Classifications

• • 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

• This invention relates to compositions used to control weeds, and in particular relates to compositions comprising N-phosphonomethylglycine, commonly known as glyphosate. More particularly the invention relates to compositions comprising salts of glyphosate, and to methods for controlling weeds using these formulations.
• Glyphosate in acid form is relatively water-insoluble, and in order to achieve significant water solubility, glyphosate has generally been formulated as a salt.
• Magin et al in US5710104 describes amine, alkali metal, alkylsulfonium alkylphosphonium, sulfonylamine and aminoguanidine salts of glyphosate.
• EP124351 describes mixed long-chain alkylammonium salts of glyphosate.
• Gaughan in EP 369076 describes trisubstitued sulfonium and sulfoxonium salts of glyphosate.
• the glyphosate salts described above generally comprise a particular cation which is present in a mole ratio of at least 0.9:1 with glyphosate.
• glyphosate salts include the "Accord”, “Roundup”, “Roundup Ultra” and “Roundup Xtra” brands of Monsanto Company. These formulations contain glyphosate as the isopropylammonium salt. Monsanto's Roundup Geoforce brand contains glyphosate sodium salt and Roundup Dry contains glyphosate ammonium salt. The “Touchdown” brand of Zeneca, contains glyphosate trimethyl sulfonium salt.
• the above commercial formulations of glyphosate all comprise particular low- molecular weight salt cations (generally of molecular weight less than 300) and a key criterion for selecting the salt in such a formulation is the capacity to achieve high loading levels of glyphosate (acid equivalent) in the formulation.
• the herbicidal activity of glyphosate salts can be enhanced by adding a certain quantity of amphiphilic agents (including amphiphilic salts) to the formulation.
• amphiphilic materials including surfactants
• Amphiphilic agents may be identified by virtue of their capacity to cause one or more of the following phenomena:
• micellar aggregates • formulation of micellar aggregates, at concentrations above the critical micellar concentration (CMC)
• Amphiphilic agents which have been claimed to enhance the herbicidal efficacy of formulations comprising glyphosate salts include the following: quaternary ammonium surfactant; etheramine surfactants; alkylether and amine surfactant combinations; acetylenic diol and alkyl(poly)glycoside surfactant combinations; lipophilic fatty amine ethoxylate surfactants; alkoxylated amine surfactants; alkyl polyglycoside agents; secondary or tertiary alcohol surfactants; silicone copolymer wetting agents and trialkylamine oxide or quaternary amine or trialkylbetaine surfactant combinations; sorbitan fatty acid ester and amine, quaternary ammonium or alkylglycoside surfactant combinations; surfactants derived from alkanethiols; polyoxyalkylene trisiloxane surfactants; super-wetting agents such as silicone-based and fluorocarbon-based surfactants
• Non-amphiphilic additives have also been claimed to enhance the bioefficacy of glyphosate, for example
• Hay (AU674464) has described the use of an alkyl-substituted ammonium sulfate
• low molecular weight non-amphiphilic cations include but are not limited to cations such as isopropylammonium, potassium, sodium, ammonium, trimethylsulfonium and monoethanolammonium cations.
• glyphosate composition comprising potassium cations and either isopropylammonium cations or monoethanolammonium cations or both.
• the composition may comprise other cations such as selected from the group consisting of ammonium, sodium, trimethylsulfonium and mixtures thereof.
• the potassium cations isopropylammonium cations, monoethanolammonium cations and optionally other low molecular weight non-amphiphilic cations act as counter-ions to glyphosate anion.
• the glyphosate composition comprises potassium and isopropylammonium cations and optionally other cations, and the mole ratio of isopropylammonium to potassium cations is less than 30:1 and greater than 1 :10, more preferably less than 15:1 and greater than 1 :2.
• the glyphosate composition comprises potassium and monoethanolammonium cations, and the mole ratio of monoethanolammonium to potassium cations is less than 30:1 and greater than 1 :10, more preferably less than 15:1 and greater than 1 :2.
• the glyphosate composition comprises potassium, monoethanolammonium and isopropylammonium cations, and the mole ratio of isopropylammonium to potassium cations is in the range of from 30:1 to 1 :10, and the mole ratio of monoethanolammonium to potassium cations in the range of 30:1 to 1 :10. More preferably the mole ratio of isopropylammonium to potassium cations is in the range of 10:1 to 1 :5, and the mole ratio of monoethanolammonium to potassium cations in the range of from 10:1 to 1 :5.
• the glyphosate compositions preferably comprises potassium, monoethanolammonium and isopropylammonium cations in the mole ratio of isopropylammonium cations to the sum of potassium, monoethanolammonium and isopropylammonium cations in the range 50:100 to 95:100.
• the mole ratio of monoethanolammonium to potassium cations in the above formulation is in the range 1 :2 to 7:1.
• a particularly preferred glyphosate composition comprises isopropylammonium, monoethanolammonium and potassium cations in the ratio 68:16:16.
• the glyphosate composition of the invention may and preferably will contain a surfactant.
• a surfactant for use with the glyphosate composition may be selected from the group consisting of: etheramine surfactants having the representative chemical structure (a)
• Ri is a straight or branched chain C 6 to about C 22 alkyl, aryl or alkylaryl group
• m is an average number from 1 to about 10
• R 2 in each of the m (O - R 2 ) groups is independently C-i-C 4 alkylene
• R 3 groups are independently C ⁇ -C 4 alkylene
• x and y are average numbers such that x+y is in the range from 2 to about 60;
• Ri is a straight or branched chain CQ to about C 22 alkyl, aryl or alkylaryl group
• m is an average number from 1 to about 10
• R 2 in each of the m (O - R 2 ) groups is independently C ⁇ -C alkylene
• R 3 groups are independently C-i-C alkylene
• R 4 is C-i-C 4 alkyl
• x and y are average numbers such that x+y is in the range from 0 to about 60 and
• a " is an agriculturally acceptable anion
• Ri is a straight or branched chain CQ to about C 22 alkyl, aryl or alkylaryl group
• m is an average number from 1 to about 10
• R 2 in each of the m (O- R 2 ) groups is independently C C 4 alkylene
• R 3 groups are independently C ⁇ -C alkylene
• x and y are average numbers such that x+y is in the range from 2 to about 60.
• the glyphosate composition of the invention may be in the form of a water soluble granule or powder, a water dispersible granule or powder, an aqueous solution or other suitable form.
• the composition is in the form of an aqueous solution containing in the range of from 0.5 to 600 g/l glyphosate mixed salt (based on glyphosate acid) and preferably from 5.0 to 600 g/l.
• the number of moles of potassium cation in the composition will be at least 1% based on the number of moles of glyphosate (determined as glyphosate acid). More preferably the amount of potassium is in the range of from 3 to 50 mole percent of total glyphosate. The amount of potassium will preferably also constitute at least 3% on a molar basis of the total number of moles of potassium, monoisopropylammonium and isopropylammonium and preferably from 3 to 50 mole percent.
• the invention provides a glyphosate composition in solid particulate form.
• the particles of the composition may be fine particles such as powder or alternatively the compositions may be in granular or prill form.
• Solid powder or granular free-flowing glyphosate compositions may include a surfactant such as at least one surfactant selected from the group consisting of
• These solid compositions may include urea, other fertilizers, such as diammonium phosphate; acidifying agents, such as anionic phosphate esters of the formula ROP(O)(OH) 2 wherein R is alkyl, alkylaryl, alkoxylated alkyl, or alkoxylated alkylaryl; and/or sticking agents, such as fatty acids, fatty acid esters or alkoxylated novolac resins.
• urea other fertilizers, such as diammonium phosphate
• acidifying agents such as anionic phosphate esters of the formula ROP(O)(OH) 2 wherein R is alkyl, alkylaryl, alkoxylated alkyl, or alkoxylated alkylaryl
• sticking agents such as fatty acids, fatty acid esters or alkoxylated novolac resins.
• the adjuvant includes urea and the composition is eutectic.
• the adducts may be formed by mixing and heating a composition containing urea to form a uniform liquid melt and then cooling the adduct into a solid, free- flowing powder.
• the solid free flowing adjuvants may be included in the composition prior to forming the melt or dry blended with glyphosate component of the composition.
• composition may also be formed into water soluble or dispersible granules by applying the surfactant preferably by spraying into a mixer containing a solid flowable mixture including mixed salts of glyphosate and optionally other additives such as fertilizers, fillers or the like and forming granules by extrusion, pan granulation or other suitable method.
• the solid adjuvant systems will most preferably use non-ionic surfactants. These surfactants may be liquids or waxy solids. Adsorbents, such as clays or silicas, may be employed but it may be desirable to avoid such insoluble additives where spray equipment is to be used as they may clog spray lines and nozzles or increase nozzle wear.
• the invention provides a method of preparation of the above described glyphosate composition.
• the glyphosate composition may be prepared by mixing salts of glyphosate such as the potassium and one or both of the isopropylamine and ethanolammonium salts in solid form or aqueous solution.
• one or more cations may be provided by combining a base with glyphosate wherein the base provides one or more of the cations in aqueous slurry of glyphosate (preferably in the form of glyphosate acid).
• the method of the invention comprises forming a slurry of glyphosate (preferably as glyphosate acid) and adding separately or in admixture bases which form the potassium and one or both of monoethanolammonium and isopropylammonium cations on addition to the slurry.
• the base may for example contain potassium hydroxide and optionally one or both of isopropylamine and monoethanolamine.
• the invention provides a method of forming a solid glyphosate composition
• a method of forming a solid glyphosate composition comprising forming a slurry of glyphosate; combining the slurry with potassium hydroxide and one or both of monoisopropropylamine and monoethanolamine to form a composition comprising the mixed salts of glyphosate.
• the resulting glyphosate mixed salt composition may in many cases be isolated by filtration for example from an aqueous/alcohol mixture. It may be formulated with suitable surfactants and optionally other additives such as urea, fertilizers, fillers and ammonium sulphate.
• the invention provides a method of preparing a glyphosate composition comprising forming a mixture of glyphosate salts including at least the potassium salts and at least one of ethanolammonium and isopropylammonium salts of glyphosate.
• the invention provides a method of controlling weeds comprising applying to the weeds a composition of glyphosate as hereinbefore described.
• the compositions of the invention generally exhibit synergy.
• the mixed salts of the invention typically provide a level of activity in controlling weeds which would not be expected from the additive effect of individual salt.
• the mixed salt glyphosate formulations of this invention may further comprise amphiphilic adjuvants known to the art, for example adjuvants desc ⁇ bed previously.
• Example 1 Preparation of Glyphosate Formulations with a Range of Non- Amphiphilic Cations
• the non-amphiphilic cations in the above formulation were I PA cations and the mole ratio of IPA cations to other non-amphiphilic cations was 100:0
• the non-amphiphilic cations in the above formulation were IPA cations and K cations, and the relative mole ratio of these cations was 40:60
• Formulation 620 consisted of • 41.99 parts of glyphosate technical, comprising 85% glyphosate, 11.6% water and 3.4% impurities;
• the non-amphiphilic cations in the above formulation were IPA and K cations, and the relative mole ratio of these cations was 60:40
• the non-amphiphilic cations in the above formulation were MEA cations, and the relative mole ratio s of these cations to other non-amphiphilic cations was 100:0
• the non-amphiphilic cations in the above formulations were MEA cations and K cations, and the relative mole ratio of these cations was 90:10
• Formulation 642 consisted of • 47.6 parts glyphosate technical, comprising 85% glyphosate, 11.6% water, 3.4% impurities; and 7.33 parts isopropylamine; and 5.65 parts ethanolamine(EA); and 1.19 parts of 90% w/w potassium hydroxide; and 7.93 parts of surfactant, TERWET 1215; and 28.71 parts water
• non-amphiphilic cations in the above formulations were K, EA, IPA and the relative mole ratios of these cations was 8:40:52
• Formulation 521 consisted of • 32.78 parts glyphosate technical material comprising 85% glyphosate, 3% impurities and 12% water
• the non-amphiphilic cations in the above formulations were IPA cations and the mole ratio of IPA cations to other non-amphiphilic cations was 100:0
• a solid formulation may be prepared by combining technical glyphosate in a slurry with potassium hydroxide, ethanolamine and isopropylamine in a molar ratio of 8:40:52.
• a mixed salt formulation may be added to a solid adjuvant containing: Wt polyoxyethylene (12) tridecyl alcohol 50% urea 48.0% water 2%
• the components may be melted at about 120°C and stirred to form a liquid melt which may be sprayed into a cooling tower or extruded to form prills or granules.
• a granular composition may also be prepared by applying a surfactant solution to a flowable powder containing the glyphosate mixed salts and extruding the composition to form pellets and drying the pellets to form granules of less than 15% by weight water content.
• Herbicide application Herbicide formulations were applied using an enclosed laboratory track-sprayer fitted with three 110° flat fan nozzles (Spraying Systems Tee Jet 11001) spaced at 50cm intervals across the boom. The boom spray moved along a fixed track at 6 km h "1 , sprayed at a water volume of 64 L ha "1 with a pressure of 200Kpa. Eight replicate treatments were sprayed per rate. Application rates of 35, 70 and 140g/ha were used. Results (g/plant) were averaged across all application rates.
• Spray solutions were prepared by combining aqueous stock solutions of glyphosate salts (all at 450g/L glyphosate acid equivalent) in the proportions shown in Table 5.11 , and adding the resultant solution to water together with TERWET 1215 (a surfactant sold by Huntsman Australia comprising an aqueous blend of alkyl polysaccharides and alkoxylated alkyl ether polyamines), to represent the application of a formulation containing 450g/L glyphosate acid equivalent and 120g/L TERWET 1215 to test plants at both 70g/ha glyphosate acid and 140g/ha glyphosate acid equivalent at 64L/ha water volume.
• TERWET 1215 a surfactant sold by Huntsman Australia comprising an aqueous blend of alkyl polysaccharides and alkoxylated alkyl ether polyamines
• Herbicide formulations were applied at 64 litres/ha using an enclosed laboratory track-sprayer fitted with three 110° flat fan nozzles (TeeJet 11001 ; 200kPa). After the application of treatments, pots were returned to the greenhouse for an additional 15 days before plants were assessed for fresh weight. Each spray treatment was replicated eight times.
• the mean fresh weight of each spray treatment was calculated.
• a predicted fresh weight was calculated from the weighted average of the individual salt fresh weight mean value. Treatments where the observed fresh weight of the mixed salt treatment is lower than the corresponding predicted value calculated from the weighted average is considered to show a synergistic effect.
• Spray solutions were prepared by combining aqueous stock solutions of glyphosate salts (all at 450g/L glyphosate acid equivalent) in the proportions shown in Table 5.11 , and adding the resultant solution to water together with TERWET 1215 (a surfactant sold by Huntsman Australia comprising an aqueous blend of alkyl polysaccharides and alkoxylated alkyl ether polyamines), to represent the application of a formulation containing 450g/L glyphosate acid equivalent and 120g/L TERWET 1215 to test plants at both 70g/ha glyphosate acid and 140g/ha glyphosate acid equivalent at 64L/ha water volume.
• TERWET 1215 a surfactant sold by Huntsman Australia comprising an aqueous blend of alkyl polysaccharides and alkoxylated alkyl ether polyamines
• Oat seeds (3/pot) were sown at 5mm depth in 10cm diameter pots filled with potting mix. One week after seedling emergence, seedlings were tinned for uniform size to one or two seedlings per pot.
• plants were grown in a temperature controlled greenhouse (14-25°C) for 16 days then outdoors for 4 days prior to spray application to simulate field conditions (3-4 leaf stage).
• Herbicide formulations were applied at 64 litres/ha using an enclosed laboratory track-sprayer fitted with three 110° flat fan nozzles (TeeJet 11001 ; 200kPa). After the application of treatments, pots were returned to the greenhouse for an additional 15 days before plants were assessed for fresh weight. Each spray treatment was replicated eight times. The mean fresh weight for each spray treatment was calculated. For each salt mixture treatment a predicted fresh weight was calculated from the weighted average of the individual salt fresh weight mean value. Treatments where the observed fresh weight of the mixed salt treatment is lower than the corresponding predicted value calculated from the weighted average are considered to show a synergistic effect. The synergy factor was calculated as in example 5.1. Treatments were the observed fresh weight of the mixed salt treatment is higher than the corresponding predicted value calculated from the weighted average are considered to show an antagonistic effect.
• Spray solutions were prepared by combining aqueous stock solutions of glyphosate salts (all at 450g/L glyphosate acid equivalent) in the proportions shown in Table 5.11 , and adding the resultant solution to water together with TERWET 1215 (a surfactant sold by Huntsman Australia comprising an aqueous blend of alkyl polysaccharides and alkoxylated alkyl ether polyamines), to represent the application of a formulation containing 450g/L glyphosate acid equivalent and 120g/L TERWET 1215 to test plants at both 70g/ha glyphosate acid and 140g/ha glyphosate acid equivalent at 64L/ha water volume.
• TERWET 1215 a surfactant sold by Huntsman Australia comprising an aqueous blend of alkyl polysaccharides and alkoxylated alkyl ether polyamines
• Canola seeds (3/pots) were sown at 5 mm depth in 10 cm diameter pots filled with potting mix. One week after seedling emergence, seedlings were thinned for uniform size to or two seedlings per pot. For efficacy studies, plants were grown in a temperature controlled greenhouse (14-25°C) for 16 days then outdoors for 4 days prior to spray application to simulate field conditions (3-4 leaf stage).
• Herbicide formulations were applied at 64> litres/ha using an enclosed laboratory track-sprayer fitted with three 110° flat fan nozzles (TeeJet 11001 ; 200 kPa). After the application of treatments, pots were retuned to the greenhouse for an additional 15 days before plants were assessed for fresh weight. Each spray treatment was replicated eight times.
• the mean fresh weight for each spray treatment was calculated.
• a predicted fresh weight was calculated from the weighted average of the individual salt fresh weight mean value. Treatments where the observed fresh weight of the mixed salt treatment is lower than the corresponding predicted value calculated from the weighted average are considered to show a synergistic effect.
• the synergy factor was calculated as in example 5.1. Treatments where the observed fresh weight of the mixed salt treatment is higher than the corresponding predicted value calculated from the weighted average are considered to show an antagonistic effect.
• Spray solutions were prepared by combining aqueous stock solutions of glyphosate salts (all at 450g/L glyphosate acid equivalent) in the proportions shown in Table 6.11, and adding the resultant solution to water together with TERWET G3780A (an ethoxylated tallow amine surfactant sold by Huntsman Australia), to represent the application of a formulation containing 450g/L glyphosate acid equivalent and 120g/L TERWET G3780A to test plants at both 70g/ha glyphosate acid and 140g/ha glyphosate acid equivalent at 64L/ha water volume.
• TERWET G3780A an ethoxylated tallow amine surfactant sold by Huntsman Australia
• Herbicide formulations were applied at 64 litres/ha using an enclosed laboratory track-sprayer fitted with three 110° flat fan nozzles (TeeJet 11001 ; 200 kPa).
• the mean fresh weight for each spray treatment was calculated.
• a predicted fresh weight was calculated from the weighted average of the individual salt fresh weight mean value.
• Treatments where the observed fresh weight of the mixed salt treatment is lower than the corresponding predicted value calculated from the weighted average are considered to show a synergistic effect.
• the synergy factor was calculated as in example 5.1. Treatments were the observed fresh weight of the mixed salt treatment is higher than the corresponding predicted value calculated from the weighted average are considered to show an antagonistic effect.
• Spray solutions were prepared by combining aqueous stock solutions (all of 360 g/L glyphosate acid equivalent) in the proportions shown in Table 7.11 and adding the resultant solution to water together with SURFONIC AGM 550 to represent the application of a formulation containing 360g/L glyphosate acid equivalent and 120g/L SURFONIC AGM 550 to test plants at both 70g/ha and/or 140g/ha glyphosate acid equivalent at 64L/ha water volume.
• the formulation 360 STD was made using glyphosate MIPA salt at 360g/L acid equivalent and adding the resultant solution to water together with ethoxylated tallow-amine to represent the application of a formulation 360g/L glyphosate acid equivalent and 120g/L ethoxylated allowamine to test plants at both 70g/ha and/or 140g/ha glyphosate acid equivalent at 64L/ha water volume.
• the bioefficacy results at 14 days after treatment are provided in Table 7.11

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• 2001
  • 2001-08-03 AU AUPR6822A patent/AUPR682201A0/en not_active Abandoned
• 2002
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  • 2002-07-31 CA CA2454869A patent/CA2454869C/en not_active Expired - Lifetime
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  • 2002-07-31 WO PCT/AU2002/001016 patent/WO2003013241A1/en not_active Ceased
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  • 2002-07-31 AU AU2002325065A patent/AU2002325065C1/en not_active Expired
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