Mitigating Necrosis in Transgenic Glyphosate-Tolerant Cotton Plants Treated with Herbicidal Glyphosate Formulations

Abstract

This invention relates generally to improved methods and herbicidal glyphosate compositions for use in controlling the growth of weeds and unwanted vegetation, and particularly for use in controlling weeds in a crop of transgenic glyphosate-tolerant cotton plants by over-the-top, foliar application of a herbicidal glyphosate formulation.

1 - 34 . (canceled) 
     
     
         35 . A herbicidal glyphosate composition useful for killing or controlling the growth of weeds in a field containing a crop of transgenic glyphosate-tolerant cotton plants, comprising:
 N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof;   N-(phosphonomethyl)iminodiacetic acid or salt thereof; and   a safening agent in a concentration sufficient to inhibit significant leaf necrosis in said crop induced by N-(phosphonomethyl)iminodiacetic acid or salt thereof present in the herbicidal glyphosate composition, said safening agent selected from the group consisting of an adjuvant, metal ions, antioxidants, humectants, light absorbing compounds, and mixtures thereof.   
     
     
         36 - 54 . (canceled) 
     
     
         55 . The herbicidal glyphosate composition of  claim 35  wherein the safening agent comprises an antioxidant selected to inhibit significant leaf necrosis in said crop of transgenic glyphosate-tolerant cotton plants induced by N-(phosphonomethyl)iminodiacetic acid or salt thereof present in said herbicidal glyphosate composition. 
     
     
         56 . The composition of  claim 55  wherein the antioxidant is selected from the group consisting of hydroquinone, resorcinol, BHA, BHT and mixtures thereof. 
     
     
         57 . The composition of  claim 55  wherein the molar ratio of antioxidant to N-(phosphonomethyl)iminodiacetic acid equivalent is from about 50:1 to about 1:1. 
     
     
         58 . The herbicidal glyphosate composition of  claim 35  wherein the safening agent comprises a humectant selected to inhibit significant leaf necrosis in said crop of transgenic glyphosate-tolerant cotton plants induced by N-(phosphonomethyl)iminodiacetic acid or salt thereof present in said herbicidal glyphosate composition. 
     
     
         59 . The composition of  claim 58  wherein the humectant is hygroscopic and substantially non-ionizable in water. 
     
     
         60 . The composition of  claim 58  wherein the humectant comprises a polyhydroxy alcohol. 
     
     
         61 . The composition of  claim 60  wherein the humectant is selected from the group consisting of sorbitol, xylitol, inositol, mannitol, pantothenol, glycerol and derivatives and mixtures thereof. 
     
     
         62 . (canceled) 
     
     
         63 . The herbicidal glyphosate composition of  claim 35  wherein the safening agent comprises a light absorbing compound selected to inhibit significant leaf necrosis in said crop of transgenic glyphosate-tolerant cotton plants induced by N-(phosphonomethyl)iminodiacetic acid or salt thereof present in said herbicidal glyphosate composition. 
     
     
         64 - 80 . (canceled) 
     
     
         81 . An aqueous herbicidal concentrate composition comprising at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof and less than 5 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)iminodiacetic acid or salt thereof, wherein:
 the composition further comprises aminomethylphosphonic acid and the weight ratio of N-(phosphonomethyl)iminodiacetic acid or a salt thereof to aminomethylphosphonic acid is not more than 0.25:1; or   the composition further comprises at least one surfactant other than an alkoxylated alkyl amine or an alkoxylated phosphate ester; or   the N-(phosphonomethyl)glycine is present predominantly in the form of the potassium, dipotassium, monoammonium, diammonium, sodium, monoethanolamine, n-propylamine, ethylamine, ethylenediamine, hexamethylenediamine or trimethylsulfonium salt thereof; or   the composition further comprises a surfactant component comprising an alkoxylated alkylamine and an alkoxylated phosphate ester; or   the N-(phosphonomethyl)glycine is present predominantly in the form of the isopropylamine salt thereof.   
     
     
         82 - 111 . (canceled) 
     
     
         112 . A technical grade glyphosate composition comprising:
 (i) at least 95 wt. % N-(phosphonomethyl)glycine acid equivalent, less than 0.15 wt. % N-(phosphonomethyl)iminodiacetic acid or a salt thereof, and a byproduct selected from not more than 0.7 wt. % N-formyl-N-(phosphonomethyl)glycine and not more than 0.03 wt. % N-methyliminodiacetic acid, the weight percentages being on a dry basis; or   (ii) at least 90 wt. % N-(phosphonomethyl)glycine acid equivalent, less than 0.6 wt. % N-(phosphonomethyl)iminodiacetic acid or a salt thereof, and aminomethylphosphonic acid, wherein the weight ratio of N-(phosphonomethyl)iminodiacetic acid or a salt thereof to aminomethylphosphonic acid is not more than 0.18:1, 0.19:1, 0.20:1, 0.21:1, 0.22:1, 0.23:1, 0.24:1 or 0.25:1, the weight percentages being on a dry basis; or   (iii) at least 90 wt. % N-(phosphonomethyl)glycine acid or salt thereof, less than 0.45 wt. % N-(phosphonomethyl)iminodiacetic acid or a salt thereof, and at least 0.02 wt. % glycine or salt thereof, the weight percentages being on a dry acid equivalent basis; or   (iv) at least 90 wt. % N-(phosphonomethyl)glycine acid equivalent, between about 0.02 wt. % and about 0.25 wt. % N-(phosphonomethyl)iminodiacetic acid or a salt thereof, and a byproduct selected from not more than 0.6 wt. % N-formyl-N-(phosphonomethyl)glycine and not more than 0.03 wt. % N-methyliminodiacetic acid, the weight percentages being on a dry acid equivalent basis.   
     
     
         113 - 159 . (canceled) 
     
     
         160 . An aqueous herbicidal concentrate composition comprising:
 (i) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof; less than 5 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)iminodiacetic acid or salt thereof; and aminomethylphosphonic acid (acid equivalent), wherein the weight ratio of N-(phosphonomethyl)iminodiacetic acid or a salt thereof to aminomethylphosphonic acid is not more than 0.25:1; or   (ii) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof, less than about 5 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)iminodiacetic acid or salt thereof, and at least one surfactant other than an alkoxylated alkyl amine or an alkoxylated phosphate ester; or   (iii) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine predominantly in the form of the potassium, dipotassium, monoammonium, diammonium, sodium, monoethanolamine, n-propylamine, ethylamine, ethylenediamine, hexamethylenediamine or trimethylsulfonium salt thereof, and less than about 5 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)iminodiacetic acid or salt thereof; or   (iv) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof, less than about 5 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)iminodiacetic acid or salt thereof, and at least one surfactant component comprising an alkoxylated alkyl amine or an alkoxylated phosphate ester; or   (v) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine predominantly in the form of the isopropylamine salt thereof, and less than about 5 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)iminodiacetic acid or salt thereof; or   (vi) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof; less than 0.45 wt. % of N-(phosphonomethyl)iminodiacetic acid or salt thereof (acid equivalent) on a glyphosate, a.e., basis; and aminomethylphosphonic acid, wherein the weight ratio of N-(phosphonomethyl)iminodiacetic acid or a salt thereof (acid equivalent) to aminomethylphosphonic acid (acid equivalent) is not more than 0.25:1; or   (vii) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof, less than about 0.45 wt. % of N-(phosphonomethyl)iminodiacetic acid or salt thereof (acid equivalent) on an N-(phosphonomethyl)glycine, a.e., basis, and at least one surfactant other than an alkoxylated alkyl amine or an alkoxylated phosphate ester; or   (viii) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine predominantly in the form of the potassium, dipotassium, monoammonium, diammonium, sodium, monoethanolamine, n-propylamine, ethylamine, ethylenediamine, hexamethylenediamine or trimethylsulfonium salt thereof, and less than about 0.45 wt. % (phosphonomethyl)iminodiacetic acid or salt thereof (acid equivalent) on an N-(phosphonomethyl)glycine, a.e., basis; or   (ix) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine or an agronomically acceptable salt thereof, less than about 0.45 wt. % N-(phosphonomethyl)iminodiacetic acid or salt thereof on an N-(phosphonomethyl)glycine basis, and at least one surfactant component comprising an alkoxylated alkyl amine or an alkoxylated phosphate ester; or   (x) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine predominantly in the form of the isopropylamine salt thereof, and less than about 0.45 wt. % N-(phosphonomethyl)iminodiacetic acid or salt thereof (acid equivalent) on an N-(phosphonomethyl)glycine, a.e., basis; or   (xi) at least about 360 grams per liter (on an acid equivalent basis) of N-(phosphonomethyl)glycine predominantly in the form of a salt thereof, less than about 0.45 wt. % N-(phosphonomethyl)iminodiacetic acid or salt (acid equivalent), and at least about 0.02 wt. % glycine or a salt thereof (acid equivalent), the weight percentages being on an acid equivalent basis relative to N-(phosphonomethyl)glycine, a.e.   
     
     
         161 - 240 . (canceled) 
     
     
         241 . A process for the preparation of glyphosate by oxidation of N-(phosphonomethyl)iminodiacetic acid wherein the glyphosate product has a low N-(phosphonomethyl)iminodiacetic acid content, the process comprising:
 contacting an aqueous reaction medium containing N-(phosphonomethyl)iminodiacetic acid with a gas comprising molecular oxygen in the presence of a catalyst for the oxidation;   recovering a glyphosate product from glyphosate obtained in the resulting product reaction solution,   wherein (i) the recovery of said glyphosate product comprises separating such product from an aqueous mixture wherein the ratio of total N-(phosphonomethyl)iminodiacetic acid content to total glyphosate content is at least 25% greater than the corresponding ratio in said product reaction solution, oxygen having been caused to flow through said aqueous reaction medium in the presence of said catalyst to an extent sufficient to reduce the N-(phosphonomethyl)iminodiacetic acid content of said product reaction solution to a level such that said recovered glyphosate product has an N-(phosphonomethyl)iminodiacetic acid content less than about 600 ppm, basis glyphosate; or (ii) oxygen having been caused to flow through said aqueous reaction medium in the presence of said catalyst to an extent sufficient to reduce the N-(phosphonomethyl)iminodiacetic acid content of said product reaction solution to a level such that said recovered glyphosate product has an N-(phosphonomethyl)iminodiacetic acid content less than about 600 ppm, basis glyphosate; and   removing said glyphosate product from the process.   
     
     
         242 - 258 . (canceled) 
     
     
         259 . A process for the preparation of glyphosate by oxidation of N-(phosphonomethyl)iminodiacetic acid wherein the glyphosate product has a low N-(phosphonomethyl)iminodiacetic acid content, the process comprising:
 oxidizing N-(phosphonomethyl)iminodiacetic acid in an aqueous reaction medium to produce a product reaction solution containing glyphosate and unreacted N-(phosphonomethyl)iminodiacetic acid; and   recovering glyphosate from said product reaction solution in a product form having a N-(phosphonomethyl)iminodiacetic acid content not greater than 600 ppm on a glyphosate basis,   wherein the recovery of said product form comprises (i) contacting an aqueous solution comprising said product reaction solution, or a solution comprising N-(phosphonomethyl)iminodiacetic acid derived from said product reaction solution, with an anion exchange resin which has a selective affinity for N-(phosphonomethyl)iminodiacetic acid in preference to glyphosate; or (ii) crystallizing glyphosate from a crystallizer feed solution comprising or derived from said product reaction solution; subjecting the resulting slurry of glyphosate crystals in mother liquor to solid/liquid separation; purging a fraction of said mother liquor for removal of N-(phosphonomethyl)iminodiacetic acid from the process; and recycling another fraction of said mother liquor to a crystallizer in which glyphosate is crystallized from said feed solution, the volume of said purge fraction relative to the volume of said recycle fraction being sufficient that the solid glyphosate crystals separated in said solid/liquid separation step have an N-(phosphonomethyl)iminodiacetic acid content lower than 600 ppm or can be contacted with an aqueous wash medium to produce a solid glyphosate product having such lower N-(phosphonomethyl)iminodiacetic acid content.   
     
     
         260 - 271 . (canceled) 
     
     
         272 . A process a set forth in  claim 259  wherein, prior to purging a fraction of said mother liquor, the mother liquor is contacted with an anion exchange resin having a selective affinity for N-(phosphonomethyl)iminodiacetic acid greater than for glyphosate. 
     
     
         273 . A process as set forth in  claim 259  wherein said mother liquor is contacted in a chloride ion exchange zone with a anion exchange resin that is selective for chloride in preference to N-(phosphonomethyl)iminodiacetic acid, and in a PMIDA ion exchange zone with an anion exchange resin that is selective N-(phosphonomethyl)iminodiacetic acid in preference to glyphosate. 
     
     
         274 - 275 . (canceled) 
     
     
         276 . A process for the preparation of glyphosate by oxidation of N-(phosphonomethyl)iminodiacetic acid wherein the glyphosate product has a low N-(phosphonomethyl)iminodiacetic acid content, the process comprising:
 (i) contacting an aqueous medium containing N-phosphonomethyl-iminodiacetic acid in a primary reaction system with a gas comprising molecular oxygen in the presence of a particulate catalyst for the oxidation to produce a product slurry comprising a product reaction solution comprising glyphosate and unreacted N-(phosphonomethyl)iminodiacetic acid, and having said particulate catalyst suspended therein; separating said catalyst from said reaction product solution to produce a filtered product reaction solution; and contacting an aqueous solution comprising said filtered product reaction solution, or derived therefrom, with an oxidizing agent in a polishing reaction zone for further conversion of N-phosphonomethyl-iminodiacetic acid to glyphosate; or   (ii) contacting an aqueous reaction medium containing N-(phosphonomethyl)iminodiacetic acid with a gas comprising molecular oxygen in the presence of a noble metal on carbon catalyst, and in the absence of a concentration of a non-noble metal promoter that would be effective to either retard the oxidation of N-(phosphonomethyl)iminodiacetic acid or causes the rate of consumption of oxygen in the oxidation of formaldehyde or formic acid to be materially increased relative to the rate of consumption of oxygen in the oxidation of N-(phosphonomethyl)iminodiacetic acid; and maintaining contact of said reaction medium with gas comprising molecular oxygen for a time sufficient to reduce the N-(phosphonomethyl)iminodiacetic acid content of the resulting product reaction solution to not greater than 250 ppm; or   (iii) oxidizing N-(phosphonomethyl)iminodiacetic acid in an aqueous reaction medium to produce a product reaction solution containing glyphosate and unreacted N-(phosphonomethyl)iminodiacetic acid; transferring said product reaction solution to a product recovery process by which a plurality of glyphosate products are produced; and operating said product recovery process to produce at least two separate glyphosate salt products of differing N-(phosphonomethyl)iminodiacetic acid content wherein the glyphosate basis N-(phosphonomethyl)iminodiacetic acid content of one of said products is less than about 1000 ppm and at least 25% lower than the N-(phosphonomethyl)iminodiacetic acid content of another of said plurality of glyphosate products; or   (iv) contacting N-(phosphonomethyl)iminodiacetic acid with an oxidizing agent in an aqueous reaction medium within an oxidation reaction zone in the presence of a catalyst for the oxidation, thereby effecting oxidation of N-(phosphonomethyl)iminodiacetic acid and producing a reaction solution comprising glyphosate or another intermediate which can be converted to glyphosate; and further processing said reaction solution to produce a glyphosate product containing not more than about 600 ppm N-(phosphonomethyl)iminodiacetic acid or salt thereof, wherein the oxidation of N-(phosphonomethyl)iminodiacetic acid in said aqueous reaction medium is continued until the concentration of N-(phosphonomethyl)iminodiacetic acid in said reaction medium has been reduced to a terminal concentration such that said further processing yields a not greater than about 600 ppm, basis glyphosate.   
     
     
         277 - 329 . (canceled) 
     
     
         330 . The herbicidal glyphosate composition of  claim 35  wherein the safening agent comprises an adjuvant and the N-(phosphonomethyl)glycine is predominantly in the form of an agronomically acceptable salt thereof selected from the group consisting of alkali metal salts, alkylamine salts and alkanolamine salts of N-(phosphonomethyl)glycine, wherein the concentration of said adjuvant in the herbicidal glyphosate formulation is selected such that the rate of transfer of N-(phosphonomethyl)iminodiacetic acid or salt thereof into the foliar tissues of said crop of transgenic glyphosate-tolerant cotton plants is sufficiently slow to inhibit significant leaf necrosis in said crop induced by N-(phosphonomethyl)iminodiacetic acid or salt thereof present in the herbicidal glyphosate formulation. 
     
     
         331 . The herbicidal glyphosate composition of  claim 330  wherein said adjuvant is selected from the group consisting of an alkyl polyglucoside, a diol, a triol, a polyol, a dialkanolamine, a trialkanolamine, a polyalkylene glycol, a dialkylene glycol, a trialkylene glycol, a polyhydric alcohol ester, an alkoxylated amide, an alkoxylated alkylphenol, an alkoxylated arylphenol, a fatty alcohol alkoxylate, an alcohol alkoxylate and mixtures thereof. 
     
     
         332 . The herbicidal glyphosate composition of  claim 331  further comprising a salt of N-(phosphonomethyl)glycine other than ammonium or diammonium.