EP1211937A1 - Mannich condensate-based surfactant adjuvants and compositions thereof - Google Patents

Mannich condensate-based surfactant adjuvants and compositions thereof

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Publication number
EP1211937A1
EP1211937A1 EP00957523A EP00957523A EP1211937A1 EP 1211937 A1 EP1211937 A1 EP 1211937A1 EP 00957523 A EP00957523 A EP 00957523A EP 00957523 A EP00957523 A EP 00957523A EP 1211937 A1 EP1211937 A1 EP 1211937A1
Authority
EP
European Patent Office
Prior art keywords
alkenylphenol
alkoxylates
mannich
composition
substituted alkylphenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00957523A
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German (de)
French (fr)
Inventor
David Charles Lewis
Howard Meyer Stridde
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Specialty Chemicals Corp
Huntsman Petrochemical LLC
Original Assignee
Huntsman Specialty Chemicals Corp
Huntsman Petrochemical LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman Specialty Chemicals Corp, Huntsman Petrochemical LLC filed Critical Huntsman Specialty Chemicals Corp
Publication of EP1211937A1 publication Critical patent/EP1211937A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2627—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aromatic or arylaliphatic amine groups
    • 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
    • A01N25/30—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 characterised by the surfactants
    • 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 surfactants, and, more particularly, to surfactants that enhance the bioefficacy of herbicides, and to herbicide compositions comprising such surfactants.
  • Herbicide compositions are often characterized according to the identity of the active ingredient, and by the mode by which the active ingredient causes vegetation necrosis. Regardless of the active ingredient, most herbicides cause vegetation necrosis by interfering with one or more vital biological processes essential to the vegetation's survival. Yet, before the active ingredient of a herbicide can interfere with such biological processes, the active ingredient must somehow be absorbed into the vegetation. Unfortunately, this absorption is often hindered by the chemical nature of the active ingredient. Accordingly, in addition to active ingredients, most herbicide compositions also comprise other components, commonly termed adjuvants, that enhance the performance and absorption of the active ingredient. One class of adjuvants that is frequently used is surfactants. Surfactants are useful in herbicide compositions because they tend to both enhance the absorbing properties of the active ingredient, as well as facilitate application of the herbicide.
  • the literature discloses various classes of surfactant adjuvants.
  • One common class of surfactants includes derivatives of alkoxylated amines.
  • U.S. Pat. No. 5,683,958 discloses surfactants comprising tallow amine ethoxylates blended with a phosphate ester of an alkylphenol or alcohol ethoxylate
  • U.S. Pat. No. 5,798,310 discloses adjuvants comprising alkoxylated quaternary ammonium surfactants
  • U.S. Pat. No. 5,668,085 discloses glyphosate formulations comprising alkoxylated amine surfactants
  • 5,118,444 discloses amide-oxide surfactants produced by oxidizing tertiary polyalkoxylated amine surfactants.
  • the literature appears to lack any reference to the use of alkoxylated alkylphenol or alkenylphenol mannich condensates, phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, or alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates as suitable herbicide adjuvants.
  • alkoxylated alkylphenol or alkenylphenol mannich condensates phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, and alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates function to improve the bioefficacy of herbicide compositions containing such surfactants.
  • herbicide formulations comprising alkoxylated alkylphenol or alkenylphenol mannich condensates, their phosphate esters, or their alkoxylated phosphate esters are expected to have a reduced tendency to cause eye irritation.
  • the present invention is directed toward surfactant adjuvants that include alkoxylated alkylphenol or alkenylphenol mannich condensates, phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, and alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, herbicide compositions comprising such surfactants, and a method of controlling unwanted weeds or vegetation using such herbicide compositions.
  • surfactant adjuvants that include alkoxylated alkylphenol or alkenylphenol mannich condensates, phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, and alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, herbicide compositions comprising such surfactants, and a method of controlling unwanted weeds or vegetation using
  • the present invention provides for surfactants that further improve the bioefficacy of herbicides.
  • the surfactants comprise (i) primarily di-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, in combination with mono-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, (ii) primarily phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, and (iii) primarily alkoxylated phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate
  • the mono-substituted alkylphenol or alkenylphenol mannich condensates (I) and the di-substituted alkylphenol or alkenylphenol mannich condensates (II) have the following general structure:
  • R x is independently hydrogen or
  • each R y is independently: (i) hydrogen, (ii) - (R 2 O) g (R 3 O) h H, (iii)
  • R j is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms;
  • R 2 and R 3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms;
  • a, b, c, d, e, f, g, and h each independently vary from zero to about thirty; and
  • a+b-r-c+d+e+f+g+h is between zero and about two hundred and forty.
  • the present invention also provides for herbicide compositions that contain a surfactant of the present invention.
  • the herbicide compositions comprise a herbicidal active ingredient, a surfactant of the present invention, and optionally, one or more formulation aids.
  • the herbicide compositions of the present invention are expected to have a reduced tendency to cause eye and skin irritation.
  • the present invention additionally provides for a method of controlling unwanted weeds or vegetation using the herbicide compositions of the present invention.
  • the present invention relates to surfactants that enhance the bioefficacy of herbicides, herbicide compositions comprising such surfactants, and a method of controlling unwanted weeds or vegetation using the herbicide compositions of the present invention.
  • the surfactants of the present invention may be used in conjunction with any number of herbicidal active ingredients.
  • the use of the surfactants of the present invention with glyphosate is of particular interest because glyphosate is probably the most widely used herbicide.
  • Glyphosate or N-phosphonomethylglycine
  • Glyphosate is a broad-spectrum herbicide that is useful on essentially all annual and perennial plants, including, grasses, broad-leaved weeds, and woody plants.
  • Glyphosate promotes plant necrosis by inhibiting aromatic amino acid biosynthesis. By inhibiting aromatic amino acid synthesis, and thereby protein synthesis, glyphosate initially suppresses plant growth, which is soon followed by plant necrosis.
  • glyphosate In its free acid form, glyphosate has a low water solubility.
  • water-based glyphosate compositions typically contain a water soluble salt of glyphosate, such as the isopropylamine salt.
  • glyphosate In its free acid form, glyphosate has a low water solubility.
  • water-based glyphosate compositions typically contain a water soluble salt of glyphosate, such as the isopropylamine salt.
  • many commercially available herbicide compositions contain the water soluble mono- isopropylamine salt of glyphosate.
  • Glyphosate, and various water soluble derivatives of glyphosate are available from numerous manufactures.
  • the surfactants of the present invention may be prepared by heating one mole of an alkylphenol or alkenylphenol and two moles of diethanolamine, at a temperature from about 100 °C to about 150 °C in a distillation pot. After the temperature reaches about 100 °C to about 150 °C, two moles of formaldehyde are gradually added. After all the formaldehyde has been added to the distillation pot, heating is continued until the water content is reduced to about 0.10%.
  • methyl Formcel® commercially available from Hoechst Celanese
  • formalin is used as a the source of the formaldehyde.
  • alkylphenol or alkenylphenol has the following general structure:
  • R j is a straight or branched chain alkyl or alkenyl group with from six to twenty carbon atoms. More preferably, the alkylphenol or alkenylphenol is nonylphenol or dodecylphenol.
  • the products of the mannich reaction described above include trace amounts of diethanolamine, and primarily di-substituted alkylphenol or alkenylphenol mannich condensates (I), in combination with mono- substituted alkylphenol or alkenylphenol mannich condensates (II), with the following general structure:
  • R j is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms.
  • R j is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms.
  • the resulting alkylphenol or alkenylphenol mannich condensates are then alkoxylated with a lower molecular weight alkylene oxide, at a temperature from about 100 °C to about 160 °C, at a pressure of about 60 psig, and in the presence of a suitable alkaline catalyst, such as, but not limited to potassium hydroxide.
  • a suitable alkaline catalyst such as, but not limited to potassium hydroxide.
  • the lower molecular weight alkylene oxide may comprise an alkylene oxide with less than about six carbon atoms.
  • the alkylene oxide comprises ethylene oxide, propylene oxide, and/or butylene oxide.
  • the resulting alkoxylated alkylphenol or alkenylphenol mannich condensates comprise primarily di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates (I), in combination with mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates (II), with the following general structure:
  • R x is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms
  • R 2 and R 3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms
  • a,b,c,d,e, and f each independently vary from zero to about thirty
  • a+b+c+d+e+f is between zero and about one hundred and eighty.
  • Rj is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms
  • R 2 and R 3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
  • the resulting alkylphenol or alkenylphenol mannich condensate alkoxylates contain from about 20% to about 80% alkylene oxide content. More preferably, the resulting alkylphenol or alkenylphenol mannich condensate alkoxylates contain from about 20% to about 80% ethylene oxide content.
  • the resulting alkoxylated alkylphenol or alkenylphenol mannich condensates surfactants may then be blended with one or more formulation aids before being combined with a herbicide.
  • formulation aids may include neutralizing agents, water, anti-freeze agents, thickening agents, or mixtures thereof.
  • the neutralizing agents may comprise any number of acids, including, but not limited to, hydrochloric acid or sulfuric acid. A sufficient amount of a neutralizing agent should be added to the surfactant to neutralize any residual basicity (i.e to achieve a pH of about 7.0).
  • the anti-freeze agents may include, but are not limited to, propylene glycol, ethylene glycol, or diethylene glycol.
  • the thickening agents may include, but are not limited to, carboxymethyl cellulose, polycarboxylates, or guar.
  • the relative amount of formulation aids that should be blended with the alkoxylated alkylphenol or alkenylphenol mannich condensate surfactants of the present invention will depend on a variety of factors, including the nature of the herbicide to be blended with the surfactant solution, the proposed mode of application of the final herbicide formulation, the nature of the vegetation to be treated, etc.
  • the alkoxylated alkylphenol or alkenylphenol mannich condensates may be reacted with either phosphorous pentoxide or polyphosphoric acid to produce phosphate esters.
  • phosphorous pentoxide or polyphosphoric acid to produce the phosphate ester.
  • about 1.90 moles of the alkylphenol or alkenylphenol mannich condensate alkoxylates are heated to a temperature of about 50 °C, under nitrogen, in a reaction vessel. Once the temperature reaches 50 °C, about 1 mole of phosphorous pentoxide or polyphosphoric acid is gradually added to the reaction vessel, as the temperature is raised to about 80 °C. After all the phosphorous pentoxide or polyphosphoric acid has been added to the reaction vessel, the reaction components are allowed to digest for at least 3 hours.
  • the resulting phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates comprise primarily phosphate monoesters (la) and diesters (lb) of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates , in combination with phosphate monoesters (Ila) and diesters (lib) of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, with the following general formula:
  • R ⁇ is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms
  • R 2 and R 3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms
  • a,b,c,d,e, and f each independently vary from zero to about thirty
  • a+b+c+d+e+f is between zero and about one hundred and eighty.
  • R ! is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms
  • R 2 and R 3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
  • the resulting phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates may then be blended with one or more formulation aids before being mixed with a herbicide.
  • formulation aids include, but are not limited to, neutralizing agents, water, anti-freeze agents, thickening agents, or mixtures thereof.
  • a sufficient amount of a neutralizing agent should be added to the phosphate ester surfactant to neutralize any residual basicity (i.e to achieve a pH of about 7.0).
  • the neutralizing agent may include, but is not limited to, the alkylphenol or alkenylphenol mannich condensate(s) prepared above.
  • the anti-freeze agents may include, but are not limited to, propylene glycol, ethylene glycol, or diethylene glycol.
  • the thickening agents may include, but are not limited to, carboxymethyl cellulose, polycarboxylates, or guar.
  • the relative amount of formulation aids that should be blended with the phosphate esters will depend on a variety of factors, including the nature of the herbicide to be blended with the surfactant solution, the proposed mode of application of the final herbicide formulation, the nature of the vegetation to be treated, etc.
  • the phosphate esters may be alkoxylated to quench their latent acidity, and achieve a pH neutral solution.
  • the phosphate ester may be alkoxylated with a lower molecular weight alkylene oxide, meaning an alkylene oxide with less than about six carbon atoms.
  • the alkylene oxide comprises ethylene oxide, propylene oxide, and/or butylene oxide.
  • the alkoxylation should be carried out at a temperature from about 80 °C to about 100 °C, and is self catalyzing.
  • alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates comprise primarily alkoxylated phosphate monoesters (la) and diesters (lb) of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters (Ila) and diesters (lib) of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates having the following general formula: (la)
  • R j is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms
  • R 2 and R 3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms
  • a, b, c, d, e, f, g, and h each independently vary from zero to about thirty
  • a+b+c+d+e+f+g+h is between zero and about two hundred and forty.
  • R 2 is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms
  • R 2 and R 3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
  • the resulting alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensate surfactants of the present invention may then be blended with one or more formulation aids before being combined with a herbicide.
  • formulation aids may include, but are not limited to, water, anti-freeze agents, thickening agents, or mixtures thereof.
  • the antifreeze agents may include, but are not limited to, propylene glycol, ethylene glycol, or diethylene glycol.
  • the thickening agents may include, but are not limited to, carboxymethyl cellulose, polycarboxylates, or guar.
  • the relative amount of formulation aids that should be blended with the alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensate surfactants of the present invention will depend on a variety of factors, including the nature of the herbicide to be blended with the surfactant solution, the proposed mode of application of the final herbicide formulation, the nature of the vegetation to be treated, etc.
  • the blended mannich condensate surfactants of the present invention may then be mixed with a herbicide.
  • the relative amount of the blended mannich condensate surfactants of the present invention that should be added to a herbicide will vary depending on a variety of factors, including the nature of the herbicide, the nature of the vegetation to be treated, the method of application, whether the herbicide is a water-based or a granular formulation, etc.
  • the resulting herbicide compositions of the present invention should include a herbicidally effective amount of a herbicidal active ingredient, and a sufficient amount of a surfactant of the present invention to enhance the effectiveness of the herbicidal active ingredient.
  • the term "herbicidally effective amount” means the amount of herbicide necessary to promote plant necrosis.
  • the surfactants of the present invention may be blended with any number of commercially available herbicides, including, but not limited to glyphosate or a salt thereof.
  • glyphosate or a salt thereof Preferably, in water-based herbicide compositions, less than about 30% of the volume of the herbicide composition should comprise the blended surfactant compositions of the present invention.
  • surfactant composition means the surfactants of the present invention blended with one or more formulation aids.
  • the herbicide compositions of the present invention may be prepared as either liquid or solid compositions.
  • Liquid compositions may include solutions ready for immediate application, aqueous concentrates intended to be diluted with water before application, or microencapsulated actives suspended in liquid media.
  • Solid compositions may include, but are not limited to, water dispersible granules, water soluble granules, microencapsulated actives, free- flowing particulate compositions, or granular-based solids that have been compressed into tablets or briquets of any desired size and shape.
  • solid compositions may include formulations where the herbicide composition is absorbed onto water soluble or water insoluble inert dry carriers, including, but not limited to, Magnesol® (commercially available from the Dallas Group of America, Inc., Whitehouse, New Jersey).
  • the herbicide compositions of the present invention may be applied to vegetation as either a liquid or solid composition.
  • Liquid herbicide compositions are typically sprayed on the vegetation to be treated, and typically comprise either liquid concentrates or dissolved or dispersed solid compositions.
  • Liquid compositions may also be injected into, or painted on the truck portion of the vegetation to be treated. Solid granular compositions may be spread on or around the vegetation to be treated.
  • Herbicide compositions comprising the surfactant compositions of the present invention are expected to have a reduced tendency to cause eye irritation. Reduced eye irritation is expected because the pH of formulations containing the mannich condensate surfactant compositions of the present invention is about 7.0. Due to the fact that herbicide formulations are often applied by humans, or in locales with humans or animals, reduced eye irritation is a desirable feature in such formulations.
  • the surfactants of the present invention are primarily discussed as being incorporated into water-based herbicide compositions, it is understood that the surfactants of the present invention may also be incorporated into dry granular herbicide formulations.
  • the surfactants of the present invention are primarily discussed as being incorporated into glyphosate solutions, the surfactants of the present invention may be incorporated into any number of other herbicide formulations, including, but not limited to, macro and micro emulsions, suspensions, suspension concentrates, and other liquid and solid formulations knows to those skilled in the art, to increase the bioefficacy of such herbicides.
  • the following examples are illustrative of the present invention, and are not intended to limit the scope of the invention in any way.
  • Example la 4230 grams of nonylphenol and 4210 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 108° C. Then, 1560 grams of methyl Formcel® were gradually added to the distillation pot, as the temperature was raised to about 120 °C. After all the methyl Formcel® had been added, the water content was reduced to about 0.10% by distillation.
  • the resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 155 °C to about 160 °C, under nitrogen, at a pressure of about 60 psig, and in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 20%, 40%, and 60% ethylene oxide content.
  • Example lb 3710 grams of nonylphenol and 3570 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 110°C.
  • the resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 105 °C to about 110°C, under nitrogen, at a pressure of about 60 psig, and in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 20%, 40%, and 60% ethylene oxide content.
  • Example 4 Alkoxylated Alkylphenol Mannich Condensates of the Present Invention Example 4 An outside laboratory tested the bioefficacy of the glyphosate solutions prepared in Example 3 on morning glory and velvet leaf weeds. For comparison, the laboratory also tested the bioefficacy of a glyphosate solution that did not contain a surfactant, namely Rodeo®.
  • a surfactant namely Rodeo®.
  • the bioefficacy testing was conducted in a greenhouse, using one foot by one foot plots, and a randomized complete block study design.
  • the subject weeds were sprayed with each of the glyphosate solutions prepared in Example 3, under the following conditions:
  • Nozzle Type flat-fan
  • the addition of the alkoxylated alkylphenol mannich condensate surfactants of the present invention to glyphosate compositions noticeably improves the herbicidal efficacy of the glyphosate.
  • alkoxylated alkylphenol mannich condensate surfactant compositions are more effective at particular concentrations, and on particular types of weeds.
  • Example 5 3710 grams of nonylphenol and 3570 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 110°C. Then, 2750 grams of formalin (a 37% aqueous formaldehyde solution) were gradually added to the distillation pot, as the temperature was reduced to about 100 °C. After all the formalin had been added, the water content was reduced to about 0.10% by distillation.
  • formalin a 37% aqueous formaldehyde solution
  • the resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 105°C to about 110°C, under nitrogen, in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 60% ethylene oxide content.
  • the resulting alkoxylated mannich condensate product was then reacted with phosphorous pentaoxide.
  • phosphorous pentaoxide 940 grams of the alkoxylated mannich condensate product were charged to a reaction vessel, and heated to a temperature of about 50 C C, under nitrogen. After the temperature reached about 50 °C, 60 grams of phosphorous pentaoxide were gradually added to the reaction vessel, as the temperature was raised to about 80 °C. The reaction components were allowed to heat at this temperature overnight.
  • Example 6 The phosphate ester of alkoxylated nonylphenol mannich condensates produced in Example 5 was blended as follows:
  • Example 7 For the surfactant solution prepared in Example 6, individual glyphosate solutions were prepared that contained about 7.5, 15, and 30% vol. of the blended surfactant solution. Rodeo® was used as the source of glyphosate. (Rodeo® contains 648 g/L of the mono-isopropylamine salt of glyphosate.)
  • the bioefficacy testing was conducted in a greenhouse, using one foot by one foot plots, and a randomized complete block study design.
  • the subject weeds were sprayed with each of the glyphosate solutions prepared in Example 7, under the following conditions:
  • Nozzle Type flat-fan
  • Rate/Unit 18 fluid ounce/acre
  • the addition of the phosphate esters of alkoxylated alkylphenol mannich condensate surfactants of the present invention to glyphosate compositions noticeably improves the herbicidal efficacy of the glyphosate.
  • the herbicidal efficacy varies according to the concentration of the surfactant in the glyphosate composition, and according to the variety of weed being treated.
  • Example 9 3710 grams of nonylphenol and 3570 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 110°C. Then, 2750 grams of formalin (a 37% aqueous formaldehyde solution) were gradually added to the distillation pot, as the temperature was reduced to about 100° C. After all the formalin had been added, the water content was reduced to about 0.10% by distillation.
  • formalin a 37% aqueous formaldehyde solution
  • the resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 105 °C to about 110°C, under nitrogen, in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 60% ethylene oxide content.
  • the resulting alkoxylated mannich condensate product was then reacted with phosphorous pentaoxide.
  • 940 grams of the alkoxylated mannich condensate product were charged to a reaction vessel, and heated to a temperature of about 50 °C, under nitrogen. After the temperature reached about 50 °C, 60 grams of phosphorous pentaoxide were gradually added to the reaction vessel, as the temperature was raised to about
  • the final alkoxylated product contained about 24% ethylene oxide and 76% of the phosphate ester product.
  • Example 10 The alkoxylated phosphate esters of alkoxylated nonylphenol mannich condensates produced in Example 9 was blended as follows:
  • Example 12 An outside laboratory tested the bioefficacy of the glyphosate solutions prepared in Example 11 on morning glory and velvet leaf weeds. For comparison, the laboratory also tested the bioefficacy of a glyphosate solution that did not contain a surfactant, namely Rodeo®.
  • the bioefficacy testing was conducted in a greenhouse, using one foot by one foot plots, and a randomized complete block study design.
  • the subject weeds were sprayed with each of the glyphosate solutions prepared in Example 11, under the following conditions:
  • Nozzle Type flat-fan
  • Rate/Unit 18 fluid ounce/acre
  • the addition of the alkoxylated phosphate esters of alkoxylated alkylphenol mannich condensate surfactants of the present invention to glyphosate compositions markedly improves the herbicidal efficacy of the glyphosate. Noticeably, the herbicidal efficacy increases as the concentration of the surfactant in the glyphosate composition is increased.

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Abstract

Surfactants that further improve the bioefficacy of herbicides. The surfactants comprise (i) primarily di-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, in combination with mono-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, (ii) primarily phosphate monoesters and diesters of di-substituted alkylpheno or alkenylphenol mannich condensates alkoxylates, in combination with phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, and (iii) primarily alkoxylated phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates. The present invention also provides for herbicide compositions that contain the surfactants of the present invention.

Description

MANNICH CONDENSATE - BASED SURFACTANT ADJUVANTS AND
COMPOSITIONS THEREOF
Technical Field This invention relates to surfactants, and, more particularly, to surfactants that enhance the bioefficacy of herbicides, and to herbicide compositions comprising such surfactants. Background of the Invention
Herbicide compositions are often characterized according to the identity of the active ingredient, and by the mode by which the active ingredient causes vegetation necrosis. Regardless of the active ingredient, most herbicides cause vegetation necrosis by interfering with one or more vital biological processes essential to the vegetation's survival. Yet, before the active ingredient of a herbicide can interfere with such biological processes, the active ingredient must somehow be absorbed into the vegetation. Unfortunately, this absorption is often hindered by the chemical nature of the active ingredient. Accordingly, in addition to active ingredients, most herbicide compositions also comprise other components, commonly termed adjuvants, that enhance the performance and absorption of the active ingredient. One class of adjuvants that is frequently used is surfactants. Surfactants are useful in herbicide compositions because they tend to both enhance the absorbing properties of the active ingredient, as well as facilitate application of the herbicide.
The literature discloses various classes of surfactant adjuvants. One common class of surfactants includes derivatives of alkoxylated amines. For example, U.S. Pat. No. 5,683,958 discloses surfactants comprising tallow amine ethoxylates blended with a phosphate ester of an alkylphenol or alcohol ethoxylate; U.S. Pat. No. 5,798,310 discloses adjuvants comprising alkoxylated quaternary ammonium surfactants; U.S. Pat. No. 5,668,085 discloses glyphosate formulations comprising alkoxylated amine surfactants; and U.S. Pat. No. 5,118,444 discloses amide-oxide surfactants produced by oxidizing tertiary polyalkoxylated amine surfactants. However, the literature appears to lack any reference to the use of alkoxylated alkylphenol or alkenylphenol mannich condensates, phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, or alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates as suitable herbicide adjuvants. Surprisingly, it was discovered that alkoxylated alkylphenol or alkenylphenol mannich condensates, phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, and alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates function to improve the bioefficacy of herbicide compositions containing such surfactants. Also, herbicide formulations comprising alkoxylated alkylphenol or alkenylphenol mannich condensates, their phosphate esters, or their alkoxylated phosphate esters are expected to have a reduced tendency to cause eye irritation. Accordingly, the present invention is directed toward surfactant adjuvants that include alkoxylated alkylphenol or alkenylphenol mannich condensates, phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, and alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates, herbicide compositions comprising such surfactants, and a method of controlling unwanted weeds or vegetation using such herbicide compositions.
Summary of the Invention The present invention provides for surfactants that further improve the bioefficacy of herbicides. The surfactants comprise (i) primarily di-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, in combination with mono-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, (ii) primarily phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, and (iii) primarily alkoxylated phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters and diesters of mono- substituted alkylphenol or alkenylphenol mannich condensates alkoxylates. The mono-substituted alkylphenol or alkenylphenol mannich condensates (I) and the di-substituted alkylphenol or alkenylphenol mannich condensates (II) have the following general structure:
(I) (R2°)a( 30)bH
I
χ
where Rx is independently hydrogen or
O
II
— P -O -R I )
O-R .
each Ry is independently: (i) hydrogen, (ii) - (R2O)g(R3O)hH, (iii)
(iv)
Rj is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a, b, c, d, e, f, g, and h each independently vary from zero to about thirty; and a+b-r-c+d+e+f+g+h is between zero and about two hundred and forty.
The present invention also provides for herbicide compositions that contain a surfactant of the present invention. The herbicide compositions comprise a herbicidal active ingredient, a surfactant of the present invention, and optionally, one or more formulation aids. The herbicide compositions of the present invention are expected to have a reduced tendency to cause eye and skin irritation.
The present invention additionally provides for a method of controlling unwanted weeds or vegetation using the herbicide compositions of the present invention.
Detail Description of the Preferred Embodiment The present invention relates to surfactants that enhance the bioefficacy of herbicides, herbicide compositions comprising such surfactants, and a method of controlling unwanted weeds or vegetation using the herbicide compositions of the present invention.
The surfactants of the present invention may be used in conjunction with any number of herbicidal active ingredients. However, the use of the surfactants of the present invention with glyphosate is of particular interest because glyphosate is probably the most widely used herbicide.
Glyphosate, or N-phosphonomethylglycine, is a broad-spectrum herbicide that is useful on essentially all annual and perennial plants, including, grasses, broad-leaved weeds, and woody plants. Glyphosate promotes plant necrosis by inhibiting aromatic amino acid biosynthesis. By inhibiting aromatic amino acid synthesis, and thereby protein synthesis, glyphosate initially suppresses plant growth, which is soon followed by plant necrosis.
In its free acid form, glyphosate has a low water solubility. As such, water-based glyphosate compositions typically contain a water soluble salt of glyphosate, such as the isopropylamine salt. For example, many commercially available herbicide compositions contain the water soluble mono- isopropylamine salt of glyphosate. Glyphosate, and various water soluble derivatives of glyphosate, are available from numerous manufactures.
The surfactants of the present invention may be prepared by heating one mole of an alkylphenol or alkenylphenol and two moles of diethanolamine, at a temperature from about 100 °C to about 150 °C in a distillation pot. After the temperature reaches about 100 °C to about 150 °C, two moles of formaldehyde are gradually added. After all the formaldehyde has been added to the distillation pot, heating is continued until the water content is reduced to about 0.10%.
Preferably, methyl Formcel® (commercially available from Hoechst Celanese) or formalin is used as a the source of the formaldehyde. Preferably, the alkylphenol or alkenylphenol has the following general structure:
where Rj is a straight or branched chain alkyl or alkenyl group with from six to twenty carbon atoms. More preferably, the alkylphenol or alkenylphenol is nonylphenol or dodecylphenol. The products of the mannich reaction described above include trace amounts of diethanolamine, and primarily di-substituted alkylphenol or alkenylphenol mannich condensates (I), in combination with mono- substituted alkylphenol or alkenylphenol mannich condensates (II), with the following general structure:
(I) (ID
where Rj is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms. Preferably, Rj is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms.
The resulting alkylphenol or alkenylphenol mannich condensates are then alkoxylated with a lower molecular weight alkylene oxide, at a temperature from about 100 °C to about 160 °C, at a pressure of about 60 psig, and in the presence of a suitable alkaline catalyst, such as, but not limited to potassium hydroxide. The lower molecular weight alkylene oxide may comprise an alkylene oxide with less than about six carbon atoms. Preferably, the alkylene oxide comprises ethylene oxide, propylene oxide, and/or butylene oxide.
The resulting alkoxylated alkylphenol or alkenylphenol mannich condensates comprise primarily di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates (I), in combination with mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates (II), with the following general structure:
(I) (ID
where Rx is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a,b,c,d,e, and f each independently vary from zero to about thirty; and a+b+c+d+e+f is between zero and about one hundred and eighty. Preferably, Rj is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms, and R2 and R3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
Preferably, the resulting alkylphenol or alkenylphenol mannich condensate alkoxylates contain from about 20% to about 80% alkylene oxide content. More preferably, the resulting alkylphenol or alkenylphenol mannich condensate alkoxylates contain from about 20% to about 80% ethylene oxide content.
The resulting alkoxylated alkylphenol or alkenylphenol mannich condensates surfactants may then be blended with one or more formulation aids before being combined with a herbicide. Such formulation aids may include neutralizing agents, water, anti-freeze agents, thickening agents, or mixtures thereof. The neutralizing agents may comprise any number of acids, including, but not limited to, hydrochloric acid or sulfuric acid. A sufficient amount of a neutralizing agent should be added to the surfactant to neutralize any residual basicity (i.e to achieve a pH of about 7.0). The anti-freeze agents may include, but are not limited to, propylene glycol, ethylene glycol, or diethylene glycol. The thickening agents may include, but are not limited to, carboxymethyl cellulose, polycarboxylates, or guar. The relative amount of formulation aids that should be blended with the alkoxylated alkylphenol or alkenylphenol mannich condensate surfactants of the present invention will depend on a variety of factors, including the nature of the herbicide to be blended with the surfactant solution, the proposed mode of application of the final herbicide formulation, the nature of the vegetation to be treated, etc.
Alternatively, the alkoxylated alkylphenol or alkenylphenol mannich condensates may be reacted with either phosphorous pentoxide or polyphosphoric acid to produce phosphate esters. To produce the phosphate ester, about 1.90 moles of the alkylphenol or alkenylphenol mannich condensate alkoxylates are heated to a temperature of about 50 °C, under nitrogen, in a reaction vessel. Once the temperature reaches 50 °C, about 1 mole of phosphorous pentoxide or polyphosphoric acid is gradually added to the reaction vessel, as the temperature is raised to about 80 °C. After all the phosphorous pentoxide or polyphosphoric acid has been added to the reaction vessel, the reaction components are allowed to digest for at least 3 hours.
The resulting phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates comprise primarily phosphate monoesters (la) and diesters (lb) of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates , in combination with phosphate monoesters (Ila) and diesters (lib) of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, with the following general formula:
(la)
(R20)a(R30)bH
I
(lb)
(
(lib) (R30)bH
where Rλ is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a,b,c,d,e, and f each independently vary from zero to about thirty; and a+b+c+d+e+f is between zero and about one hundred and eighty. Preferably, R! is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms, and R2 and R3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
The resulting phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates may then be blended with one or more formulation aids before being mixed with a herbicide. Such formulation aids include, but are not limited to, neutralizing agents, water, anti-freeze agents, thickening agents, or mixtures thereof. A sufficient amount of a neutralizing agent should be added to the phosphate ester surfactant to neutralize any residual basicity (i.e to achieve a pH of about 7.0). The neutralizing agent may include, but is not limited to, the alkylphenol or alkenylphenol mannich condensate(s) prepared above. The anti-freeze agents may include, but are not limited to, propylene glycol, ethylene glycol, or diethylene glycol. The thickening agents may include, but are not limited to, carboxymethyl cellulose, polycarboxylates, or guar.
The relative amount of formulation aids that should be blended with the phosphate esters will depend on a variety of factors, including the nature of the herbicide to be blended with the surfactant solution, the proposed mode of application of the final herbicide formulation, the nature of the vegetation to be treated, etc.
Alternatively, the phosphate esters may be alkoxylated to quench their latent acidity, and achieve a pH neutral solution. The phosphate ester may be alkoxylated with a lower molecular weight alkylene oxide, meaning an alkylene oxide with less than about six carbon atoms. Preferably, the alkylene oxide comprises ethylene oxide, propylene oxide, and/or butylene oxide. The alkoxylation should be carried out at a temperature from about 80 °C to about 100 °C, and is self catalyzing. The resulting alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensates comprise primarily alkoxylated phosphate monoesters (la) and diesters (lb) of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters (Ila) and diesters (lib) of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates having the following general formula: (la)
(lb)
(Ha)
(lib)
where Rj is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a, b, c, d, e, f, g, and h each independently vary from zero to about thirty; and a+b+c+d+e+f+g+h is between zero and about two hundred and forty. Preferably, R2 is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms, and R2 and R3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
The resulting alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensate surfactants of the present invention may then be blended with one or more formulation aids before being combined with a herbicide. Such formulation aids may include, but are not limited to, water, anti-freeze agents, thickening agents, or mixtures thereof. The antifreeze agents may include, but are not limited to, propylene glycol, ethylene glycol, or diethylene glycol. The thickening agents may include, but are not limited to, carboxymethyl cellulose, polycarboxylates, or guar.
The relative amount of formulation aids that should be blended with the alkoxylated phosphate esters of alkoxylated alkylphenol or alkenylphenol mannich condensate surfactants of the present invention will depend on a variety of factors, including the nature of the herbicide to be blended with the surfactant solution, the proposed mode of application of the final herbicide formulation, the nature of the vegetation to be treated, etc. The blended mannich condensate surfactants of the present invention may then be mixed with a herbicide. The relative amount of the blended mannich condensate surfactants of the present invention that should be added to a herbicide will vary depending on a variety of factors, including the nature of the herbicide, the nature of the vegetation to be treated, the method of application, whether the herbicide is a water-based or a granular formulation, etc. In any case, the resulting herbicide compositions of the present invention should include a herbicidally effective amount of a herbicidal active ingredient, and a sufficient amount of a surfactant of the present invention to enhance the effectiveness of the herbicidal active ingredient. The term "herbicidally effective amount" means the amount of herbicide necessary to promote plant necrosis. The surfactants of the present invention may be blended with any number of commercially available herbicides, including, but not limited to glyphosate or a salt thereof. Preferably, in water-based herbicide compositions, less than about 30% of the volume of the herbicide composition should comprise the blended surfactant compositions of the present invention. The term "surfactant composition" means the surfactants of the present invention blended with one or more formulation aids.
The herbicide compositions of the present invention may be prepared as either liquid or solid compositions. Liquid compositions may include solutions ready for immediate application, aqueous concentrates intended to be diluted with water before application, or microencapsulated actives suspended in liquid media. Solid compositions may include, but are not limited to, water dispersible granules, water soluble granules, microencapsulated actives, free- flowing particulate compositions, or granular-based solids that have been compressed into tablets or briquets of any desired size and shape. Optionally, solid compositions may include formulations where the herbicide composition is absorbed onto water soluble or water insoluble inert dry carriers, including, but not limited to, Magnesol® (commercially available from the Dallas Group of America, Inc., Whitehouse, New Jersey). Accordingly, the herbicide compositions of the present invention may be applied to vegetation as either a liquid or solid composition. Liquid herbicide compositions are typically sprayed on the vegetation to be treated, and typically comprise either liquid concentrates or dissolved or dispersed solid compositions. Liquid compositions may also be injected into, or painted on the truck portion of the vegetation to be treated. Solid granular compositions may be spread on or around the vegetation to be treated.
Herbicide compositions comprising the surfactant compositions of the present invention are expected to have a reduced tendency to cause eye irritation. Reduced eye irritation is expected because the pH of formulations containing the mannich condensate surfactant compositions of the present invention is about 7.0. Due to the fact that herbicide formulations are often applied by humans, or in locales with humans or animals, reduced eye irritation is a desirable feature in such formulations.
It is understood that variations may be made in the foregoing with departing from the scope of the invention. For example, although the surfactants of the present invention are primarily discussed as being incorporated into water-based herbicide compositions, it is understood that the surfactants of the present invention may also be incorporated into dry granular herbicide formulations. In addition, although the surfactants of the present invention are primarily discussed as being incorporated into glyphosate solutions, the surfactants of the present invention may be incorporated into any number of other herbicide formulations, including, but not limited to, macro and micro emulsions, suspensions, suspension concentrates, and other liquid and solid formulations knows to those skilled in the art, to increase the bioefficacy of such herbicides. The following examples are illustrative of the present invention, and are not intended to limit the scope of the invention in any way.
Preparation of the Alkoxylated Alkylphenol Mannich Condensates
Example la 4230 grams of nonylphenol and 4210 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 108° C. Then, 1560 grams of methyl Formcel® were gradually added to the distillation pot, as the temperature was raised to about 120 °C. After all the methyl Formcel® had been added, the water content was reduced to about 0.10% by distillation. The resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 155 °C to about 160 °C, under nitrogen, at a pressure of about 60 psig, and in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 20%, 40%, and 60% ethylene oxide content. Example lb 3710 grams of nonylphenol and 3570 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 110°C. Then, 2750 grams of formalin (a 37% aqueous formaldehyde solution) were gradually added to the distillation pot, as the temperature was reduced to about 100 °C. After all the formalin had been added, the water content was reduced to about 0.10% by distillation.
The resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 105 °C to about 110°C, under nitrogen, at a pressure of about 60 psig, and in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 20%, 40%, and 60% ethylene oxide content.
Preparation of the Alkoxylated Alkylphenol Mannich Condensate Surfactant Solutions Example 2
The alkoxylated alkylphenol mannich condensates produced in Examples la and lb were blended as follows (in grams):
Surfactant Solution
Component A B
Alkoxylated alkylphenol mannich condensate 272 0 from Example la (with a 20% ethylene oxide content)
Alkoxylated alkylphenol mannich condensate 0 293.6 from Example lb (with a 60% ethylene oxide content)
Concentrated HC1 60 32.8
Water 68 73.6
Preparation of Glyphosate Solutions Containing the Alkoxylated Alkylphenol Mannich Condensates of the Present Invention Example 3 For each surfactant solution prepared in Example 2, a glyphosate solution was prepared that contained about 7.5, 15, and 30% vol. of the blended surfactant solution. Rodeo® was used as the source of glyphosate. (Rodeo® contains 648 g/L of the mono-isopropylamine salt of glyphosate.)
Bioefficacy Testing of Glyphosate Solutions Containing the
Alkoxylated Alkylphenol Mannich Condensates of the Present Invention Example 4 An outside laboratory tested the bioefficacy of the glyphosate solutions prepared in Example 3 on morning glory and velvet leaf weeds. For comparison, the laboratory also tested the bioefficacy of a glyphosate solution that did not contain a surfactant, namely Rodeo®.
The bioefficacy testing was conducted in a greenhouse, using one foot by one foot plots, and a randomized complete block study design. The subject weeds were sprayed with each of the glyphosate solutions prepared in Example 3, under the following conditions:
Application Pressure: 40 psi
Nozzle Type: flat-fan
Nozzle Size: 8002E
Boom Height, Unit: 18 inches
Ground Speed, Unit: 4 mph
Carrier: water
Spray Volume: lO gpa
Propellant: air
Rate/Unit: 18 fluid ounce/ac
Twenty-one days after treatment, the green mass of each treated plant was weighed, and compared to the weight of the green mass of an untreated sample. From this comparison, the percent control or percent of plant injury was extrapolated. For each glyphosate solution, three plots of weeds were tested, and the results are expressed in terms of a mean for the three plots. The results of the bioefficacy testing completed on velvet leaf and morning glory weeds are summarized in Table 1. The results are expressed in terms of percent control, where 0% represents no plant injury, and 100% represents complete plant injury.
Table 1
% control % control velvet leaf morning glory
Glyphosate solution without a 51 50 surfactant (Rodeo®)
Glyphosate solution containing 57 83 7.5% of surfactant solution A
Glyphosate solution containing 69 90 15% of surfactant solution A
Glyphosate solution containing 60 80 30% of surfactant solution A
Glyphosate solution containing 76 95 7.5% of surfactant solution B
Glyphosate solution containing 94 91 15% of surfactant solution B
Glyphosate solution containing 88 94 30% of surfactant solution B
Referring to Table 1, the addition of the alkoxylated alkylphenol mannich condensate surfactants of the present invention to glyphosate compositions noticeably improves the herbicidal efficacy of the glyphosate.
Additionally, certain alkoxylated alkylphenol mannich condensate surfactant compositions are more effective at particular concentrations, and on particular types of weeds.
Preparation of Phosphate Esters of an Alkoxylated Alkylphenol Mannich Condensate
Example 5 3710 grams of nonylphenol and 3570 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 110°C. Then, 2750 grams of formalin (a 37% aqueous formaldehyde solution) were gradually added to the distillation pot, as the temperature was reduced to about 100 °C. After all the formalin had been added, the water content was reduced to about 0.10% by distillation.
The resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 105°C to about 110°C, under nitrogen, in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 60% ethylene oxide content.
The resulting alkoxylated mannich condensate product was then reacted with phosphorous pentaoxide. Particularly, 940 grams of the alkoxylated mannich condensate product were charged to a reaction vessel, and heated to a temperature of about 50 CC, under nitrogen. After the temperature reached about 50 °C, 60 grams of phosphorous pentaoxide were gradually added to the reaction vessel, as the temperature was raised to about 80 °C. The reaction components were allowed to heat at this temperature overnight.
Preparation of the Surfactant Solution Containing a Phosphate Ester of
Alkoxylated Alkylphenol Mannich Condensates Example 6 The phosphate ester of alkoxylated nonylphenol mannich condensates produced in Example 5 was blended as follows:
Component Amount (grams)
Phosphate ester of alkoxylated nonylphenol 272 mannich condensates produced in Example 5
Nonylphenol mannich condensate produced 48 in Example 5
Water 80
Preparation of Glyphosate Solutions Containing the Phosphate
Esters of Alkoxylated Alkylphenol Mannich
Condensates of the Present Invention
Example 7 For the surfactant solution prepared in Example 6, individual glyphosate solutions were prepared that contained about 7.5, 15, and 30% vol. of the blended surfactant solution. Rodeo® was used as the source of glyphosate. (Rodeo® contains 648 g/L of the mono-isopropylamine salt of glyphosate.)
Bioefficacy Testing of the Glyphosate Solutions Containing the Phosphate Esters of Alkoxylated Alkylphenol Mannich Condensates of the Present Invention Example 8 An outside laboratory tested the bioefficacy of the glyphosate solutions prepared in Example 7 on morning glory and velvet leaf weeds. For comparison, the laboratory also tested the bioefficacy of a glyphosate solution that did not contain a surfactant, namely Rodeo®.
The bioefficacy testing was conducted in a greenhouse, using one foot by one foot plots, and a randomized complete block study design. The subject weeds were sprayed with each of the glyphosate solutions prepared in Example 7, under the following conditions:
Application Pressure: 40 psi
Nozzle Type: flat-fan
Nozzle Size: 8002E
Boom Height, Unit: 18 inches
Ground Speed, Unit: 4 mph
Carrier: water
Spray Volume: lO gpa
Propellant: air
Rate/Unit: 18 fluid ounce/acre
Twenty-one days after treatment, the green mass of each treated plant was weighed, and compared to the weight of the green mass of an untreated sample. From this comparison, the percent control or percent of plant injury was extrapolated. For each glyphosate solution, three plots of weeds were tested, and the results are expressed in terms of a mean for the three plots.
The results of the bioefficacy testing completed on velvet leaf and morning glory weeds are summarized in Table 2. The results are expressed in terms of percent control, where 0% represents no plant injury, and 100% represents complete plant injury.
Table 2
% control % control velvet leaf morning glory
Glyphosate solution without a 51 50 surfactant (Rodeo®)
Glyphosate solution 72 94 containing 7.5% of the surfactant solution prepared in Example 6
Glyphosate solution 92 88 containing 15% of the surfactant solution prepared in Example 6
Glyphosate solution 78 95 containing 30% of the surfactant solution prepared in Example 6
Referring to Table 2, the addition of the phosphate esters of alkoxylated alkylphenol mannich condensate surfactants of the present invention to glyphosate compositions noticeably improves the herbicidal efficacy of the glyphosate. The herbicidal efficacy varies according to the concentration of the surfactant in the glyphosate composition, and according to the variety of weed being treated.
Preparation of Alkoxylated Phosphate Esters of Alkoxylated Alkylphenol Mannich Condensates
Example 9 3710 grams of nonylphenol and 3570 grams of diethanolamine were added to a 12 liter distillation pot, and the pot was heated to a temperature of about 110°C. Then, 2750 grams of formalin (a 37% aqueous formaldehyde solution) were gradually added to the distillation pot, as the temperature was reduced to about 100° C. After all the formalin had been added, the water content was reduced to about 0.10% by distillation.
The resulting mannich condensate product was then reacted with ethylene oxide, at a temperature from about 105 °C to about 110°C, under nitrogen, in the presence of a 45% aqueous potassium hydroxide solution, to produce ethoxylated mannich condensates with a 60% ethylene oxide content. The resulting alkoxylated mannich condensate product was then reacted with phosphorous pentaoxide. Particularly, 940 grams of the alkoxylated mannich condensate product were charged to a reaction vessel, and heated to a temperature of about 50 °C, under nitrogen. After the temperature reached about 50 °C, 60 grams of phosphorous pentaoxide were gradually added to the reaction vessel, as the temperature was raised to about
80 °C. The reactions components were then allowed to heat at this temperature overnight. The resulting phosphate ester product was then reacted with ethylene oxide, at a temperature of 100 °C, until the solution had a pH of about 7.0.
The final alkoxylated product contained about 24% ethylene oxide and 76% of the phosphate ester product.
Preparation of a Surfactant Solution Containing the Alkoxylated Phosphate Esters of Alkoxylated Alkylphenol Mannich Condensates
Example 10 The alkoxylated phosphate esters of alkoxylated nonylphenol mannich condensates produced in Example 9 was blended as follows:
Component Amount (grams) Alkoxylated phosphate ester of alkoxylated 80 nonylphenol mannich condensates produced in Example 9
Water 20
Preparation of Glyphosate Solutions Containing the Alkoxylated Phosphate Esters of Alkoxylated Alkylphenol Mannich Condensates of the Present Invention Example 11 For the surfactant solution prepared in Example 10, individual glyphosate solutions were prepared that contained about 7.5, 15, and 30% vol. of the blended surfactant solution. Rodeo® was used as the source of glyphosate. (Rodeo® contains 648 g/L of the mono-isopropylamine salt of glyphosate.)
Bioefficacy Testing of the Glyphosate Solutions Example 12 An outside laboratory tested the bioefficacy of the glyphosate solutions prepared in Example 11 on morning glory and velvet leaf weeds. For comparison, the laboratory also tested the bioefficacy of a glyphosate solution that did not contain a surfactant, namely Rodeo®.
The bioefficacy testing was conducted in a greenhouse, using one foot by one foot plots, and a randomized complete block study design. The subject weeds were sprayed with each of the glyphosate solutions prepared in Example 11, under the following conditions:
Application Pressure: 40 psi
Nozzle Type: flat-fan
Nozzle Size: 8002E
Boom Height, Unit: 18 inches
Ground Speed, Unit: 4 mph
Carrier: water
Spray Volume: lO gpa
Propellant: air
Rate/Unit: 18 fluid ounce/acre
Twenty-one days after treatment, the green mass of each treated plant was weighed, and compared to the weight of the green mass of an untreated sample. From this comparison, the percent control or percent of plant injury was extrapolated. For each glyphosate solution, three plots of weeds were tested, and the results are expressed in terms of a mean for the three plots.
The results of the bioefficacy testing completed on velvet leaf and morning glory weeds are summarized in Table 3. The results are expressed in terms of percent control, where 0% represents no plant injury, and 100% represents complete plant injury.
Table 3
% control % control velvet leaf morning glory
Glyphosate solution without a 51 50 surfactant (Rodeo®)
Glyphosate solution 69 77 containing 7.5% of the surfactant solution prepared in Example 10
Glyphosate solution 92 91 containing 15% of the surfactant solution prepared in Example 10
Glyphosate solution 95 96 containing 30% of the surfactant solution prepared in Example 10
Referring to Table 3, the addition of the alkoxylated phosphate esters of alkoxylated alkylphenol mannich condensate surfactants of the present invention to glyphosate compositions markedly improves the herbicidal efficacy of the glyphosate. Noticeably, the herbicidal efficacy increases as the concentration of the surfactant in the glyphosate composition is increased.
Although illustrative embodiments have been shown and described, a wide range of modification, changes, and substitution is contemplated in the foregoing disclosure. In some instances, some features of the disclosed embodiments may be employed without a corresponding use of the other features. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention.

Claims

Claims
A herbicide composition that comprises: a. a herbicidally effective amount of a herbicidal active ingredient; and b. a sufficient amount of a surfactant component that enhances the effectiveness of the herbicidal active ingredient, wherein the surfactant component comprises either (i) primarily di- substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, in combination with mono-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, (ii) primarily phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with phosphate monoesters and diesters of mono- substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, or (iii) primarily alkoxylated phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters and diesters of mono- substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, where the mono-substituted alkylphenol or alkenylphenol mannich condensates (I) and the di-substituted alkylphenol or alkenylphenol mannich condensates (II) have the general formula:
(I)
χ
(ID
where Rx is independently hydrogen or
O
II
-P-O-R. I O-R,
each R is independently:
(i) hydrogen,
(ii) - (R2O)g(R3O)hH,
(iii)
(R20)a(R30)bH
(iv)
Rj is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a, b, c, d, e, f, g, and h each independently vary from zero to about thirty; and a+b+c+d+e+f+g+h is between zero and about two hundred and forty.
2. The composition of claim 1, wherein the herbicidal active ingredient comprises glyphosate or a salt thereof.
3. The composition of claim 1, wherein the surfactant component further comprises a formulation aid.
4. The composition of claim 3, wherein the formulation aid is selected from the group consisting of neutralizing agents, water, anti-freeze agents, thickening agents, and mixtures thereof.
5. The composition of claim 3, wherein the herbicide composition has a reduced tendency to cause eye irritation.
6. The composition of claim 3, wherein less than about 30% of the volume of the herbicide composition comprises the surfactant component.
7. The composition of claim 1, wherein Rx is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms.
8. The composition of claim 1, wherein R2 and R3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms. A surfactant for increasing the bioefficacy of a herbicide wherein the surfactant comprises (i) primarily di-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, in combination with mono-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, (ii) primarily phosphate monoesters and diesters of di- substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, or (iii) primarily alkoxylated phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, where the mono- substituted alkylphenol or alkenylphenol mannich condensates (I) and the di-substituted alkylphenol or alkenylphenol mannich condensates (II) have the general formula:
(I)
(R2o)a(R3o)bH
I
χ
(ID
where R^ is independently hydrogen or
O
II
- P -0 ~Ry O-Ry
each Ry is independently: (i) hydrogen, (ii) - (R2O)g(R3O)hH, (iii)
(iv)
Rj is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a, b, c, d, e, f, g, and h each independently vary from zero to about thirty; and a+b+c+d+e-t-f+g+h is between zero and about two hundred and forty.
10. The surfactant of claim 9, wherein R is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms.
11. The surfactant of claim 9, wherein R2 and R3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
12. A surfactant composition for increasing the bioefficacy of a herbicide that comprises: a. a surfactant component comprising (i) primarily di-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, in combination with mono-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, (ii) primarily phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, or (iii) primarily alkoxylated phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters and diesters of mono-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, where the mono-substituted alkylphenol or alkenylphenol mannich condensates (I) and the di-substituted alkylphenol or alkenylphenol mannich condensates (II) have the general formula:
(I)
(R20)a(R30)bH I
χ
(ID
where Rx is independently hydrogen or
O
II
- P-O -R I 0-R„
each Ry is independently: (i) hydrogen, (ii) - (R2O)g(R3O)hH, (iii)
(iv)
Rj is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a, b, c, d, e, f, g, and h each independently vary from zero to about thirty; and a+b+c+d+e+f+g+h is between zero and about two hundred and forty; and b. a formulation aid.
13. The composition of claim 12, wherein the formulation aid is selected from the group consisting of neutralizing agents, water, anti-freeze agents, thickening agents, and mixtures thereof.
14. The surfactant composition of claim 12, wherein Rj is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms.
15. The surfactant composition of claim 12, wherein R2 and R3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
16. A herbicide composition that comprises: a. a herbicidally effective amount of glyphosate or a salt thereof; and b. a sufficient amount of a surfactant component that enhances the effectiveness of the herbicidal active ingredient, wherein the surfactant component comprises either (i) primarily di- substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, in combination with mono-substituted alkylphenol or alkenylphenol mannich condensate alkoxylates, or (ii) primarily phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with phosphate monoesters and diesters of mono- substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, or (iii) primarily alkoxylated phosphate monoesters and diesters of di-substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, in combination with alkoxylated phosphate monoesters and diesters of mono- substituted alkylphenol or alkenylphenol mannich condensates alkoxylates, where the mono-substituted alkylphenol or alkenylphenol mannich condensates (I) and the di-substituted alkylphenol or alkenylphenol mannich condensates (II) have the general formula:
where Rx is independently hydrogen or
O
II
— P -O -R, I ]
O-R..
each Ry is independently: (i) hydrogen, (ii) - (R2O)g(R3O)hH, (iii)
(iv)
Rj is a straight or branched chain alkyl or alkenyl group with from about six to about twenty carbon atoms; R2 and R3 are each independently linear or branched alkenyl groups with from about two to about six carbon atoms; a, b, c, d, e, f, g, and h each independently vary from zero to about thirty; and a+b+c+d+e+f+g+h is between zero and about two hundred and forty.
17. The composition of claim 16, wherein the surfactant component further comprises a formulation aid.
18. The composition of claim 17, wherein the formulation aid is selected from the group consisting of neutralizing agents, water, anti-freeze agents, thickening agents, and mixtures thereof.
19. The composition of claim 17, wherein the herbicide composition has a reduced tendency to cause eye irritation.
20. The composition of claim 17, wherein less than about 30% of the volume of the herbicide composition comprises the surfactant component.
21. The composition of claim 16, wherein R: is a straight or branched chain alkyl or alkenyl group with from about nine to about twelve carbon atoms.
22. The composition of claim 16, wherein R2 and R3 are each independently linear or branched alkenyl groups with from about two to about four carbon atoms.
23. A method of killing or controlling weeds or unwanted vegetation comprising the step of applying a herbicidally effective amount of the composition of claim 1 to the foliage or tissue of the weeds or unwanted vegetation.
24. A method of killing or controlling weeds or unwanted vegetation comprising the step of applying a herbicidally effective amount of the composition of claim 16 to the foliage or tissue of the weeds or unwanted vegetation.
EP00957523A 1999-08-18 2000-08-17 Mannich condensate-based surfactant adjuvants and compositions thereof Withdrawn EP1211937A1 (en)

Applications Claiming Priority (7)

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US14955599P 1999-08-18 1999-08-18
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US149543P 1999-08-18
US149555P 1999-08-18
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US3297597A (en) * 1963-06-17 1967-01-10 Jefferson Chem Co Inc Production of rigid polyurethane foam
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RO87062B1 (en) * 1983-04-20 1985-05-30 Mircea Leonte Agents actifs de surface et procede de preparation
US4952732A (en) * 1984-06-15 1990-08-28 Texaco Inc. Mannich condensates of a substituted phenol and an alkylamine containing internal alkoxy groups
US5703015A (en) * 1990-08-09 1997-12-30 Monsanto Company Pesticidal compositions of polyoxyalkylene alkylamine surfactants having reduced eye irritation
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