible, volunteer crop plants and/or weeds growing in a field of (iii) glufosinate and auxin resistant or tolerant crop plants.
  • glyphosate and glufosinate (or glufosinate-P) co-herbicides are combined with an auxin herbicide
  • the crop plant is a species that comprises a glyphosate-resistant trait and a glufosinate-resistant trait
  • the crop plant is further either (i) a plant species not susceptible to auxin herbicides or (ii) comprises a dicamba resistant trait.
  • glyphosate and at least one ALS inhibitor herbicide are combined with an auxin herbicide
  • the crop plant is a species that comprises a glyphosate-resistant trait and an ALS-resistant trait
  • the crop plant is further either (i) a plant species not susceptible to auxin herbicides or (ii) comprises a dicamba resistant trait.
  • glufosinate or glufosinate-P
  • at least one ALS inhibitor herbicide or salts or esters thereof
  • the crop plant is a species that comprises a glufosinate-resistant trait and an ALS-resistant trait
  • the crop plant is further either (i) a plant species not susceptible to auxin herbicides or (ii) comprises a dicamba resistant trait.
  • glyphosate, glufosinate (or glufosinate-P) and ALS inhibitor co-herbicides are combined with an auxin herbicide (e.g., dicamba) and the crop plant possesses glyphosate, glufosinate and ALS resistant traits and the crop plant is further either (i) a plant species not susceptible to auxin herbicides or (ii) comprises a dicamba resistant trait.
  • an auxin herbicide e.g., dicamba
  • an application mixture typically comprising from about 0.1 to about 50 g a.e./L herbicide, is formed and then applied to the foliage of a plant or plants at an application rate sufficient to give a commercially acceptable rate of weed control.
  • Application mixtures are typically prepared from aqueous concentrate formulations by dilution with water to achieve the desired concentration. This application rate is usually expressed as amount of auxin herbicide per unit area treated, e.g., grams acid equivalent per hectare (g a.e./ha).
  • the period of time required to achieve a commercially acceptable rate of weed control can be as short as a week or as long as three weeks, four weeks or 30 days. Typically a period of about two to three weeks is needed for the auxin herbicide to exert its full effect.
  • the formulations of the present invention can be applied pre-planting of the crop plant, such as from about 2 to about 3 weeks before planting auxin-susceptible crop plants or crop plants not having a dicamba-resistant trait.
  • Crop plants that are not susceptible to certain auxin herbicides, such as corn, or plants having the dicamba-resistant trait typically have no pre-planting restriction and the formulations of the present invention can be applied immediately before planting such crops.
  • the formulations of the present invention can be applied at planting or post-emergence to crop plants having a dicamba-resistant trait to control auxin-susceptible weeds in a field of the crop plants and/or adjacent to a field of the crop plants.
  • the formulations of the present invention can also be applied post-emergence to crop plants and/or adjacent to crop plants not having a dicamba resistant trait, such as corn, but that are not susceptible to auxin herbicides.
  • herbicidal effectiveness data set forth herein report “inhibition” as a percentage following a standard procedure in the art which reflects a visual assessment of plant mortality and growth reduction by comparison with untreated plants, made by technicians specially trained to make and record such observations. In all cases, a single technician makes all assessments of percent inhibition within any one experiment or trial. Such measurements are relied upon and regularly reported by Monsanto Technology LLC in the course of its herbicide business.
  • auxin herbicides are biologically effective for a specific auxin herbicide.
  • Useful application rates for the auxin herbicides employed can depend upon all of the above conditions. With respect to the use of the method of this invention, much information is known about appropriate auxin application rates, and a weed control practitioner can select auxin application rates that are herbicidally effective on particular species at particular growth stages in particular environmental conditions.
  • Effectiveness in greenhouse tests is a proven indicator of consistency of field performance at normal use rates.
  • a pattern of enhancement emerges over a series of greenhouse tests; when such a pattern is identified this is strong evidence of biological enhancement that will be useful in the field.
  • formulations of the present invention can be applied to plants by spraying, using any conventional means for spraying liquids, such as spray nozzles, atomizers, or the like.
  • Formulations of the present invention can be used in precision farming techniques, in which apparatus is employed to vary the amount of exogenous chemical applied to different parts of a field, depending on variables such as the particular plant species present, soil composition, and the like.
  • a global positioning system operated with the spraying apparatus can be used to apply the desired amount of the formulation to different parts of a field.
  • the formulation, at the time of application to plants, is preferably dilute enough to be readily sprayed using standard agricultural spray equipment.
  • Preferred application rates for the present invention vary depending upon a number of factors, including the type and concentration of active ingredient and the plant species involved.
  • Useful rates for applying an aqueous formulation to a field of foliage can range from about 25 to about 1,000 liters per hectare (1/ha) by spray application.
  • the preferred application rates for aqueous solutions are in the range from about 50 to about 300 l/ha.
  • exogenous chemicals including auxin herbicides
  • auxin herbicides must be taken up by living tissues of the plant and translocated within the plant in order to produce the desired biological (e.g., herbicidal) effect.
  • an herbicidal formulation not be applied in such a manner as to excessively injure and interrupt the normal functioning of the local tissue of the plant so quickly that translocation is reduced.
  • some limited degree of local injury can be insignificant, or even beneficial, in its impact on the biological effectiveness of certain exogenous chemicals.
  • the experiments were carried out in greenhouse testing.
  • the herbicidal formulations were applied postemergence to weeds having a height of about 10-15 cm using plot sprayers.
  • Test formulations were applied at a spray volume 93 L/ha applied by means of a Flatfan 9501E nozzle (Spraying Systems Co., Wheaton, Ill., USA) at 165 kPa pressure.
  • the greenhouse temperature was 21-29° C. at approximately 30% relative humidity. Evaluation was done by visual scoring. The effects on the plant species were estimated in comparison with untreated control plots using a percentage scale (0-100%).
  • Aqueous formulations comprising MEA dicamba were typically prepared by mixing water and monoethanolamine for 5 min followed by addition of dicamba acid (98.3% purity) in one portion. The resulting suspensions were stirred until all of the solids had dissolved by visual inspection, typically between 60 min and overnight. Relative amounts of dicamba and MEA used to give 61% by wt solutions of dicamba are reported in Table 1a. These and MEA dicamba solutions prepared using this procedure were subsequently used in preparation of MEA dicamba formulations containing polyimine polymers and/or surfactants.
  • CLARITY contains 56.8 wt % active ingredient (a.i.) (38.5 wt % a.e.) of the diglycolamine salt of dicamba.
  • BANVEL contains 48.2 wt % a.i. of the dimethylamine salt of dicamba.
  • Dicamba Comp. Form. concentration Component conc. 925S3J 48 wt % Surf1 10 wt % MEA dicamba 926Y7O 48 wt % Surf2 10 wt % MEA dicamba 931F5L 40 wt % Poly1 4.2 wt % MEA dicamba 956N5T 48 wt % Surf3 10 wt % MEA dicamba 933C3S 40 wt % Poly5 4.2 wt % MEA dicamba 942T3R 55 wt % None — DGA Dicamba 944L8M 40 wt % None — DGA dicamba 957Y2S 61 wt % None — MEA dicamba 959C9L 48 wt % Surf4 10 wt % MEA dicamba 960U4V 40 wt % Surf5 10 wt % MEA dicamba 961X6A 48 wt 960S
  • Formulations from Table 1b and CLARITY were sprayed over the top of soybeans having both dicamba resistant and Roundup Ready® (RR) traits to investigate any possible injury at application rates of 561 (the labeled rate), 1120 and 2244 grams acid equivalent per hectare (kg a.e./ha) in the equivalent of 93 liters per hectare (L/ha) water. Ratings were taken at 4 days after treatment (DAT). The data is presented in Table 1c in an ANOVA summary of formulations mean comparisons by rate.
  • Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY 59.2 68 72 962P0H 55 70.8 75 925S3J 57 76 94.2 926Y7O 62 79 91.3 956N5T 65 78 94.7 959C9L 64 75 95 960U4V 63.3 72.5 93 961X6A 67.5 70 96.7 963E2Z 67.5 87.5 99 929P6H 71.7 80.8 93.8 908D1S 63.3 72.5 100 LSD 8.7 11 7
  • formulations containing polyimine polymers provided equivalent herbicide performance as compared to formulations comprising a surfactant.
  • the result of the efficacy trials, in % control, on CHEAL is reported in Table 1g.
  • the CHEAL was at the 9-12 leaf growth stage and was 10-15 cm in height.
  • the result of the efficacy trials, in % control, on IPOLA is reported in Table 1h.
  • the IPOLA was at the 1-2 leaf growth stage and was 5-10 cm in height.
  • 926Y7O was slightly less efficacious than the other formulations.
  • the result of the efficacy trials, in % control at 15 DAT, on IPOLA is reported in Table 11.
  • the IPOLA was at the 1-2 leaf growth stage and was 5-10 cm in height.
  • 926Y7O was slightly less efficacious than the other formulations.
  • the result of the efficacy trials, in % control at 18 DAT, on ABUTH is reported in Table 1j.
  • the ABUTH was at the 5-6 leaf growth stage and was 10-15 cm in height.
  • the result of the efficacy trials, in % control at 21 DAT, on ABUTH is reported in Table 1k.
  • the ABUTH was at the 5-6 leaf growth stage and was 10-15 cm in height.
  • TRFRE White clover
  • Tables 1b through 1k show that the herbicidal performance of dicamba can be improved as compared to the commercial products CLARITY and BANVEL.
  • the etheramine surfactant Surfonic AGM 550 surfactant and surf2 comprising a mixture of a cationic alkyl ether amine surfactant and an anionic alkyl ether phosphate surfactant, provided the greatest dicamba herbicidal activity.
  • the alkylpolyglucoside gave the least improvement also ABUTH control was improved as compared to CLARITY.
  • the data further show that polymers can give substantially equivalent dicamba efficacy enhancement as do surfactants.
  • Formulation 140 g ae/ha 280 g ae/ha 560 g ae/ha 943Q1H 60.0 70.8 83.3 944L8M 65.8 78.3 85.0 7601W8J 70.0 79.2 91.7 7602G5V 61.7 69.2 80.0 7603A1D 60.0 68.3 74.2 7604P0K 58.3 68.3 79.2 7605L6Y 60.8 65.8 73.3 7606M4R 56.7 61.7 67.5 CLARITY 56.7 70.8 82.5 962P0H 63.3 66.7 74.2
  • formulation mean comparisons by rate indicated that at 140 g/L and 280 g/L 944L8M was more efficacious than CLARITY.
  • Formulation 7601W8J was more efficacious than CLARITY at all 3 rates tested.
  • formulations 7605L6Y and 7606M4R were less efficacious than CLARITY.
  • Potassium dicamba formulations from Table 1b, CLARITY, and 480 g/L MEA dicamba were tested for their post-emergent control of 15 cm velvetleaf at 70, 140, 280 and 560 grams a.e./ha.
  • the results of the efficacy trial in % control at 22 DAT are reported in Table 1n.
  • Aqueous formulations comprising MEA dicamba and various coco and tallow di- and tri-amine ethoxylates were prepared as indicated in Table 2a wherein the dicamba concentration in each formulation was 633 g a.e./ha (47.9 wt % a.e.) and the concentration of the other components in wt % is indicated in parenthesis.
  • Solutions of each of the sodium, potassium, DMA, MEA, IPA and DGA salts of dicamba were prepared as 10% stock solutions at a mole ratio of approximately 1:1 dicamba acid to base. To alter the pH, either dicamba acid was added or base was added. The pH was measured on a standard Orion Model 320 pH meter of each neat solution. For the distillations, the salt solutions were diluted to obtain a dicamba concentration of 5%, 2%, and 1% a.e. while compensating for any added base or dicamba acid to adjust pH.
  • the Diglycolamine salt solutions were prepared using Clarity®, a 38.5% a.e. dicamba solution.
  • the distillate was collected and analyzed for dicamba concentration using HPLC/Mass Spectroscopy (MS).
  • the HPLC column was an Agilent Zorbax Eclipse XDB-C8, 4.6 ⁇ 150 mm, 5u, PN 993967-90.
  • Mobile phase A was 0.1% formic acid in D.I. water.
  • Mobile phase B was 0.1% formic acid in acetonitrile.
  • a flow rate of 1.2 mL/min was used and an injection volume of 5, 10, 15 or 25 ul was used depending on the dicamba level in the sample.
  • the following gradient was used:
  • Time % A % B 0 100 0 7.5 0 100 10 0 100 10.1 100 0 15 100 0
  • the MS parameters were as follows: Type SIR; ES ⁇ ion mode; 0.05 second inter channel delay; 0.05 second interscan time; 0.5 span (Da); 10 minutes elapsed time; and 6-6000 ppb calibration range.
  • Tables 4a through 4f summarize the data for all experiments. These tables show the mean values of Dicamba concentration in the distillate from the triplicate distillations. The standard deviation is shown.
  • the more volatile cations IPA and DMA show more dicamba in the distillate at higher pH because as the solution distills, a significant amount of the cation (DMA or IPA) is distilling from the solution. This leads to an effectively lower pH in the solution being distilled and a resultant higher amount of dicamba being distilled from the solution.
  • the volatile cations are co-distilling from the solutions with dicamba, particularly when the original pH of the distillation solution is greater than 7.
  • Table 4h provides a summary of dicamba in the distillate of 5% a.e. Dicamba solutions at approximately neutral pH. While it is difficult to directly compare the values as the pH of each solution is slightly different, the relative difference are clear that the more volatile amine salts have a higher concentration of dicamba in the distillate compared to the lower volatile cation salts DGA Na, K, and MEA. These lower volatility salts also showed a pH dependent trend of lower amounts of dicamba in the distillate as the pH increases.
  • Dicamba salt a.e. ⁇ g/mL dicamba air air sodium (pH 2.7) 35.8 3.55 71 9.86 4.46 ⁇ 10 ⁇ 11 potassium (pH 10.5) 35.8 0.24 4.8 0.67 3.02 ⁇ 10 ⁇ 12 MEA 35.8 0.02 0.4 0.056 2.51 ⁇ 10 ⁇ 13 BANVEL (DMA salt) 40 0.42 8.4 1.17 5.28 ⁇ 10 ⁇ 12 dicamba acid 99 15.3 305.4 42.4 1.92 ⁇ 10 ⁇ 10
  • the MEA salt showed a dicamba concentration in the gas phase above the solution lower than the acid or the sodium, potassium and DMA salts.
  • the MEA salt had a gas concentration on the order of 20 times less than the commercial product BANVEL.
  • PUF Polyurethane Foam
  • Procedure The procedure took place in a growth chamber at a temperature of 35° C. and relative humidity of 30%.
  • a PUF was placed into the glass tube.
  • the top of the tube was wrapped with parafilm such that it would fit snuggly into the top of the centrifuge tube.
  • 10 mL of the dicamba a.e. solution prepared to be approximately 20% a.e. dicamba was placed into the centrifuge tube.
  • the tube was attached to the ring stand and held in a vertical position.
  • the glass tube was fitted into the top of the centrifuge tube.
  • a tygon tube was connected to the nipple on the glass tube. This tube was connected to an air pump through a needle valve to control the air flow at 2 liters per minute (about 0.2 L air/min-mL sample).
  • the air pump was started and air pulled through the tube for 24 hours. After 24 hours, the pump was turned off and the PUF removed from the glass tube. The PUF was placed into 20 mL of methanol to extract the dicamba. The amount of dicamba was quantified by LC/Mass Spectrometric analysis.
  • formulations 506C3N, 5851AR and 566E7H each contained Lupasol SK polymer (poly5) at a 1:1 weight ratio of dicamba a.e. to polymer and formulations 5851BT and 565B8I each contained dicamba MEA in the absence of polymer.
  • the reported results for formulation 506C3N is the average of 6 samples, each tested in duplicate, and the remaining results represent the average of 4 samples, each tested in duplicate.
  • “S.D.” refers to standard deviation
  • % RSD refers to percent relative standard deviation
  • Formulam. pH refers to the pH of the dicamba formulation.
  • the data indicate that Lupasol reduced MEA dicamba volatilization by about 25% at a pH of about 9.5 and by about 1000% at a pH of about 7.
  • dicamba solutions “SD” refers to standard deviation, “pH” refers to the pH of the formulation, “Test mL” refers to the volume of dicamba solution tested and “Ratio” refers to the weight ratio of dicamba a.e. to polymer where the identity of the polymer is indicated in parentheses.
  • Aqueous formulations comprising 601 g a.e./L MEA dicamba (48.3 wt % a.e.) were combined with from 1 to 10 wt % polyimine polymers having a range of molecular weights as indicated in Table 5a below. Each of the formulations was a clear solution.
  • Component 1 Component 2 Formulation Polymer wt % Surfactant wt % 151J6M — — — — — 152F5X — — Surf3 6 153P0L Poly1 5 — — 154V4V Poly1 5 Surf3 6 161L8I Poly2 5 — — 162N4R Poly2 5 Surf3 6 163L1K Poly3 5.7 — — 164A2D Poly3 5 Surf3 6 171H3P Poly4 7.6 — — 172G5F Poly4 7.6 Surf3 6
  • formulations from Table 5a previously described formulations 962P0H, 926Y7O, 956N5T, formulation 962-2A (containing 480 g a.e./L (40 wt % a.e.) MEA dicamba with no surfactant, and CLARITY were applied postemergence at rates of 140, 280 and 561 g a.e./ha on 10-15 cm high Velvetleaf and evaluated 18 days after treatment. The results in % control are reported in Table 5b below.
  • the bioefficacy data shows an increase in dicamba activity at an application rate of 140 g a.e./ha and no reduction in dicamba activity at application rates of 280 and 561 g a.e./ha for the formulations comprising the polymers as compared to formulations comprising a surfactant in the absence of a polymer or the combination of a surfactant and a polymer.
  • formulations 151J6M, 153P0L, 154V4V, 161L8I, 163L1K and 172G5F were significantly more efficacious than CLARITY.
  • Aqueous formulations comprising 600 g a.e./L MEA dicamba (48.3 wt % a.e.) were prepared as indicated in Table 6a below where “Form” refers to formulation. All of the formulations were clear, homogeneous solutions. The formulations were evaluated for spraying characteristics.
  • Component 1 Form polymer wt % Surfactant wt % 019A8J Poly5 3.5 — — 019B6Y Poly5 3.5 Surf3 6 019C9J Poly5 6 — —
  • Formulation 140 g a.e./ha 280 g a.e./ha 561 g a.e./ha CLARITY 60.0 83.3 96.5 962P0H 68.3 84.2 98.5 926Y7O 71.7 87.5 97.7 956N5T 70.0 92.5 96.3 019A8J 71.7 88.3 96.3 019B6Y 72.5 91.7 98.3 019C9J 75.8 89.2 96.7 151J6M 75.0 87.5 95.5 152F5X 80.8 90.8 98.0 LSD 6.5 2.4 2.2
  • the formulations and the comparative formulation CLARITY were diluted in water to a dicamba concentration of 0.77 wt % a.e.
  • the diluted formulations were sprayed using the method for greenhouse efficacy testing on plant, as describe above, on water sensitive paper that changes color (to blue) where a spray drop contacts the paper.
  • the CLARITY composition produced more color on the paper as compared to experimental formulations 019A8J, 019B6Y and 019C9J.
  • the experimental formulations show a comparably more consistent drop size, but still provide good coverage over the paper.
  • the results suggest that polyimines may result in fewer fine droplet particles as compared to CLARITY and can therefore provide some drift control properties to the formulations.
  • aqueous formulations comprising 480 g a.e./L MEA dicamba and 5 wt % polymer formulated at varied mole ratios of MEA to dicamba was evaluated.
  • approximately 50 mL of each formulation was placed into a glass bottle. The bottle were placed in an oven or freezer and evaluated after 1 and 4 weeks of storage and observed for any layering, crystal formation or freezing.
  • the pH was evaluated by measurement after dilution to 1 wt % a.e. dicamba.
  • the formulation of the formulations and test results are reported in Table 7a below wherein “MEA:dicamba” refers to the molar ratio of MEA base to dicamba acid, “stable” refers to no phase separation, “Clr. Sln.” refers to clear solution, and “layer” refers to phase separation.
  • Aqueous formulations comprising 480 and 600 g a.e./L MEA dicamba were formulated with varying amounts of Lupasol SK polymer (poly5). Viscosity was measured at 10° C. using a Haake VT550 viscometer @45 RPM. The viscosity results are reported in Table 8a in centipoise.
  • Lupasol SK (wt %) 480 g a.e./L dicamba 600 g a.e./L dicamba 0 — 20 1.5 — 105 2 55 — 3 — 280 4 160 460 5 — 700 6 335 — 8 650 — 8.5 770 —
  • MEA dicamba and tank mixes containing MEA dicamba with Roundup WeatherMAX® or Roundup PowerMAX® with the drift control agents Gardian®, Gardian Plus®, Dri-Gard®, Pro-One XLTM, ArrayTM, CompadreTM, In-Place®, Bronc® Max EDT, EDT ConcentrateTM, Coverage® and Bronc® Plus Dry EDT was evaluated.
  • Aqueous formulations were prepared as described in Table 9a below where “Form” refers to the formulation, “Drift Cont.” refers to the drift control agent, “Amt” refers to the amount, “W.MAX” refers to ROUNDUP WEATHERMAX, and “P.MAX” refers to ROUNDUP POWERMAX.
  • Table 9a formulations were evaluated for compatibility by observing the appearance after storage at room temperature after one hour. After one hour, the solutions were poured through a 150 micron sieve and observed for the presence of solids. The results are reported in Table 9b below.
  • GARDIAN, GARDIAN PLUS, COMPADRE, BRONC MAX EDT and EDT CONCENTRATE were compatible with all of the mixtures and dicamba alone. Each created clear solutions with no separation and left little to no particles on a 150 um sieve. DRI-GARD dissolved well, but the solutions were all hazy. PRO-ONE XL did create clear solutions but some particles would not dissolve in the tests containing ROUNDUP WEATHER MAX. In all cases ARRAY appeared to suspend for a few hours, but precipitated with time leaving a large amount of residue on the Nessler tubes. IN-PLACE and COVERAGE created emulsions that separated quickly. BRONC PLUS DRY EDT did not dissolve completely.
  • PRO-ONE XL and BRONC PLUS MAX EDT were the only formulations to show clear differences in compatibility between ROUNDUP WEATHER MAX and ROUNDUP POWER MAX.
  • PRO-ONE XL dissolved better in ROUNDUP POWER MAX and BRONC PLUS MAX EDT created a clear solution with Power Max but created a hazy solution with ROUNDUP WEATHER MAX.
  • aqueous solubility of the various salts of dicamba prepared from the bases sodium, potassium, DGA, MEA and hexamethylene diamine (HMDA) salt of dicamba was measured.
  • the maximum solubility was measured by taking a solution of that salt containing salt crystals and equilibrating the solution at 20° C. and 0° C. for 5 to 7 days. The solution was then passed through a 0.45 micron filter and assayed by HPLC for soluble dicamba.
  • Table 10a where “salt” refers to the dicamba salt, the solubility in reported in wt % acid equivalent (a.e.) and wt % active ingredient (a.i.).
  • the solutions of the MEA and DGA salts were found to be particularly difficult to get to form crystals.
  • the MEA salt solution did not form crystals and it took several weeks for a DGA salt solution at ⁇ 57% a.e. to start to form crystals. It should be noted that, when these salt solutions dry on a glass surface, in some experiments a sticky residue is left that does not form crystals. In other experiments crystals did form upon drying MEA dicamba solutions. The data show that it can be difficult to initiate crystal growth from MEA dicamba solutions.
  • the Na and K salts formed crystals very readily on a glass surface. As the solution dried, a powdery residue of salt formed quickly and readily.
  • Aqueous tank mix compatibility of the Na, MEA and DGA dicamba salts with potassium glyphosate was measured.
  • a 35.8% a.e. aqueous solution of the dicamba salt solution was added to an aqueous solution comprising 7.7% Roundup POWERMAX® herbicide (containing 540 g a.e./L potassium glyphosate) until precipitation was noted.
  • the weight of the dicamba solution that caused precipitation was noted.
  • the results are reported in Table 12a below where “salt” refers to the dicamba salt and “g to crystals” refers to the total amount of grams of dicamba a.e. that were required to induce crystallization or precipitation of crystals.
  • Formulation 11BB was discovered to have low viscosity demonstrating that a 600 g/L a.e. MEA dicamba formulation containing 10% surfactant has a low viscosity and would be easily pumpable.
  • the viscosity as a function of temperature was measured and the results are reported in Table 12b below.
  • the polymer may precipitate upon dilution, particularly at low pH. Addition of APA surfactants to these formulations was evaluated to determine if polyimine polymer dissolution could be facilitated.
  • a MEA dicamba solution was prepared by mixing together 799.9 grams (64% w/w/) dicamba acid, 198.6 grams (15.9% w/w) MEA and 251.4 grams (20.1% w/w) water until dissolved.
  • a 16.6% Lupasol P (Poly1) solution was prepared by mixing together 58.2 grams (33.1% w/w) Lupasol P (50%) and 117.5 grams (66.9% w/w water) until dissolved.
  • Formulations of MEA dicamba containing Lupasol P, and Armeen APA 8, 10 were prepared by combining, in order, the MEA dicamba solution, water, the Armeen APA, and the Lupasol P solution using the amounts reported in Table 13a.
  • formulations containing APA surfactant showed little or no precipitation of the polymer compared to formulations containing no APA surfactant.
  • Aqueous formulations comprising MEA dicamba, Lupasol SK, and APA surfactants were formulated as indicated in Table 13c wherein each formulation contained 480 g a.e./L MEA dicamba, 4.15% a.i. Lupasol SK and 2% APA surfactant.
  • the dicamba formulation containing the polyimine polymer had reduced volatility compared to both MEA dicamba and CLARITY formulations.
  • aqueous tank mixtures containing dicamba salt and Roundup POWERMAX® were measured.
  • Aqueous formulations were prepared as described in table 14b. The tank mixtures were evaluated for dicamba concentration in the gas phase (air) through air sampling while being exposed to constant temperature and humidity in humidome in growth chambers.
  • Humidomes were purchased from Hummert International (Part Nos 14-3850-2 for humidomes and 11-3050-1 for 1020 flat tray) and modified by cutting a 2.2 centimeter (cm) diameter hole on one end approx 5 cm from the top to allow for insertion of glass air sampling tube (22 mm OD) containing a polyurethane foam (PUF) filter.
  • the sampling tube was secured with a Viton o-ring on each side of the humidome wall.
  • the air sampling tube external to the humidome was fitted with tubing that was connected to a vacuum manifold immediately prior to sampling.
  • Formulations containing dicamba were introduced into the humidome in one of two ways. Solutions containing dicamba formulations (20 mL) were placed in a petri dish which was positioned on the flat tray beneath the humidome. Alternatively, the flat tray beneath the humidome was filled 1 liter of sifted dry or wet 50/50 soil (50% Redi-Earth and 50% US 10 Field Soil) to a depth of about 1 cm and dicamba formulations were sprayed over the soil using a track sprayer at a rate of 10 gallons per acre (GPA). To avoid contamination of the sides of the flat tray each tray was nested in an empty tray prior to spraying. In some evaluations, potted soybean or velvetleaf plants were placed on top of the soil.
  • sifted dry or wet 50/50 soil 50% Redi-Earth and 50% US 10 Field Soil
  • the flat tray bottom containing the dicamba formulation in a petri dish or on soil was covered with a humidome lid and the lid was secured with clamps.
  • the assembled humidomes were placed in a temperature and humidity controlled environment and connected to a vacuum manifold through the air sampling line. Air was drawn through the humidome and PUF at a rate of 2 liters per minutes (LPM) for 24 hours at which point the air sampling was stopped. The humidomes were then removed from the controlled environment and the PUF filter was removed.
  • LPM 2 liters per minutes
  • the PUF filter was extracted with 20 mL of methanol and the solution was analyzed for dicamba concentration using liquid chromatography-mass spectroscopy methods known in the art. The reported results are an average of 3-6 samples.
  • Aqueous formulations were prepared as indicated in Table 14b below and humidome results are indicated in Table 14c below.
  • Each formulation contained a combination of the indicated dicamba formulation and POWERMAX and having concentrations of 0.5 wt % a.e. dicamba and 1.5 wt % a.e. glyphosate.
  • “Form. No.” refers to formulation number and “Dicamba form.” refers to dicamba formulation.
  • T refers to temperature in degrees centigrade
  • RH relative humidity
  • SD relative humidity
  • ng/L refers to the air sample dicamba concentration in nanograms per liter
  • Petri refers to petri dish
  • soil refers to 50/50 soil (50% Redi-Earth and 50% US 10 Field Soil)
  • si refers to soybean
  • vel refers to velvetleaf.
  • Dicamba salt pH 14(1) CLARITY DGA 4.46 14(2) BANVEL DMA 4.47 14(3) 968Q3W MEA 4.5 14(4) 933C3S MEA 4.81
  • composition 968Q3W containing MEA dicamba
  • BANVEL showed the highest volatility in this humidome test.
  • 933C3S containing MEA dicamba and Lupasol SK polymer
  • Plant injury data was inconclusive in this test.
  • aqueous formulations were prepared as indicated in Table 14d below. Each formulation contained a combination of the indicated dicamba formulation and POWERMAX and having concentrations of 1 wt % a.e. dicamba and 3 wt % a.e.
  • Formula. No.” refers to formulation number
  • Dicamba form.” refers to dicamba formulation.
  • T refers to temperature in degrees centigrade
  • RH relative humidity
  • SD relative humidity
  • ng/L refers to the air sample dicamba concentration in nanograms per liter
  • soil refers to 50/50 soil (50% Redi-Earth and 50% US 10 Field Soil) wherein the compositions are applied to the soil
  • RR soy refers to ROUNDUP READY soybean wherein the compositions are applied to the plant canopy
  • DT soy refers to dicamba tolerant soybean wherein the compositions are applied to the plant canopy.
  • Dicamba salt pH 14(5) CLARITY DGA 4.41 14(6) 968Q3W MEA 4.43 14(7) 944L8M DGA 4.48 14(8) 933C3S MEA 4.81
  • aqueous formulations were prepared as indicated in Table 14f below.
  • “Form. No.” refers to formulation number and “Dicamba form.” refers to dicamba formulation.
  • Each Table 14f formulation contained 2 wt % a.e. dicamba and 6 wt % a.e. glyphosate.
  • Glyphosate “K salt” refers to the potassium salt of glyphosate wherein the glyphosate source was an aqueous solution containing 47.9 wt % a.e. potassium glyphosate;
  • POWERMAX refers to ROUNDUP POWERMAX®; and WEATERMAX refers to ROUNDUP WEATHERMAX®.
  • “SD” refers to standard deviation and “ng/L” refers to the air sample dicamba concentration in nanograms per liter.
  • the Table 14g data show that the addition of PEI reduces the volatility of CLARITY (DGA dicamba), BANVEL (DMA dicamba) and potassium dicamba with LUPASOL FG providing the largest reduction.
  • the data further show that lower molecular weight LUPASOL PEIs provide the greatest volatility reduction for MEA dicamba.
  • the data further show that a weight ratio of dicamba a.e. to PEI polymer of about 10:1 provides the best volatility reduction.
  • the data still further show that PEI polymers having a molecular weight in excess of about 5,000 Daltons are preferred.
  • compositions of the present invention and comparative compositions were measured using an Aerometrics phase doppler particle analysis (PDPA) system.
  • PDPA Aerometrics phase doppler particle analysis
  • the samples were each diluted in 15 L tap water at 20.0° C. to a final equivalent kilogram per hectare (kg/ha) value based on an application rate of 93 liters per hectare (L/ha).
  • the kg/ha values are disclosed in Table 15a below.
  • a corresponding concentration in grams acid equivalent per liter can be calculated from the application rate of 93 L/ha.
  • values of 0.073, 0.09, 0.28 and 0.56 kg/ha reported in table 15a below correspond to 0.78, 0.97, 3 and 6 g a.e./L, respectively.
  • the drift control agents GARDIAN and INTERLOCK are indicated, the concentration is reported in % v/v based on the final diluted formulation.
  • Each mixture was sprayed through a Teejet XR8003VS nozzle tip at 276 kPa (40 psi) at a height of 30 cm above the probe volume of the Aerometrics PDPA laser system.
  • the size range scanned was from 25.7 ⁇ m-900.0 ⁇ m.
  • the voltage for the photo-multiplier tube (PMT) was set to 325V.
  • This data was run through a macro program to generate data including (i) average velocity (in meters per second for the entire spray cloud); (ii) D10 (arithmetic mean diameter); (iii) D20 (area mean); (iv) D30 (volume mean); (v) D32 (sauter mean); (vi) 10% and 90% points (The droplet particle size below which 10% (or 90%) of the volume of the measured particles lie); (vii) Volume Median Diameter (Dv0.5—The droplet particle size below which 50% of the volume of particles are contained); (viii) Number Median Diameter (NMD—The particle size below which 50% of the number of droplet particles are contained); (ix) relative span [(90% point—10% point)/VMD, wherein, the smaller the number, the more narrow (monodispersed) the distribution]; (x) percent by volume and number ⁇ 100 and ⁇ 150 ⁇ m (the proportion of the volume of the spray cloud/number of droplet particles contained within (above/below) a given size range); and
  • the PDPA particle size data for a second set of experiments is reported in Table 15c below wherein the dicamba final kg/ha values for formulation 926Y7O Samples 5, 6 and 7 were 0.072, 0.35 and 0.7 kg/ha, respectively.
  • the eye irritation potential of an aqueous formulation of the present invention was evaluated.
  • a formulation consisting 61 wt % a.e. aqueous MEA dicamba solution having a pH of 8.5 was prepared. Eye irritation testing was done according to the methods provided in U.S. Environmental Protection Agency Office of Prevention, Pesticides and Toxic Substances, Health Effects Test Guidelines: OPPTS 870.2400 Acute Eye Irritation.
  • OPPTS 870.2400 Acute Eye Irritation.
  • the eyes of 3 rabbit animals were treated with the formulation and were scored for effects on the cornea, iris, and conjunctivae (redness, swelling and discharge).
  • the eyes of 3 rabbit animals were treated with each formulation to determine the potential for formulations 908D1S and 929P6H to produce irritation from a single instillation via the ocular route.
  • Prior to testing of the formulations one drop of 2% ophthalmic fluorescein sodium was instilled into both eyes of each rabbit. After about 30 seconds, the eyes were rinsed with physiological saline (0.9% NaCl) and then evaluated and scored for corneal damage and abnormalities using an ultraviolet light source. Three healthy rabbits, not previously tested and without preexisting ocular irritation, were selected for testing.
  • 2-3 drops of ocular anesthetic Tetracaine Hydrochloride Ophthalmic Solution 0.5%) were placed in each of both eyes of each rabbit.
  • the time interval with the highest mean score (Maximum Mean Total Score—MMTS) for all rabbits was used to classify the test substance by the system of Kay and Calandra (Kay, J. H. and Calandra, J. C., Interpretation of eye irritation tests, J. Soc. Cos. Chem., 13:281-289 (1962)).
  • Formulation 929P6H is classified as mildly irritating to the eye and meets the requirements for the EC classification of “No classification for ocular irritation.
  • Iris A Values 0 0 0 0 A ⁇ 5 0 0 0 0 III. Conjunctivae A. Redness 2 0 0 0 B. Chemosis 1 0 0 0 C. Discharge 2 1 0 0 (A + B + C) ⁇ 2 10 2 0 0 Total 10 2 0 0 a 2% ophthalmic fluorscein used to evaluate the extent or verify the absence of corneal opacity
  • Formulation 908D1S is classified as mildly irritating to the eye and meets the requirements for the EC classification of “No classification for ocular irritation.”

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US11503826B2 (en) 2022-11-22
WO2011019652A3 (fr) 2011-06-30
WO2011019652A2 (fr) 2011-02-17

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