EP3893641A1 - Alkyl polyglycerylamine based surfactants for agricultural use - Google Patents

Alkyl polyglycerylamine based surfactants for agricultural use

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Publication number
EP3893641A1
EP3893641A1 EP19817721.4A EP19817721A EP3893641A1 EP 3893641 A1 EP3893641 A1 EP 3893641A1 EP 19817721 A EP19817721 A EP 19817721A EP 3893641 A1 EP3893641 A1 EP 3893641A1
Authority
EP
European Patent Office
Prior art keywords
agricultural composition
alkyl
polyglycerylamine
agrochemical
surfactants
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.)
Pending
Application number
EP19817721.4A
Other languages
German (de)
French (fr)
Inventor
Hanamanthsa Bevinakatti
Shawn Zhu
Mojahedul Islam
Karen Lee White
Christine Puglisi
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.)
Nouryon Chemicals International BV
Original Assignee
Nouryon Chemicals International BV
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Filing date
Publication date
Application filed by Nouryon Chemicals International BV filed Critical Nouryon Chemicals International BV
Publication of EP3893641A1 publication Critical patent/EP3893641A1/en
Pending legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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

Definitions

  • the present disclosure generally relates to nitrogen containing glycidol surfactants as adjuvants for pesticide formulations.
  • Adjuvants can be used, for example, as a potentiator which is able to enhance the bioefficacy of the pesticides, a wetting agent, an emulsifier, a spreading agent, a deposition aid, a drift control agent, a water conditioner, a crystal inhibitor, a suspension aid, a thickener, or a dispersant.
  • the bioefficacy of pesticides can be enhanced by the addition of appropriate surfactant adjuvants.
  • surfactants such as alkyl amine alkoxylate surfactants.
  • Examples of nitrogen containing surfactants as potentiator adjuvants for herbicides can be found in US4528023 and US5226943. US5226943 also mentions that the activity of fungicide compositions can be improved by incorporating certain nitrogen containing surfactants.
  • Examples of nitrogen containing surfactants as potentiator adjuvants for insecticides can be found in WO 201280099.
  • Examples of nitrogen containing surfactants as emulsifiers in pesticide emulsions can be found in US5565409 and US 8097563.
  • Examples of nitrogen containing surfactants as thickeners in glyphosate formulations can be found in W0201020599.
  • Examples of nitrogen containing surfactants as drift control agents in pesticide emulsions can be found in W02013098220.
  • alkylamine ethoxylates are made by reacting ethylene oxide and alkylamines.
  • Ethylene oxide (EO) is a hazardous gaseous chemical (boiling point 10.7 °C). At room temperature it is a flammable, irritating, and anaesthetic gas. Because of its volatile nature, EO is commonly handled and shipped as a refrigerated liquid to reduce the risk of fire or explosions. This increases transportation and storage costs. Because of the hazardous nature of EO, the production of alkylamine ethoxylates requires special design of the reactor requiring a pressured reactor with a gas feeding pipe.
  • alkylamine ethoxylates are difficult to manufacture, they are one of the most used adjuvants in pesticide formulations.
  • An alkylamine ethoxylate molecule contains a hydrophilic portion (a tertiary nitrogen with various EO units) and a hydrophobic portion (hydrocarbon group) as shown for example in the following general structure:
  • R is a hydrocarbon group (i.e., the hydrophobic portion) of various chain lengths and x and y can adopt various values. It is this molecular structure that creates usefulness as adjuvants in agricultural applications. It is well known that the physical properties of an alkylamine ethoxylate can be altered by varying the hydrocarbon chain length and the number of EO units to suit various application needs.
  • alkylamine ethoxylates are in glyphosate herbicide formulations as a potentiator adjuvant. It is known in the art that, in the alkylamine ethoxylate family, an alkylamine ethoxylate with a longer hydrocarbon chain length (about Cl 8 or longer) and a higher number of EO units (higher than about 10) is more efficacious for glyphosate. It is also a common practice to use high load glyphosate formulations [e.g., 540 g/1 ae (acid equivalent) glyphosate in water] to minimize transportation costs and storage costs because high load formulations carry less water.
  • high load glyphosate formulations e.g., 540 g/1 ae (acid equivalent) glyphosate in water
  • An effective formulation requires a sufficient amount of adjuvants, typically > ⁇ 10% in formulations.
  • a hydrotrope or compatibility agent generally must be used (W02010036996).
  • hydrotropes or compatibility agents do not significantly contribute to bioefficacy enhancing effect and their use increases the total costs of formulations.
  • alkylamine derivatives useful for agricultural applications, hydrocarbons with various chain lengths are readily available, but hydrophilic groups have limited choices besides ethylene oxide. It is desirable to have alkylamine derivatives that behave similarly to alkylamine ethoxylates in agricultural applications but that also: (1) are less hazardous while handling the components; (2) allow easier manufacturing conditions; and (3) possess better compatibility in high load pesticide formulations. The subject matter of the current disclosure provides these advantages over what is currently known in the art.
  • the present disclosure generally relates to nitrogen containing surfactants, i.e., alkyl polyglycerylamine (or alkylamine glycidol surfactant), obtained by the reaction of alkylamine and glycidol.
  • alkyl polyglycerylamine surfactants of the present disclosure have better compatibility than alkylamine ethoxylates in high load agricultural formulations without the need for compatibility agents.
  • alkyl polyglycerylamine surfactants of the present disclosure are compatible in high load herbicide formulations containing herbicides such as 2,4-D salt, dicamba salt, glyphosate salt, and glufosinate salt without the need for a hydrotrope (compatibility agent) and can be used as a (co) emulsifier in pesticide formulations.
  • Alkyl polyglycerylamine obtained by reacting an alkylamine with glycidol, is an improvement over alkylamine ethoxylates.
  • Glycidol is a liquid and is less hazardous than ethylene oxide based upon its classifications by various government bodies. Therefore, the handling of glycidol and the manufacturing of alkyl polyglycerylamine are easier compared to the handling of EO and the manufacture of alkylamine ethoxylates.
  • the present disclosure is an agricultural composition
  • R is C4 - C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups;
  • x is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5;
  • y is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; and
  • x is from 0 to 30 and y is from 0 to 30 wherein x + y > 2 and up to 30.
  • x is from 0 to 30 and y is from 0 to 30 wherein x + y > 3 and up to 30.
  • Gly is a glyceryl residue.
  • the polyglyceryl moiety formed when x or y is greater than 1 can be linear or branched.
  • a linear polyglyceryl moiety could have the following formula (II).
  • a branched poly glyceryl moiety could have the following formula (III).
  • the polyglyceryl moiety can include both branched and linear segments.
  • the present disclosure is a pesticide composition
  • a pesticide composition comprising at least one pesticide and at least one alkyl polyglycerylamine surfactant of structure (I).
  • the present disclosure is a composition
  • a composition comprising the alkyl polyglycerylamine surfactant of structure (I) and a diluent selected from water, glycols, or liquid alcohol alkoxylate.
  • Figure 1 is a graph showing the results of the bio-efficacy study of Example 9.
  • R is C4 - C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups; x is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; y is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; and x + y > 2.
  • R is C16-C18.
  • R is C12-C16.
  • R is a hydrocarbon group derived from tallow, coco, oleyl, and combinations thereof.
  • x is from 0 to 30 and y is from 0 to 30 wherein x + y > 2 and up to 30.
  • x is from 0 to 30 and y is from 0 to 30 wherein x + y > 3 and up to 30.
  • the alkylamine glycidol surfactant may be described as an alkylamine polyglycidol surfactant.
  • Gly is a glyceryl residue.
  • the polyglyceryl moiety formed when x or y is greater than 1 can be linear or branched.
  • a linear polyglyceryl moiety could have the following formula (II).
  • a branched poly glyceryl moiety could have the following formula (III).
  • Propagation of the polyglyceryl moiety can be from the terminal primary hydroxyl of a glyceryl residue (resulting in a linear segment), or from the non-terminal secondary hydroxyl of the glyceryl residue (resulting in a branched segment).
  • the surfactant may be further defined as a soyalkylamine based polyglycerylamine, as understood by one of skill in the art.
  • a soyalkylamine based polyglycerylamine as understood by one of skill in the art.
  • soybean oil is as follows:
  • Soybean oil 14% saturated; 81% unsaturated
  • the“R” group described above may reflect, be, or represent one or more of these substituents of soybean oil.
  • R may be formed from, or be chosen from, a palmitic moiety, a stearic moiety, an oleic moiety, a linoleic moiety, a linolenic moiety, or combinations thereof.
  • the R group may be a described as a fatty group that is chosen from any one or more of the those set forth above.
  • combinations of different soyalkylamine based polyglycerylamines may be formed wherein each includes one or more of the aforementioned groups.
  • an agrochemical is a chemical used in agricultural formulations.
  • agrochemicals include fertilizers, micronutrients, activator adjuvants or potentiators, drift control agents, emulsifiers, deposition aids, water conditioners, wetting agents, dispersants, compatibility agents, suspension aids, pesticides such as herbicides, fungicides, and insecticides, and growth inhibitors.
  • One embodiment of the present disclosure is a herbicide formulation containing the alkyl polyglycerylamine surfactants of the present disclosure.
  • Suitable herbicides include, but are not limited to, acetochlor, acifluorfen, aclonifen, alachlor, ametryn, amidosulfuron, aminopyralid, amitrole, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benfluralin, bensulfuron-methyl, bentazone, bifenox, binalafos, bispyribac-sodium, bromacil, bromoxynil, butachlor, butroxidim, cafenstrole, carbetamide, carfentrazone-ethyl, chloridazon, chlorimuron-ethyl, chlorobromuron, chlorotoluron, chlorsulfuron, cinidon-ethyl, cino
  • Preferred herbicides are acetochlor, atrazine, dicamba, glufosinate, paraquat, glyphosate, 2,4-D and mixtures and combinations thereof. More preferred herbicides are 2,4-D, atrazine, dicamba, glyphosate, and glufosinate and mixtures and combinations thereof. The most preferred herbicides are glyphosate and glufosinate.
  • the herbicide is an acid, it can be used in the acid form though it is preferred that the herbicide be in the salt form selected from at least one of the group of an amine, lithium, sodium, ammonium or potassium. It shall be pointed out that when a pesticide appears in the text as a general name without specifying the counterions, it means both its acid form and salt form throughout the specification.
  • fungicide formulation containing the alkyl polyglycerylamine surfactants of the present disclosure.
  • suitable fungicides include, but are not limited to, acibenzolar-S-methyl, aldimorph, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benthiavalicarb, binapacryl, biphenyl, bitertanol, blasticidin-S, boscalid, bromuconazole, bupirimate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, copper, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocy
  • Still another embodiment of the present disclosure is an insecticide formulation containing the alkylamine glycidol surfactants of the present disclosure.
  • suitable insecticides include, but are not limited to, kerosene or borax, botanicals or natural organic compounds (nicotine, pyrethrin, strychnine and rotenone), chlorinated hydrocarbon (DDT, lindane, chlordane), organophosphates (malathion and diazinon), carbamates (carbaryl and propoxur), fumigants (naphthalene) and benzene (mothballs), synthetic pyrethroids, and mixtures and combinations thereof.
  • kerosene or borax botanicals or natural organic compounds (nicotine, pyrethrin, strychnine and rotenone), chlorinated hydrocarbon (DDT, lindane, chlordane), organophosphates (malathion and diazinon), carbamates (carbaryl and propoxur), fum
  • One embodiment of the present disclosure is a surfactant composition
  • a surfactant composition comprising alkyl polyglycerylamine of structure (I) and a diluent, wherein the concentration of the alkyl polyglycerylamine is from about 30 - 90%, preferably from 40 - 80%, or more preferably from 50 - 75%.
  • the diluent is selected from water, glycols, liquid alcohol alkoxylate, or combinations thereof.
  • Yet still another embodiment of the present disclosure is a mixture containing any herbicide, fungicide, and insecticide selected from the above groups and further containing one or more alkyl polyglycerylamine surfactants of the present disclosure.
  • alkyl polyglycerylamine surfactants of the present disclosure can be used as a tank- mix additive or formulated in an in-can formulation. They are suitable in solid pesticide formulations and, particularly, in liquid pesticide formulations.
  • additives that can be present in the formulations of the present disclosure are defoamers, diluents, compatibility agents, biocides, thickeners, drift control agents, dyes, fragrances, and chelating agents.
  • a compatibility agent may not be necessary due to the high compatibility of alkyl polyglycerylamine surfactants in high load pesticide formulations.
  • the use concentration of the alkyl polyglycerylamine surfactant of the present disclosure in an in-can pesticide formulation may be from about 0.005 % to about 30 %, preferably about 0.05 %to about 20 %, and more preferably about 0.5 % to about 15 % in weight %.
  • the pesticide concentration is from about 5 % to 65 %, preferably from 10 % to 60 %, and more preferably from 30 % to 55 %, and still more preferably from 40 % to 55 %, based on weight % active ingredient.
  • the use concentration of the alkyl polyglycerylamine surfactant of the present disclosure in a tank mix pesticide spray solution may be from about 0.001 % to about 5 %, preferably about 0.01 % to about 2 %, and more preferably about 0.1 % to about 1 % (in weight % surfactant basis) in the total spray solution.
  • the method comprises applying an effective amount of the agricultural composition to plants (particularly crops) to kill or control pests.
  • the agricultural composition listed above is contacted with the pest.
  • the agricultural composition may be used in the above listed form or diluted with water or an appropriate diluent.
  • the surfactants of the disclosure may also be used with other surfactants such as alkylamine alkoxylates and their quaternaries, anionic surfactants such as alkyl or ether sulfate, alkyl or aryl sulfonate, phosphate ester and ethoxylated phosphate ester, nonionic surfactants such as alcohol alkoxylates, alkyl (C6-C18) polyglucoside, amphoteric surfactants, quaternary surfactants, and silicone surfactants.
  • anionic surfactants such as alkyl or ether sulfate, alkyl or aryl sulfonate, phosphate ester and ethoxylated phosphate ester
  • nonionic surfactants such as alcohol alkoxylates, alkyl (C6-C18) polyglucoside
  • amphoteric surfactants quaternary surfactants
  • silicone surfactants such as silicone surfactants.
  • the disclosure provides an agricultural composition comprising at least one agrochemical and at least one alkylamine glycidol surfactant of the structure I:
  • R is C4 - C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups; x is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; y is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; x + y > 2 and up to 30, and Gly is a glyceryl residue.
  • x + y > 3 and up to 30.
  • x + y is from 5 to 20.
  • x + y is from 2 to 10.
  • the agrochemical is a pesticide, herbicide, fungicide, or insecticide.
  • the agrochemical is an organophosphorus herbicide, preferably glyphosate or glufosinate.
  • the agrochemical is an auxin herbicide, preferably dicamba or 2,4-D.
  • the agrochemical is a conazole fungicide, preferably a triazole fungicide, and more preferably it is tebuconazole.
  • the agrochemical is a pyrethroid insecticide, preferably a pyrethroid ester insecticide.
  • the pyrethroid ester insecticide is bifenthrin.
  • R is C16-C18.
  • R is C12-C16.
  • R is a hydrocarbon group derived from tallow, coco, oleyl, and combinations thereof.
  • x is from 0 to 30 and y is from 0 to 30 wherein x + y > 2 and up to 30. In other embodiments, x is from 0 to 30 and y is from 0 to 30 wherein x + y > 3 and up to 30.
  • the alkylamine glycidol surfactant may be described as an alkylamine polyglycidol surfactant. In various non-limiting embodiments, it is expressly contemplated that all values and ranges of values including and between those set forth above are herein expressly contemplated for use. It is contemplated that two or more of these surfactants may be combined together in a surfactant composition.
  • This disclosure also provides a method of treating vegetation, wherein the method comprises applying an effective amount of the agricultural composition as described above to vegetation.
  • This disclosure also contemplates the surfactant itself apart from the agricultural composition, i.e., any embodiment of the surfactant above.
  • T for“tallowamine”,“O” for oleylamine”,“C” for“cocoamine”, and G for Glycerol units.
  • T-5G i.e., tallowamine 5G
  • T-5G means tallowamine with 5 glycerol units.
  • C-2G i.e, cocoamine 2G
  • cocoamine 2G means cocoamine with 2 glycerol units
  • the products thus obtained can optionally be further diluted by adding necessary amount of water or other solvents/diluents.
  • Samples #2-#8 the process for Sample #1 was repeated using the indicated amine in the relevant molar ratio with glycidol.
  • the process of Sample #1 was repeated using a molar ratio of 1:10 for tailowamine and glycidol
  • Sample #3 used a molar ratio of 1:6 for oleylamine and glycidol
  • Sample #4 used a molar ratio of 1:8 for oleylamine and glycidol, and so forth.
  • alkyl polyglycerylamine samples active ingredient plus biproducts such as polyglycerols
  • honey-like products very high viscosity
  • these products can form hard gels when added to water (or an aqueous solution) and the gels can take a long time to dissolve.
  • These surfactants can be converted into easy to handle products in practice.
  • Several diluents were found to be effective in reducing the viscosity of the products and minimizing the gel forming potential. The examples are shown in Table 2.
  • alkyl polyglycerylamine surfactants of the disclosure can be diluted to improve handling and workability.
  • Example 3 Alkyl polyglycerylamine in aqueous high load pesticide formulations
  • High load pesticide formulations have advantages of shipping less water and using less material for shipping containers. However, high load formulations can be difficult to incorporate the amount of adjuvants necessary for efficacy because the high load formulation frequently becomes separated at > 55° C storage temperature. Typically, the amount of the adjuvant in formulation preferably is at least 8 wt% for acceptable efficacy.
  • Emulpon CO-360 is castor oil ethoxylate, a well-known emulsifier.
  • alkyl polyglycerylamine in Table 3 have better compatibility in high load pesticide formulations than their counterparts based on alkylamine ethoxylates. In some cases (e.g. samples 3.26, 3.27), they can even function as a hydrotrope (an ability to help dissolve more incompatible components). In other cases (3.22), the alkyl polyglycerylamine shows emulsification ability.
  • Example 4 Synergy in emulsion performance between emulsifiers (alkyl polyglycerylamine / alkyl EO-PO block copolymer) in tebuconazole fungicide emulsifiable concentrate formulations.
  • EC emulsifier concentrate
  • alkyl polyglycerylamine surfactants of the disclosure as potential emulsifiers, two tebuconazole emulsifiable concentrates (EC-1 and EC-2) containing 0-8G, were mixed at various ratios.
  • the emulsion was obtained by adding 1 g EC into 19 g water (5% dilution) in a 8-dram vial and inverting 10 times.
  • the bloom of the emulsion i.e., the ability to form white clouds immediately after adding to water
  • emulsion quality were evaluated according to 4 scales: excellent, good, OK (fair), and bad.
  • the emulsion performance results are shown in Table 4.
  • EC-1 15 % 0-8G + 85 % tebuconazole pre-mix (30 % tebuconazole in 70 % Armid DM- 10 CIO dimethylamide)
  • EC-2* 15 % Ethylan NS-500LQ (Alkyl EO-PO block copolymer) + 85 % tebuconazole pre-mix (30 % tebuconazole in 70 % Armid DM- 10)
  • Ethylan NS-500LQ a butyl EO/PO copolymer
  • Armid DM- 10 is a well-known hydropholic solvent.
  • EC-1 contains the 0-8G alkyl polyglycerylamine of the disclosure.
  • EC-2* is a comparative example.
  • Example 5 Synergy in emulsion performance among emulsifiers (alkyl polyglycerylamine/ alkyl EO-PO block copolymer / Ca DDBS) in tebuconazole fungicide emulsifiable concentrate formulations.
  • tebuconazole emulsifiable concentrates EC-1, EC-2, and EC-3, were mixed at various ratios.
  • the emulsion was obtained by adding 1 g EC into 19 g water (5% dilution) in a 8 dram vial and inverting 10 times. Bloom and emulsion quality were evaluated according to 4 scales: excellent, good, OK (fair), and bad. The emulsion performance results are shown in Table 5.
  • EC-1 and EC-2 were the same as in example 4.
  • Witconate P-1220EH is a well-known emulsifier containing -60% Ca dodecylbenzene sulfonate.
  • alkyl polyglycerylamine surfactants such as 0-8G
  • alkyl polyglycerylamine surfactants have the potential as a (co)emulsifier in a tebuconazole fungicide EC.
  • Example 6 Synergy in emulsion performance between emulsifiers (alkyl polyglycerylamine and alkyl EO-PO block copolymer) in bifenthrin insecticide emulsifiable concentrate formulations.
  • EC-4 and EC-5 Two bifenthrin emulsifiable concentrates, EC-4 and EC-5, were mixed at various ratios. The emulsion was obtained by adding 1 g EC into 19 g water (5% dilution) in a 8 dram vial and inverting 10 times. Bloom and emulsion quality were evaluated according to 4 scales: excellent, good, OK (fair), and bad. The emulsion performance results are shown in Table 6. [0075] EC-4: 8.1% O-10G + 91.9% bifenthrin pre-mix (10% bifenthrin + 40% Aromatic 200 + 50% Armid DM- 10)
  • alkyl polyglycerylamine surfactants such as O- 10G
  • O- 10G alkyl polyglycerylamine surfactants
  • Example 7 Synergy in emulsion performance among emulsifiers (alkyl polyglycerylamine / alkyl EO-PO block copolymer / Ca-DDBS) in insecticide emulsifiable concentrate formulations
  • emulsifiers alkyl polyglycerylamine / alkyl EO-PO block copolymer / Ca-DDBS
  • EC-4 and EC-5 were the same as in example 6.
  • EC-6* 8.1% Witconate P-1220EH (60% Ca DDBS) + 91.9% bifenthrin pre-mix (10% bifenthrin + 40% Aromatic 200 + 50% Aramid DM- 10).
  • alkyl polyglycerylamine surfactants such as O-l 0G
  • O-l 0G alkyl polyglycerylamine surfactants
  • Example 8 Ability of alkyl polyglycerylamine surfactants to form microemulsions.
  • 10G can be used to form microemulsions.
  • Example 9 Bio-efficacy of IPA-glyphosate with and without alkyl polyglycerylamine surfactants in green house trial 2 weeks after treatment.
  • Ethomeen T/25 tallowamine ethoxylate a well-known adjuvant in pesticide formulations
  • the glyphosate only sample was used as the negative control.
  • the wheat (a model plant) was sprayed at three rates: 150 g ae/H, 300 g ae/H and 600 g ae/H. The rating was obtained 2 weeks after treatment (WAT).
  • the bioefficacy results as illustrated in the graph of Figure 1 showed that alkyl polyglycerylamine, exemplified by T-5G, T-10G, C-2G, and 0-8G, had better weed control performance than the glyphosate alone sample.
  • the performance of T-5G, T-10G, C-2G, and 0-8G were comparable to Ethomeen T/25.

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Abstract

This disclosure provides an agricultural composition comprising at least one agrochemical and at least one alkylamine glycidol surfactant of the structure I: where R is C4 – C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups; x is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; y is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; x + y ≥ 2 and up to 30, and Gly is a glyceryl residue.

Description

ALKYL POLY GLY CERYLAMINE BASED SURFACTANTS FOR
AGRICULTURAL USE
FIELD OF THE DISCLOSURE
[0001] The present disclosure generally relates to nitrogen containing glycidol surfactants as adjuvants for pesticide formulations.
BACKGROUND OF THE DISCLOSURE
[0002] Many surfactants are used as adjuvants in pesticide formulations. Adjuvants can be used, for example, as a potentiator which is able to enhance the bioefficacy of the pesticides, a wetting agent, an emulsifier, a spreading agent, a deposition aid, a drift control agent, a water conditioner, a crystal inhibitor, a suspension aid, a thickener, or a dispersant. The bioefficacy of pesticides can be enhanced by the addition of appropriate surfactant adjuvants. For example, it is well known that the bioefficacy of herbicides, fungicides, and insecticides can be enhanced by nitrogen containing surfactants such as alkyl amine alkoxylate surfactants. Examples of nitrogen containing surfactants as potentiator adjuvants for herbicides can be found in US4528023 and US5226943. US5226943 also mentions that the activity of fungicide compositions can be improved by incorporating certain nitrogen containing surfactants. Examples of nitrogen containing surfactants as potentiator adjuvants for insecticides can be found in WO 201280099. Examples of nitrogen containing surfactants as emulsifiers in pesticide emulsions can be found in US5565409 and US 8097563. Examples of nitrogen containing surfactants as thickeners in glyphosate formulations can be found in W0201020599. Examples of nitrogen containing surfactants as drift control agents in pesticide emulsions can be found in W02013098220.
[0003] The production of alkylamine ethoxylates requires a high degree of care and skill. Alkylamine ethoxylates are made by reacting ethylene oxide and alkylamines. Ethylene oxide (EO) is a hazardous gaseous chemical (boiling point 10.7 °C). At room temperature it is a flammable, irritating, and anaesthetic gas. Because of its volatile nature, EO is commonly handled and shipped as a refrigerated liquid to reduce the risk of fire or explosions. This increases transportation and storage costs. Because of the hazardous nature of EO, the production of alkylamine ethoxylates requires special design of the reactor requiring a pressured reactor with a gas feeding pipe.
[0004] Even though alkylamine ethoxylates are difficult to manufacture, they are one of the most used adjuvants in pesticide formulations. An alkylamine ethoxylate molecule contains a hydrophilic portion (a tertiary nitrogen with various EO units) and a hydrophobic portion (hydrocarbon group) as shown for example in the following general structure:
(CH2-CH20)X H
(CH2-CH20)y H where R is a hydrocarbon group (i.e., the hydrophobic portion) of various chain lengths and x and y can adopt various values. It is this molecular structure that creates usefulness as adjuvants in agricultural applications. It is well known that the physical properties of an alkylamine ethoxylate can be altered by varying the hydrocarbon chain length and the number of EO units to suit various application needs.
[0005] One of the well-known applications of alkylamine ethoxylates is in glyphosate herbicide formulations as a potentiator adjuvant. It is known in the art that, in the alkylamine ethoxylate family, an alkylamine ethoxylate with a longer hydrocarbon chain length (about Cl 8 or longer) and a higher number of EO units (higher than about 10) is more efficacious for glyphosate. It is also a common practice to use high load glyphosate formulations [e.g., 540 g/1 ae (acid equivalent) glyphosate in water] to minimize transportation costs and storage costs because high load formulations carry less water. An effective formulation requires a sufficient amount of adjuvants, typically > ~ 10% in formulations. However, an alkylamine ethoxylate with a long carbon chain length (>= ~ Cl 8) and with an EO unit >= ~ 5 may not be compatible in a high load formulation, leading to a low cloud point (the temperature at which the sample turns from clear to hazy as the temperature increases) and eventual phase separation. To be able to include a sufficient amount of an effective alkylamine ethoxylate adjuvant in the high load formulations, a hydrotrope or compatibility agent generally must be used (W02010036996). However, hydrotropes or compatibility agents do not significantly contribute to bioefficacy enhancing effect and their use increases the total costs of formulations.
[0006] To produce alkylamine derivatives useful for agricultural applications, hydrocarbons with various chain lengths are readily available, but hydrophilic groups have limited choices besides ethylene oxide. It is desirable to have alkylamine derivatives that behave similarly to alkylamine ethoxylates in agricultural applications but that also: (1) are less hazardous while handling the components; (2) allow easier manufacturing conditions; and (3) possess better compatibility in high load pesticide formulations. The subject matter of the current disclosure provides these advantages over what is currently known in the art.
SUMMARY OF THE DISCLOSURE
[0007] The present disclosure generally relates to nitrogen containing surfactants, i.e., alkyl polyglycerylamine (or alkylamine glycidol surfactant), obtained by the reaction of alkylamine and glycidol. Unexpectedly, the alkyl polyglycerylamine surfactants of the present disclosure have better compatibility than alkylamine ethoxylates in high load agricultural formulations without the need for compatibility agents. In particular, alkyl polyglycerylamine surfactants of the present disclosure are compatible in high load herbicide formulations containing herbicides such as 2,4-D salt, dicamba salt, glyphosate salt, and glufosinate salt without the need for a hydrotrope (compatibility agent) and can be used as a (co) emulsifier in pesticide formulations.
[0008] Alkyl polyglycerylamine, obtained by reacting an alkylamine with glycidol, is an improvement over alkylamine ethoxylates. Glycidol is a liquid and is less hazardous than ethylene oxide based upon its classifications by various government bodies. Therefore, the handling of glycidol and the manufacturing of alkyl polyglycerylamine are easier compared to the handling of EO and the manufacture of alkylamine ethoxylates.
[0009] In one embodiment, the present disclosure is an agricultural composition comprising at least one agrochemical and at least one alkyl polyglycerylamine surfactant selected from the following general structure (I):
(Structure I) where R is C4 - C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups; x is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; y is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; and x + y > 2. In various embodiments, x is from 0 to 30 and y is from 0 to 30 wherein x + y > 2 and up to 30. In other embodiments, x is from 0 to 30 and y is from 0 to 30 wherein x + y > 3 and up to 30.
[0010] Gly is a glyceryl residue. The polyglyceryl moiety formed when x or y is greater than 1 can be linear or branched. A linear polyglyceryl moiety could have the following formula (II).
[0011] A branched poly glyceryl moiety could have the following formula (III).
[0012] In some embodiments, the polyglyceryl moiety can include both branched and linear segments.
[0013] In another embodiment, the present disclosure is a pesticide composition comprising at least one pesticide and at least one alkyl polyglycerylamine surfactant of structure (I).
[0014] In still another embodiment, the present disclosure is a composition comprising the alkyl polyglycerylamine surfactant of structure (I) and a diluent selected from water, glycols, or liquid alcohol alkoxylate.
DESCRIPTION OF THE FIGURE
[0015] The present disclosure will hereinafter be described in conjunction with the following Figure, wherein Figure 1 is a graph showing the results of the bio-efficacy study of Example 9.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0016] The alkyl polyglycerylamine surfactant of the disclosure has the following general structure (I):
(Structure I) where R is C4 - C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups; x is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; y is 0 to 100, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; and x + y > 2. In one embodiment R is C16-C18. In one embodiment R is C12-C16. In one embodiment, R is a hydrocarbon group derived from tallow, coco, oleyl, and combinations thereof. In various embodiments, x is from 0 to 30 and y is from 0 to 30 wherein x + y > 2 and up to 30. In other embodiments, x is from 0 to 30 and y is from 0 to 30 wherein x + y > 3 and up to 30. In such embodiments, the alkylamine glycidol surfactant may be described as an alkylamine polyglycidol surfactant. In various non-limiting embodiments, it is expressly contemplated that all values and ranges of values including and between those set forth above are herein expressly contemplated for use. It is contemplated that two or more of these surfactants may be combined together in a surfactant composition.
[0017] Gly is a glyceryl residue. The polyglyceryl moiety formed when x or y is greater than 1 can be linear or branched. A linear polyglyceryl moiety could have the following formula (II).
A branched poly glyceryl moiety could have the following formula (III).
[0018] Propagation of the polyglyceryl moiety can be from the terminal primary hydroxyl of a glyceryl residue (resulting in a linear segment), or from the non-terminal secondary hydroxyl of the glyceryl residue (resulting in a branched segment).
[0019] In still other embodiments, the surfactant may be further defined as a soyalkylamine based polyglycerylamine, as understood by one of skill in the art. For example, is it known that the typical composition of soybean oil is as follows:
Soybean oil: 14% saturated; 81% unsaturated
% Fatty group
10 palmitic 16:0 saturated C16
4 stearic 18:0 saturated C18
23 oleic 18:1 n-9 mono-unsaturated Cl 8
51 linoleic 18:2 n-6 Di-unsaturated C18
7 linolenic 18:3 n-3 Tri-unsaturated C18 Accordingly, it is contemplated that the“R” group described above may reflect, be, or represent one or more of these substituents of soybean oil. For example, R may be formed from, or be chosen from, a palmitic moiety, a stearic moiety, an oleic moiety, a linoleic moiety, a linolenic moiety, or combinations thereof. Alternatively, the R group may be a described as a fatty group that is chosen from any one or more of the those set forth above. Even further, combinations of different soyalkylamine based polyglycerylamines may be formed wherein each includes one or more of the aforementioned groups.
[0020] As used herein, an agrochemical is a chemical used in agricultural formulations. Non limiting examples of agrochemicals include fertilizers, micronutrients, activator adjuvants or potentiators, drift control agents, emulsifiers, deposition aids, water conditioners, wetting agents, dispersants, compatibility agents, suspension aids, pesticides such as herbicides, fungicides, and insecticides, and growth inhibitors.
[0021] One embodiment of the present disclosure is a herbicide formulation containing the alkyl polyglycerylamine surfactants of the present disclosure. Suitable herbicides include, but are not limited to, acetochlor, acifluorfen, aclonifen, alachlor, ametryn, amidosulfuron, aminopyralid, amitrole, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benfluralin, bensulfuron-methyl, bentazone, bifenox, binalafos, bispyribac-sodium, bromacil, bromoxynil, butachlor, butroxidim, cafenstrole, carbetamide, carfentrazone-ethyl, chloridazon, chlorimuron-ethyl, chlorobromuron, chlorotoluron, chlorsulfuron, cinidon-ethyl, cinosulfuron, clethodim, clomazone, clopyralid, cloransulam-methyl, clorsulfuron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, dalapon, desmedipham, dicamba, dichlobenil, dichlormid, diclosulam, diflufenican, dimefuron, dimepipeate, dimethachlor, dimethenamid, diquat, diuron, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fentrazamide, flazasulfuron, florasulam, fluchloralin, flufenacet, flumetsulam, flumioxazin, fluometuron, flupyrsulfuron-methyl, flurochloridone, fluroxypyr, flurtamone, fomesafen, foramsulfuron, glufosinate, hexazinone, imazamethabenz-m, imazamox, mazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, ioxynil, isoproturon, isoxaben, isoxaflutole, Lactofen, lenacil, linuron, mefenacet, mesosulfuron-methyl, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, MSMA, napropamide, nicosulfuron, norflurazon, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxyfluorfen, paraquat, pendimethalin, phenmedipham, picloram, pretilachlor, profoxydim, prometryn, propanil, propisochlor, propoxycarbazone, propyzamide, prosulfocarb, prosulfuron, pyraflufen-ethyl, pyrazosulfuron, pyridate, pyrithiobac, quinclorac, quinmerac, rimsulfuron, sethoxydim, simazine, s-metolachlor, sulcotrione, sulfentrazone, sulfosulfuron, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-allate, triasulfuron, tribenuron-methyl, triclopyr, trifloxysulfuron, trifluralin, triflusulfuron-methyl, tritosulfuron, and mixtures and combinations thereof. Preferred herbicides are acetochlor, atrazine, dicamba, glufosinate, paraquat, glyphosate, 2,4-D and mixtures and combinations thereof. More preferred herbicides are 2,4-D, atrazine, dicamba, glyphosate, and glufosinate and mixtures and combinations thereof. The most preferred herbicides are glyphosate and glufosinate. When the herbicide is an acid, it can be used in the acid form though it is preferred that the herbicide be in the salt form selected from at least one of the group of an amine, lithium, sodium, ammonium or potassium. It shall be pointed out that when a pesticide appears in the text as a general name without specifying the counterions, it means both its acid form and salt form throughout the specification.
[0022] Another embodiment of the present disclosure is a fungicide formulation containing the alkyl polyglycerylamine surfactants of the present disclosure. Examples of suitable fungicides include, but are not limited to, acibenzolar-S-methyl, aldimorph, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benthiavalicarb, binapacryl, biphenyl, bitertanol, blasticidin-S, boscalid, bromuconazole, bupirimate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, copper, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, dodemorph, dodine, edifenphos, enestrobin, epoxiconazole, etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-Al, fthalide, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, iodocarb, ipconazole, iprobenfos (IBP), iprodione, iprovalicarb, isoprothiolane, isotianil, kasugamycin, kresoxim-methyl, laminarin, mancozeb, mandipropamid, maneb, material of biological, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, metiram, metominostrobin, metrafenone, mineral oils, organic oils, myclobutanil, naftifine, nuarimol, octhilinone, ofurace, origin, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, pefurazoate, penconazole, pencycuron, penthiopyrad, phophorous acid and, picoxystrobin, piperalin, polyoxin, potassium bicarbonate, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, quintozene (PCNB), salts, silthiofam, simeconazole, spiroxamine, streptomycin, sulphur, tebuconazole, teclofthalam, tecnazene (TCNB), terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofosmethyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valiphenal, vinclozolin, zineb, ziram, and zoxamide, and mixtures and combinations thereof.
[0023] Still another embodiment of the present disclosure is an insecticide formulation containing the alkylamine glycidol surfactants of the present disclosure. Examples of suitable insecticides include, but are not limited to, kerosene or borax, botanicals or natural organic compounds (nicotine, pyrethrin, strychnine and rotenone), chlorinated hydrocarbon (DDT, lindane, chlordane), organophosphates (malathion and diazinon), carbamates (carbaryl and propoxur), fumigants (naphthalene) and benzene (mothballs), synthetic pyrethroids, and mixtures and combinations thereof.
[0024] One embodiment of the present disclosure is a surfactant composition comprising alkyl polyglycerylamine of structure (I) and a diluent, wherein the concentration of the alkyl polyglycerylamine is from about 30 - 90%, preferably from 40 - 80%, or more preferably from 50 - 75%. Preferably the diluent is selected from water, glycols, liquid alcohol alkoxylate, or combinations thereof.
[0025] Yet still another embodiment of the present disclosure is a mixture containing any herbicide, fungicide, and insecticide selected from the above groups and further containing one or more alkyl polyglycerylamine surfactants of the present disclosure.
[0026] The alkyl polyglycerylamine surfactants of the present disclosure can be used as a tank- mix additive or formulated in an in-can formulation. They are suitable in solid pesticide formulations and, particularly, in liquid pesticide formulations.
[0027] Other additives that can be present in the formulations of the present disclosure are defoamers, diluents, compatibility agents, biocides, thickeners, drift control agents, dyes, fragrances, and chelating agents. The use of a compatibility agent may not be necessary due to the high compatibility of alkyl polyglycerylamine surfactants in high load pesticide formulations.
[0028] The use concentration of the alkyl polyglycerylamine surfactant of the present disclosure in an in-can pesticide formulation may be from about 0.005 % to about 30 %, preferably about 0.05 %to about 20 %, and more preferably about 0.5 % to about 15 % in weight %. The pesticide concentration is from about 5 % to 65 %, preferably from 10 % to 60 %, and more preferably from 30 % to 55 %, and still more preferably from 40 % to 55 %, based on weight % active ingredient.
[0029] The use concentration of the alkyl polyglycerylamine surfactant of the present disclosure in a tank mix pesticide spray solution may be from about 0.001 % to about 5 %, preferably about 0.01 % to about 2 %, and more preferably about 0.1 % to about 1 % (in weight % surfactant basis) in the total spray solution.
[0030] Also disclosed is a method of treating plants or vegetation with the compositions of the disclosure. The method comprises applying an effective amount of the agricultural composition to plants (particularly crops) to kill or control pests. The agricultural composition listed above is contacted with the pest. The agricultural composition may be used in the above listed form or diluted with water or an appropriate diluent.
[0031] All units are in weight percent (i.e., wt %).
[0032] The surfactants of the disclosure may also be used with other surfactants such as alkylamine alkoxylates and their quaternaries, anionic surfactants such as alkyl or ether sulfate, alkyl or aryl sulfonate, phosphate ester and ethoxylated phosphate ester, nonionic surfactants such as alcohol alkoxylates, alkyl (C6-C18) polyglucoside, amphoteric surfactants, quaternary surfactants, and silicone surfactants.
[0033] In additional embodiments, the disclosure provides an agricultural composition comprising at least one agrochemical and at least one alkylamine glycidol surfactant of the structure I:
(Structure I) where R is C4 - C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups; x is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; y is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; x + y > 2 and up to 30, and Gly is a glyceryl residue.
[0034] In one embodiment, x + y > 3 and up to 30.
[0035] In another embodiment, x + y is from 5 to 20. [0036] In another embodiment, x + y is from 2 to 10.
[0037] In another embodiment, x and/or y >1 such that the poly glyceryl moiety is linear, branched or has both linear and branched segments.
[0038] In another embodiment, the agrochemical is a pesticide, herbicide, fungicide, or insecticide.
[0039] In another embodiment, the agrochemical is an organophosphorus herbicide, preferably glyphosate or glufosinate.
[0040] In a further embodiment, the agrochemical is an auxin herbicide, preferably dicamba or 2,4-D.
[0041] In still another embodiment, the agrochemical is a conazole fungicide, preferably a triazole fungicide, and more preferably it is tebuconazole.
[0042] In another embodiment, the agrochemical is a pyrethroid insecticide, preferably a pyrethroid ester insecticide.
[0043] In another embodiment, the pyrethroid ester insecticide is bifenthrin.
[0044] In another embodiment, R is C16-C18.
[0045] In a further embodiment, R is C12-C16.
[0046] In another embodiment, R is a hydrocarbon group derived from tallow, coco, oleyl, and combinations thereof.
[0047] In various embodiments, x is from 0 to 30 and y is from 0 to 30 wherein x + y > 2 and up to 30. In other embodiments, x is from 0 to 30 and y is from 0 to 30 wherein x + y > 3 and up to 30. In such embodiments, the alkylamine glycidol surfactant may be described as an alkylamine polyglycidol surfactant. In various non-limiting embodiments, it is expressly contemplated that all values and ranges of values including and between those set forth above are herein expressly contemplated for use. It is contemplated that two or more of these surfactants may be combined together in a surfactant composition.
[0048] This disclosure also provides a method of treating vegetation, wherein the method comprises applying an effective amount of the agricultural composition as described above to vegetation.
[0049] This disclosure also contemplates the surfactant itself apart from the agricultural composition, i.e., any embodiment of the surfactant above.
[0050] The following non-limiting examples are presented to further illustrate and explain the present disclosure. EXAMPLES
[0051] Example 1. Synthesis of alkyl polyglycerylamine surfactants
Raw-materials used
Tallowamine Armeen TM-97 (AkzoNobel)
Oleylamine Armeen OM-97 (AkzoNobel)
Cocoalkylamine Armeen CD (AkzoNobel)
Glycidol Acros
Abbreviations Used
“T” for“tallowamine”,“O” for oleylamine”,“C” for“cocoamine”, and G for Glycerol units. For example:
T-5G (i.e., tallowamine 5G) means tallowamine with 5 glycerol units.
0-6G (i.e., oleylamine 6G) means oleylamine with 6 glycerol units.
C-2G (i.e, cocoamine 2G) means cocoamine with 2 glycerol units.
Table 1. Synthesis / Compound Examples
Synthesis Procedure
[0052] The following procedure was used to create sample #1, and similar procedures were used to synthesize the additional samples, with the relevant fatty acid amine and glycidol molar ratios adjusted appropriately (as discussed below).
[0053] Glycidol (44.4 g, 0.6 mol) was added dropwise over a period of 3 hrs to tallowamine (32.04 g, 0.12 mol) stirred in a round bottom flask under nitrogen atmosphere keeping the temperature of the reaction mixture between 80° to 120° C. The reaction mixture was further stirred for about an hour at around 110°-120° C until IR analysis showed no more epoxide peaks around 840 cm 1 due to glycidol. A clear pale brown viscous liquid product thus obtained was collected.
[0054] The products thus obtained can optionally be further diluted by adding necessary amount of water or other solvents/diluents.
[0055] For Samples #2-#8, the process for Sample #1 was repeated using the indicated amine in the relevant molar ratio with glycidol. For example, for Sample #2, the process of Sample #1 was repeated using a molar ratio of 1:10 for tailowamine and glycidol, Sample #3 used a molar ratio of 1:6 for oleylamine and glycidol, Sample #4 used a molar ratio of 1:8 for oleylamine and glycidol, and so forth.
[0056] It is to be expected that side products such as polyglycerol can be formed in the final product. The samples described herein and in the following examples were used without further purification.
Example 2. Diluted alkyl polyglycerylamine compositions
[0057] Some alkyl polyglycerylamine samples (active ingredient plus biproducts such as polyglycerols) are honey-like (very high viscosity) and are difficult to handle. Moreover, these products can form hard gels when added to water (or an aqueous solution) and the gels can take a long time to dissolve. These surfactants can be converted into easy to handle products in practice. Several diluents were found to be effective in reducing the viscosity of the products and minimizing the gel forming potential. The examples are shown in Table 2.
Table 2. Effect of diluent on gel formation
[0058] As shown in Table 2, alkyl polyglycerylamine surfactants of the disclosure can be diluted to improve handling and workability.
[0059] Example 3. Alkyl polyglycerylamine in aqueous high load pesticide formulations
[0060] Compatibilities of various alkyl polyglycerylamine surfactants with comparative examples in high load pesticide formulations were obtained in Table 3.
[0061] High load pesticide formulations have advantages of shipping less water and using less material for shipping containers. However, high load formulations can be difficult to incorporate the amount of adjuvants necessary for efficacy because the high load formulation frequently becomes separated at > 55° C storage temperature. Typically, the amount of the adjuvant in formulation preferably is at least 8 wt% for acceptable efficacy.
Table 3. Compatibilities of various alkyl polyglycerylamines with comparative examples in high load pesticide formulations
*: comparative example
**: Emulpon CO-360 is castor oil ethoxylate, a well-known emulsifier.
[0062] The results show that the alkyl polyglycerylamine in Table 3 have better compatibility in high load pesticide formulations than their counterparts based on alkylamine ethoxylates. In some cases (e.g. samples 3.26, 3.27), they can even function as a hydrotrope (an ability to help dissolve more incompatible components). In other cases (3.22), the alkyl polyglycerylamine shows emulsification ability.
Example 4. Synergy in emulsion performance between emulsifiers (alkyl polyglycerylamine / alkyl EO-PO block copolymer) in tebuconazole fungicide emulsifiable concentrate formulations.
[0063] It is generally known in the art that three emulsifiers working together are generally needed to form a good emulsifier concentrate (EC). In some cases, only two emulsifiers may be necessary. In rare situations, one emulsifier can be sufficient. The performance of ECs depends on proper selection of the emulsifiers and concentration of the emulsifiers.
[0064] To evaluate the alkyl polyglycerylamine surfactants of the disclosure as potential emulsifiers, two tebuconazole emulsifiable concentrates (EC-1 and EC-2) containing 0-8G, were mixed at various ratios. The emulsion was obtained by adding 1 g EC into 19 g water (5% dilution) in a 8-dram vial and inverting 10 times. The bloom of the emulsion (i.e., the ability to form white clouds immediately after adding to water) and emulsion quality were evaluated according to 4 scales: excellent, good, OK (fair), and bad. The emulsion performance results are shown in Table 4.
[0065] EC-1: 15 % 0-8G + 85 % tebuconazole pre-mix (30 % tebuconazole in 70 % Armid DM- 10 CIO dimethylamide)
[0066] EC-2*: 15 % Ethylan NS-500LQ (Alkyl EO-PO block copolymer) + 85 % tebuconazole pre-mix (30 % tebuconazole in 70 % Armid DM- 10)
[0067] Ethylan NS-500LQ, a butyl EO/PO copolymer, is a well-known emulsifier. Armid DM- 10 is a well-known hydropholic solvent. EC-1 contains the 0-8G alkyl polyglycerylamine of the disclosure. EC-2* is a comparative example.
Table 4. Synergy in emulsion performance between emulsifiers (alkyl polyglycerylamine/ alkyl EO-PO block copolymer) in tebuconazole fungicide emulsifiable concentrate formulations
[0068] The result from table 4 indicates that 0-8G has the potential to be a (co)emulsifier in a tebuconazole fungicide EC.
Example 5. Synergy in emulsion performance among emulsifiers (alkyl polyglycerylamine/ alkyl EO-PO block copolymer / Ca DDBS) in tebuconazole fungicide emulsifiable concentrate formulations.
[0069] Three tebuconazole emulsifiable concentrates, EC-1, EC-2, and EC-3, were mixed at various ratios. The emulsion was obtained by adding 1 g EC into 19 g water (5% dilution) in a 8 dram vial and inverting 10 times. Bloom and emulsion quality were evaluated according to 4 scales: excellent, good, OK (fair), and bad. The emulsion performance results are shown in Table 5.
[0070] EC-1 and EC-2 were the same as in example 4.
[0071] EC-3*: 15% Witconate P-1220EH (60% Ca DDBS) + 85% tebuconazole pre-mix (30% tebuconazole in 70% Armid DM- 10)
[0072] Witconate P-1220EH is a well-known emulsifier containing -60% Ca dodecylbenzene sulfonate.
Table 5. Synergy in emulsion performance among emulsifiers (alkyl polyglycerylamine/alkyl EO-PO block copolymer / Ca DDBS) in tebuconazole fungicide emulsifiable concentrate formulations
[0073] The result from Table 5 indicates again that alkyl polyglycerylamine surfactants (such as 0-8G) have the potential as a (co)emulsifier in a tebuconazole fungicide EC.
Example 6. Synergy in emulsion performance between emulsifiers (alkyl polyglycerylamine and alkyl EO-PO block copolymer) in bifenthrin insecticide emulsifiable concentrate formulations.
[0074] Two bifenthrin emulsifiable concentrates, EC-4 and EC-5, were mixed at various ratios. The emulsion was obtained by adding 1 g EC into 19 g water (5% dilution) in a 8 dram vial and inverting 10 times. Bloom and emulsion quality were evaluated according to 4 scales: excellent, good, OK (fair), and bad. The emulsion performance results are shown in Table 6. [0075] EC-4: 8.1% O-10G + 91.9% bifenthrin pre-mix (10% bifenthrin + 40% Aromatic 200 + 50% Armid DM- 10)
[0076] EC-5*: 8.1% Ethylan NS-500LQ + 91.9% bifenthrin pre-mix (10% bifenthrin + 40% Aromatic 200 + 50% Armid DM- 10)
Table 6. Synergy in emulsion performance between emulsifiers (alkyl polyglycerylamine and alkyl EO-PO block copolymer) in insecticide emulsifiable concentrate formulations.
0077] The result from Table 6 indicates that alkyl polyglycerylamine surfactants (such as O- 10G) have the potential as a (co)emulsifier in a bifenthrin insecticide EC.
Example 7. Synergy in emulsion performance among emulsifiers (alkyl polyglycerylamine / alkyl EO-PO block copolymer / Ca-DDBS) in insecticide emulsifiable concentrate formulations [0078] Three emulsifiable concentrates, EC-4, EC-5, and EC-6, were mixed at various ratios. The emulsion was obtained by adding 1 g EC into 19 g water (5% dilution) in a 8-dram vial and inverting 10 times. Bloom and emulsion quality were evaluated according to 4 scales: excellent, good, OK (fair), and bad. The emulsion performance results are shown in Table 7.
[0079] EC-4 and EC-5 were the same as in example 6.
[0080] EC-6*: 8.1% Witconate P-1220EH (60% Ca DDBS) + 91.9% bifenthrin pre-mix (10% bifenthrin + 40% Aromatic 200 + 50% Aramid DM- 10).
Table 7. Synergy in emulsion performance among emulsifiers (alkylamine glycidol / alkyl EO-PO block copolymer / Ca DDBS) in insecticide emulsifiable concentrate formulations
[0081] The result from Table 7 indicates again that alkyl polyglycerylamine surfactants (such as O-l 0G) have the potential as a (co)emulsifier in a bifenthrin insecticide EC.
Example 8. Ability of alkyl polyglycerylamine surfactants to form microemulsions.
The following microemulsions were created:
[0082] The result from Table 8 indicates that alkyl polyglycerylamine surfactants (such as O-
10G) can be used to form microemulsions.
Example 9. Bio-efficacy of IPA-glyphosate with and without alkyl polyglycerylamine surfactants in green house trial 2 weeks after treatment.
[0083] In this example, Ethomeen T/25 tallowamine ethoxylate, a well-known adjuvant in pesticide formulations, was used as a positive control. The glyphosate only sample was used as the negative control. The wheat (a model plant) was sprayed at three rates: 150 g ae/H, 300 g ae/H and 600 g ae/H. The rating was obtained 2 weeks after treatment (WAT). The bioefficacy results as illustrated in the graph of Figure 1 showed that alkyl polyglycerylamine, exemplified by T-5G, T-10G, C-2G, and 0-8G, had better weed control performance than the glyphosate alone sample. The performance of T-5G, T-10G, C-2G, and 0-8G were comparable to Ethomeen T/25.
[0084] It is expressly contemplated that, in various non-limiting embodiments, all combinations of the aforementioned components, compositions, method steps, and options for various substituents are contemplated for use herein every if they are not described in the same paragraph or expressly related to one another within a single embodiment set forth above.
[0085] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims.

Claims

CLAIMS What is claimed is:
1. An agricultural composition comprising at least one agrochemical and at least one alkylamine glycidol surfactant of the structure I:
(Structure I) where R is C4 - C22 linear or branched, saturated or non-saturated hydrocarbon group with or without pendant hydroxyl groups; x is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; y is 0 to 30, preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5; x + y > 2 and up to 30, and Gly is a glyceryl residue.
2. The agricultural composition of claim 1 wherein x + y > 3 and up to 30.
3. The agricultural composition of claim 1 wherein x + y is from 5 to 20.
4. The agricultural composition of claim 1 wherein x + y is from 2 to 10.
5. The agricultural composition of any one of the preceding claims wherein x and/or y >1 such that the poly glyceryl moiety is linear, branched or has both linear and branched segments.
6. The agricultural composition of any one of the preceding claims wherein the agrochemical is a pesticide, herbicide, fungicide, or insecticide.
7. The agricultural composition of any one of the preceding claims wherein the agrochemical is an organophosphorus herbicide, preferably glyphosate or glufosinate.
8. The agricultural composition of any one of claims 1-5 wherein the agrochemical is an auxin herbicide, preferably dicamba or 2,4-D.
9. The agricultural composition of any one of claims 1-5 wherein the agrochemical is a conazole fungicide, preferably a triazole fungicide, and more preferably it is tebuconazole.
10. The agricultural composition of any one of claims 1-5 wherein the agrochemical is a pyrethroid insecticide, preferably a pyrethroid ester insecticide.
11. The agricultural composition of claim 10 wherein the pyrethroid ester insecticide is bifenthrin.
12. The agricultural composition of any one of the preceding claims wherein R is C16-C18.
13. The agricultural composition of any one of claims 1-11 wherein R is C12-C16.
14. The agricultural composition of any one of claims 1-11 wherein R is a hydrocarbon group derived from tallow, coco, oleyl, and combinations thereof.
15. A method of treating vegetation, wherein the method comprises applying an effective amount of the agricultural composition of any one of claims 1-14 to the vegetation.
EP19817721.4A 2018-12-12 2019-12-12 Alkyl polyglycerylamine based surfactants for agricultural use Pending EP3893641A1 (en)

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BR112021011238A2 (en) 2021-08-24
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