ALKYL AMIDOAMINE POLYGLYCEROL SURFACTANTS

An agrochemical composition includes an agrochemical and a surfactant that has a structure (I)-(VI). The surfactant may be described as an alkyl amidoamine glycerol surfactant, an oxide thereof, or as a quaternary ammonium compound thereof.

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Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National-Stage entry under 35 U.S.C. § 371 based on International Application No. PCT/EP2021/061051, filed Apr. 28, 2021 which was published under PCT Article 21(2) and which claims the benefit of U.S. Provisional Application Nos. 63/017,830; 63/017,835; and 63/017,836, each of which was filed on Apr. 30, 2020, and each of which is expressly incorporated by reference herein in its entirety.

FIELD OF THE DISCLOSURE

The present disclosure generally relates to alkyl amidoamine polyglycerol surfactants. More specifically, this disclosure relates to surfactants that are particular alkyl amidoamine polyglycerols, their oxides, and quaternary ammonium compounds.

BACKGROUND OF THE DISCLOSURE

Many surfactants are used as adjuvants in pesticide compositions. 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 including surfactants such as alkyl amine alkoxylate surfactants. Examples of nitrogen including surfactants as potentiator adjuvants for herbicides can be found in U.S. Pat. Nos. 4,528,023, 5,226,943. U.S. Pat. No. 5,226,943 also discloses that the activity of fungicide compositions can be improved by incorporating certain nitrogen including surfactants. Examples of nitrogen including surfactants as potentiator adjuvants for insecticides can be found in WO 201280099. Examples of nitrogen including surfactants as emulsifiers in pesticide emulsions can be found in U.S. Pat. Nos. 5,565,409, 8,097,563. Examples of nitrogen including surfactants as thickeners in glyphosate compositions can be found in WO201020599. Examples of nitrogen including surfactants as drift control agents in pesticide emulsions can be found in WO2013098220.

Alkyl amidoamine alkoxylates and their further derivatives are well-known surfactants useful in many industries such as agrochemicals, mining, cleaning, etc. In particular, ethoxylated alkyl amidoamines have been disclosed as adjuvants in pesticide formulations (WO199705779, U.S. Pat. No. 8,828,911, and US2010279870).

The production of alkyl amidoamine ethoxylates requires a high degree of care and skill. Alkyl amidoamine ethoxylates are made by reacting ethylene oxide and alkyl amidoamines. Ethylene oxide (EO) is a hazardous gaseous chemical (boiling point 10.7° C.). At room temperature, ethylene oxide is a flammable, irritating, and anesthetic gas. Because of its volatile nature, ethylene oxide 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 ethylene oxide, the production of alkyl amidoamine ethoxylates requires special design of the reactor requiring a pressured reactor with a gas feeding pipe.

Even though alkyl amidoamine ethoxylates are difficult to manufacture, they are one of the most used adjuvants in pesticide compositions. An alkyl amidoamine ethoxylate molecule contains a hydrophilic portion (a tertiary nitrogen with various ethylene oxide units) and a hydrophobic portion (hydrocarbon group) as shown for example in the following general formula:

where R is a hydrocarbon group (i.e., the hydrophobic portion) of various chain lengths, (AO)x is a linear or branched C2 to C4 alkoxylate group, x>0, and m is typically 0 to 4. It is this molecular structure that creates usefulness as adjuvants in agricultural applications.

To produce alkyl amidoamine derivatives, hydrocarbons with various chain lengths are readily available, but hydrophilic groups have limited choices besides ethylene oxide. It is desirable to have alkyl amidoamine derivatives that behave similarly to alkyl amidoamine ethoxylates 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 compositions.

SUMMARY OF THE DISCLOSURE

This disclosure provides an agrochemical composition that includes an agrochemical and at least one surfactant having the structure:

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30;
wherein each O is independently optionally present so long as at least one O is present;
wherein each B− is independently optionally present and when present is R1X−, so long as at least one B− is present;
wherein each R1 is independently optionally present and when present is a methyl or ethyl group; and
wherein each X− is independently Cl−, Br−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

This disclosure also provides one or more of the aforementioned surfactants independent from the agrochemical composition. In addition, other objects, desirable features and characteristics will become apparent from the summary and detailed description, and the appended claims, taken in conjunction with the accompanying drawings and the background.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and is not intended to limit the present disclosure or the application and uses of the present disclosure. Furthermore, there is no intention to be bound by any theory presented in the preceding background of the present disclosure or the following detailed description. It is to be appreciated that all numerical values as provided herein, save for the actual examples, are approximate values with endpoints or particular values intended to be read as “about” or “approximately” the value as recited.

This disclosure provides an agrochemical composition that includes at least one surfactant as described below. This disclosure also provides the surfactant itself.

In various embodiments, the surfactant has the structure:

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a; and
wherein each a is independently of from about 1 to about 30;
wherein each O is independently optionally present so long as at least one O is present;
wherein each B− is independently optionally present and when present is R1X−, so long as at least one B− is present;
wherein each R1 is independently optionally present and when present is a methyl or ethyl group; and
wherein each X− is independently Cl−, Br−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

In one embodiment, the surfactant has the structure (I):

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a; and
wherein each a is independently of from about 1 to about 30.

In one embodiment, the surfactant has the structure (II):

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30; and wherein each a is independently optionally present so long as at least one O is present.

In one embodiment, the surfactant has the structure (IV):

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30; and
wherein each O is independently optionally present so long as at least one O is present.

In one embodiment, the surfactant has the structure (IV):

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30;
wherein each O is independently optionally present so long as at least one O is present;
wherein each B− is independently optionally present and when present is R1X−, so long as at least one B− is present;
wherein each R1 is independently optionally present and when present is a methyl or ethyl group; and
wherein each X− is independently Cl−, Br−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

In one embodiment, the surfactant has the structure (V):

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30; and
wherein each O is independently optionally present so long as at least one O is present.

In one embodiment, the surfactant has the structure (VI):

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30;
wherein each O is independently optionally present so long as at least one O is present;
wherein each B− is independently optionally present and when present is R1X−, so long as at least one B− is present;
wherein each R1 is independently optionally present and when present is a methyl or ethyl group; and
wherein each X− is independently Cl−, Br−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

It is contemplated that any one of the surfactants (I)-(VI) above may be combined with any one or more surfactants (I)-(VI) above. Therefore, combinations of two or three or more surfactants (I)-(VI) above are hereby contemplated. Furthermore, each one of the surfactants (I)-(VI) above may be utilized as a single surfactant or as a combination of two or more surfactants of each of the types (I)-(VI) above. Moreover, so long as at least one of the surfactants (I)-(VI) above is utilized, any compositions or formulations can be free of any of one or more of the other of the surfactants (I)-(VI) above, or variants thereof, or can include one or more variants of one or more of the other of the surfactants (I)-(VI) above.

It is contemplated that a surfactant component may be utilized herein, e.g. in a formulation or agrochemical composition, wherein the surfactant component includes one or more of the surfactants (I)-(VI) above. For example, the surfactant component may include, be, consist essentially of, or consist of, one or more of the surfactants (I)-(VI) above.

In the aforementioned embodiments, each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group. For example, each R may have about 6 to about 22, about 7 to about 21, about 8 to about 20, about 9 to about 19, about 10 to about 18, about 11 to about 17, about 12 to about 16, about 13 to about 15, about 14 to about 15, or about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, carbon atoms. In various non-limiting embodiments, all values, both whole and fractional, and ranges of values, including and between those set forth above, are hereby expressly contemplated for use herein.

In one embodiment, one or more R groups is a linear hydrocarbon group

In one embodiment, one or more R groups is a branched hydrocarbon group

In one embodiment, one or more R groups is a saturated hydrocarbon group

In one embodiment, one or more R groups is an unsaturated hydrocarbon group

In one embodiment, each R is independently a C8-C18 group. In another embodiment, each R is independently a C8-C16 group. In another embodiment, each R is independently a C8-C14 group. In another embodiment, each R is independently a C8-C12 group. In another embodiment, each R is independently a C8-C10 group. In another embodiment, each R is independently a C10-C18 group. In another embodiment, each R is independently a C10-C16 group. In another embodiment, each R is independently a C10-C14 group. In another embodiment, each R is independently a C10-C12 group. In another embodiment, each R is independently a C12-C18 group. In another embodiment, each R is independently a C12-C16 group. In another embodiment, each R is independently a C12-C14 group. In another embodiment, each R is independently a C14-C18 group. In another embodiment, each R is independently a C14-C16 group. In another embodiment, each R is independently a C16-C18 group. In another embodiment, each R is independently a C10-C18 group.

In another embodiment, each R is independently a hydrocarbon group derived from an animal source, a vegetable source, a microbial/algae source, and combinations thereof. In one embodiment, each R is independently a hydrocarbon group derived from a vegetable source. In one embodiment, each R is independently a hydrocarbon group derived from an animal source. In one embodiment, each R is independently a hydrocarbon group derived from a microbial/algae source.

In other embodiments, each m is independently 0, 1, 2, 3, or 4, e.g. about 0 to about 4, about 0 to about 2, about 0 to about 1, about 1 to about 4, about 1 to about 3, about 1 to about 2, about 2 to about 4, about 2 to about 3, or about 3 to about 4. In various non-limiting embodiments, all values, both whole and fractional, and ranges of values, including and between those set forth above, are hereby expressly contemplated for use herein.

In one embodiment, the surfactant has structure (I) and m is 1 and a is 1 to 15. In another embodiment, the surfactant has structure (II) and m is 1 and a is 1 to 15.

In various embodiments, each Z is independently a glyceryl residue (glyceryl)a or H. In various embodiments, at least one Z must be (glyceryl)a. In various embodiments, each a is independently of from about 1 to about 30. For example, in various embodiments, each a is independently from about 2 to about 29, about 3 to about 28, about 4 to about 27, about 5 to about 26, about 6 to about 27, about 7 to about 26, about 8 to about 25, about 9 to about 24, about 10 to about 23, about 11 to about 22, about 12 to about 21, about 13 to about 20, about 14 to about 19, about 15 to about 18, or about 16 to about 17. In other embodiments, each a is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30. In various non-limiting embodiments, all values, both whole and fractional, and ranges of values, including and between those set forth above, are hereby expressly contemplated for use herein.

In one embodiment, each glyceryl residue independently comprises a linear portion, a branched portion, and a cyclic portion. In another embodiment, each glyceryl residue independently comprises a linear portion. In another embodiment, each glyceryl residue independently comprises a branched portion. In another embodiment, each glyceryl residue independently comprises a cyclic portion.

In one embodiment, a polyglyceryl moiety can be linear or branched or cyclic. In another embodiment, a linear polyglyceryl moiety can have the following formula:

In still another embodiment, a branched polyglyceryl moiety can have the following formula:

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).

In other embodiments, each O is independently optionally present so long as at least one O is present.

Moreover, in various embodiments, each B− is independently optionally present and when present is R1X−, so long as at least one B− is present. Therefore, each R1 is independently nothing, e.g. optionally present, and, if present, is a methyl or ethyl group. In one embodiment, one or more R groups is a methyl group. In another embodiment, one or more R1 groups is an ethyl group. In a further embodiments, one or more R1 groups is a methyl group and one or more R1 groups is an ethyl group.

As described above, each R1 is independently optionally present and when present is a methyl or ethyl group. Moreover, each X− is independently Cl−, Br, CH3OSO3−, or CH3CH2OSO3−, or is not present if R1 is not present, so long as at least one R1X− is present as B−. In one embodiment, each X− is independently Cl−, Br−, CH3OSO3−, CH3CH2OSO3−. In one embodiment, each X− is independently Cl−. In another embodiment, each X− is independently Br−. In another embodiment, each X− is independently CH3OSO3−. In another embodiment, each X− is independently CH3CH2OSO3−. Alternatively, one or more X− can be nothing so long as at least one R1X− is present.

In one embodiment, the surfactant may be further defined as alkyl amidoamine polyglycerol or alkyl amido polyamine polyglycerol, or alkyl amido polyglyceryl polyamine as described above. In another embodiment, the surfactant may be further defined as an amine oxide, as also described above. In another embodiment, the surfactant may be further defined as a quat or quaternary ammonium compound.

In various embodiments, each a is independently from about 1 to about 20. For example, in various embodiments, each a is independently from about 1 to about 10 or about 1 to about 4. In another embodiment, each glyceryl residue independently comprises a linear portion, a branched portion, and a cyclic portion. In another embodiment, each R is independently a C8-C18 group. In another embodiment, each R is independently a C10-C18 group. In another embodiment, each R is independently a hydrocarbon group derived from an animal source, a vegetable source, a microbial/algae source, and combinations thereof. In another embodiment, m is 1, Z is (glycerol)a, and wherein each a is from 1 to 7. In another embodiment, R1 is CH3 and X− is Cl−.

In various embodiments, the surfactant is the derivative of the reaction product or reaction product of glycidol and at least one amidoamine having the following structures:

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group; and wherein each m is independently of from about 0 to about 4.

As is known in the art, for polymers, subscripts are typically not whole numbers and may be fractional values, e.g. because they are average values. Accordingly, it is expressly contemplated that all subscripts values herein may be average values or may be fractional values including and between all values and ranges of values described herein, in various non-limiting embodiments. Alternatively one or more subscripts may be whole numerical values and may also still be average values.

In various embodiments, the condition for the reaction with glycidol to obtain alkyl amidoamine polyglycerols is similar to the reaction condition of alkylamines with glycidol known in the art. Typically, the reaction proceeds at a temperature of from about 65° C. to about 165° C. with or without nitrogen atmosphere. Reaction can proceed without a catalyst or with a base catalyst such as for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide etc.

In other embodiments, the reaction condition for the oxide reaction of alkyl amidoamine polyglycerols is similar to the well-known oxidation reaction conditions of alkyl amine alkoxylates. For example, the oxidation reaction of alkyl amidoamine polyglycerols with hydrogen peroxide can proceed at a temperature preferably below 70° C. A solvent such as water, a glycol or alcohol is typically used to reduce the viscosity of the product. The reaction can proceed without any catalysts.

In still other embodiments, the condition for the quaternization of alkyl amidoamine polyglycerols is similar to the well-known quaternization condition of alkyl amine alkoxylates. For example, the quaternization of alkyl amidoamine polyglycerols with methyl chloride can proceed at a temperature below 110° C. in a sealed reactor. Reaction can proceed without a catalyst. A solvent such as water, a glycol or alcohol can be used to reduce the viscosity of the product.

It is contemplated that the surfactant of the instant present disclosure is not limited to any one particular method of forming and may involve any known suitable reactants and reaction conditions, as would be appreciated by one of skill in the art. In addition to the above reaction, other reactions to form oxides, and quaternary ammonium compounds may be utilized. For example, these reactions may proceed as described above or by any mechanism as would be appreciated by one of skill in the art.

In various embodiments, the surfactant is obtainable by reacting an alkyl amidoamine with glycidol which is an improvement over alkyl amidoamine 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 the surfactants of this disclosure are easier compared to the handling of ethylene oxide and the manufacture of alkyl amidoamine ethoxylates. It is desirable to have alkyl amidoamine polyglycerol derivatives that behave similarly to alkyl amidoamine ethoxylates in various applications but that also: (1) are less hazardous while handling the components; and (2) allow easier manufacturing conditions.

Agrochemical Composition:

This disclosure also provides an agrochemical composition that include one or more of the aforementioned surfactants and an agrochemical. In one embodiment, the agrochemical composition consists essentially of one or more of the aforementioned surfactants and the agrochemical. In such embodiments, the composition may be free of any surfactants that do not fall within the description of the surfactants herein.

As used herein, an agrochemical is a chemical used in agricultural compositions. 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.

In one embodiment, the agrochemical is chosen from herbicides, fungicides, insecticides and combinations thereof. In another embodiment, the herbicide is chosen from glyphosate, dicamba, glufosinate, 2,4-D, and combinations thereof.

In another embodiment, the agrochemical is glyphosate or glufosinate.

One embodiment of the present disclosure is an herbicide composition including one or more of the 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, 14pprox., 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 combinations and combinations thereof. Typical herbicides are acetochlor, atrazine, dicamba, glufosinate, paraquat, glyphosate, 2,4-D and combinations and combinations thereof. More typical herbicides are 2,4-D, atrazine, dicamba, glyphosate, and glufosinate and combinations and combinations thereof. The most typical herbicides are glyphosate and glufosinate. When the herbicide is an acid, it can be used in the acid form though it is typical that the herbicide be in the salt form chosen 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.

Another embodiment of the present disclosure is a fungicide composition including one or more of the 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 combinations and combinations thereof.

Still another embodiment of the present disclosure is an insecticide composition including the alkyl polyamine polyglycerol surfactants of the present disclosure. Examples of suitable insecticides include, but are not limited to, kerosene or borax, botanicals or natural organic compounds (such as nicotine, pyrethrin, strychnine and rotenone), chlorinated hydrocarbon (such as DDT, lindane, chlordane), organophosphates (such as malathion and diazinon), carbamates (such as carbaryl and propoxur), fumigants (such as naphthalene) and benzene (such as mothballs), synthetic pyrethroids (such as bifenthrin and permethrin), neonicotinoids (such as imidacloprid, clothianidin, terpenoid (such as 16pprox.16ne), and mixtures and combinations thereof.

One embodiment of the present disclosure is a surfactant composition comprising the surfactant and a diluent, wherein the concentration of the surfactant is from about 30 to about 90%, typically from about 40 to about 80%, or more typically from about 50 to about 75%. Typically, the diluent is chosen from water, glycols, liquid alcohol alkoxylate, and combinations thereof. In various non-limiting embodiments, all values, both whole and fractional, and ranges of values, including and between those set forth above, are hereby expressly contemplated for use herein.

Yet still another embodiment of the present disclosure is a combination including any herbicide, fungicide, and insecticide chosen from the above groups and further including one or more surfactants of the present disclosure.

The surfactants of the present disclosure can be used as a tank-mix additive or formulated in an in-can composition. They are suitable in solid pesticide compositions and, particularly, in liquid pesticide compositions.

Other additives that can be present in the compositions 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 surfactants in high load pesticide compositions.

The use concentration of the surfactant of the present disclosure in an in-can pesticide composition may be from about 0.005% to about 30%, typically about 0.05% to about 20%, and more typically about 0.5% to about 15% in weight %. The pesticide concentration is from about 5% to about 90%, typically from about 10% to about 60%, and more typically from about 30% to about 55%, and still more typically from about 40% to about 55%, based on weight % agrochemical. In various non-limiting embodiments, all values, both whole and fractional, and ranges of values, including and between those set forth above, are hereby expressly contemplated for use herein.

The use concentration of the surfactant of the present disclosure in a tank mix pesticide spray solution may be from about 0.001% to about 5%, typically about 0.01% to about 2%, and more typically about 0.1% to about 1% (in weight % surfactant basis) in the total spray solution. In various non-limiting embodiments, all values, both whole and fractional, and ranges of values, including and between those set forth above, are hereby expressly contemplated for use herein.

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.

Typically, all units described herein are in weight percent (i.e., wt. %).

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.

The following non-limiting examples are presented to further illustrate and explain the present disclosure.

Examples

Raw-Materials Used

Glycidol Sigma TOFA-DETA Amide (Armohib 210) Nouryon Soya DETA Amide Nouryon Oleic DETA Amide Nouryon Tallow DETA Amide Nouryon

Abbreviations Used

“xG” means the alkyl amidoamine polyglycerol with x mole of glycerol in the molecule.

TABLE 1 Synthesis/Compound Examples of the alkyl amidoamine polyglycerol surfactants Description Sample (Alkyl amidoamine + 18 pprox . . . theoretical # average glycerol units) 1 TOFA DETA Amide 3G 2 TOFA DETA Amide 6G 3 TOFA DETA Amide 9G 4 TOFA DETA Amide 12G 5 Soya DETA Amide 6G 6 Soya DETA Amide 10G 7 Oleic DETA Amide 6G 8 Tallow DETA Amide 6G 9 Tallow DETA Amide 10G

TOFA DETA amides are commercially available from Nouryon. The other three were made as described in the references set forth below, each of which is expressly incorporated herein by reference relative to various non-limiting embodiments:

Fatty amidoamine derivatives: N,N-dimethyl-N-(3-alkylamidopropyl)amines and their salts, T. M. Muzyczko, S. Shore & J. A. Loboda, Journal of the American Oil Chemists' Society volume 45, pages 720-725(1968); and

Stern et al, Method of preparing amidoamine alkoxylates and compositions thereof, US210279870 and US2018289002.

Synthesis Procedure to Prepare Alkyl Amido-Amine Polyglycerol Surfactants

Glycidol (96% purity) (37 g after purity correction, 0.48 mol) was added dropwise over a period of about 2 hours to TOFA DETA amide (58.72 g, 0.16 mol) stirred in a round bottom flask under nitrogen atmosphere keeping the temperature of the reaction mixture between 130° to 155° C. The reaction mixture was further stirred for about an hour at around 120°−130° C. until IR analysis showed no more epoxide peaks around 840 cm-1 due to glycidol. A clear pale brown viscous liquid product obtained was collected.

The process for Sample #1 was repeated using the indicated alkyl amidoamine in the relevant molar ratio with glycidol as shown in Table 1 to prepare samples #2-9. For example, for sample #2, the process used for sample #1 was repeated using molar ratio of 1:6 for TOFA DETA amide and glycidol, sample #3 used a molar ratio of 1:9 for TOFA DETA amide and glycidol, and sample #4 used a molar ratio of 1:12 for TOFA DETA amide and glycidol. While Soya DETA amide was used with specified molar ratios of glycidol as shown in Table 1 to prepare samples #5 and 6, sample 7 was made using oleic DETA amide, and samples #8 and 9 were made using tallow DETA amide using the same procedure as mentioned above for sample #1.

The products thus obtained can optionally be further diluted by adding necessary amount of water or other solvents/diluents.

For glycidol addition, various addition temperature ranges can be used from about 60° C. to about 160° C. Moreover, the rate of addition can be varied from about 5 ml per hour to about 3 to 4 days, depending on the scale of the reaction. 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.

TABLE 2 Pesticide Formulation composition containing alkyl amidoamine polyglyerols Comment Sample wt % of Name of wt % or Cloud # Pesticide Pesticide Surfactant Surfactant APA-7* water point, ° C. 2.1 Ammonium 90 TOFA 10 RT - 80 C. glufosinate DETA- clear (50% ai) 6G 2.2 Ammonium 80 TOFA 20 RT - 80 C. glufosinate DETA- clear (50% ai) 12G 2.3 Base camp 90 TOFA 10 0-80 C. Amine 4 DETA- clear (46.8% 2,4-D 3G DMA) 2.4 Base camp 90 TOFA 10 0-80 C. Amine 4 DETA- clear (46.8% 2,4-D 12G DMA) 2.5 Dicamba IPA 90 TOFA 10 0-80 C. (40% ae) DETA- clear 3G 2.6 Dicamba IPA 90 TOFA 10 0-80 C. (40% ae) DETA- clear 12G 2.7 K-glyphosate, 82.2 Soya 8.7 1.3 7.8  50 C. 48.2% ae DETA amide 6G 2.8 K-glyphosate, 82.2 Soya 8.2 1.8 7.8 >80 C. 48.2% ae DETA 6G 2.9 K-glyphosate, 82.2 Soya 9 1.0 7.8 >80 C. 48.2% ae DETA 10G 2.10 K-glyphosate, 82.2 Oleic 8.7 1.3 7.8  60 C. 48.2% ae DETA 6G 2.11 K-glyphosate, 82.2 Tallow 8.6 1.4 7.8 >80 C. 48.2% ae DETA 6G 2.12 K-glyphosate, 82.2 Tallow 9.5 0.5 7.8 >80 C. 48.2% ae DETA 10G *APA-7: alkyl-amidopropyl amine of C7 fatty acid

The results demonstrate that the surfactants of this disclosure are compatible with various pesticides.

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.

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 of the various embodiments 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 as contemplated herein. 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 of the various embodiments as set forth in the appended claims.

Claims

1. An agrochemical composition comprising:

an agrochemical; and
at least one surfactant having the structure:
wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30;
wherein each O is independently optionally present so long as at least one O is present;
wherein each B− is independently optionally present and when present is R1X−, so long as at least one B− is present;
wherein each R1 is independently optionally present and when present is a methyl or ethyl group; and
wherein each X− is independently Cl−, Br, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

2. The agrochemical composition of claim 1 wherein each a is independently from about 1 to about 20.

3. The agrochemical composition of claim 1 wherein each a is independently from about 1 to about 4.

4. The agrochemical composition according to claim 1 wherein each glyceryl residue independently comprises a linear portion, a branched portion, and a cyclic portion.

5. The agrochemical composition according to claim 1 wherein each R is independently a C8-C18 group.

6. The agrochemical composition according to claim 1 wherein each R is independently a C10-C18 group.

7. The agrochemical composition according to claim 1 wherein each R is independently a hydrocarbon group derived from an animal source, a vegetable source, a microbial/algae source, and combinations thereof.

8. The agrochemical composition of claim 1 wherein the surfactant has structure (I) and wherein m is 1 and a is from about 1 to about 15.

9. The agrochemical composition of claim 1 wherein the surfactant has structure (II) and wherein m is 1 and a is from about 1 to about 15.

10. The agrochemical composition according to claim 1 wherein the surfactant is the derivative of the reaction product or reaction product of glycidol and an alkyl amidoamine of the structure:

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group; and wherein each m is independently of from about 0 to about 4.

11. The agrochemical composition according to claim 1 wherein said agrochemical is chosen from herbicides, fungicides, insecticides and combinations thereof.

12. The agrochemical composition of claim 11 wherein the herbicide is selected from glyphosate, dicamba, glufosinate, 2,4-D, or combinations thereof.

13. The agrochemical composition according to claim 1 wherein said agrochemical is glyphosate or glufosinate.

14. A method of forming the agrochemical composition according to claim 1, said method comprising the step of combining the at least one surfactant and the agrochemical.

15. A method of treating vegetation comprising the step of applying the agrochemical composition according to claim 1 to the vegetation.

16. A surfactant having the structure:

wherein each R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 0 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)a or H so long as at least one Z is a glyceryl residue (glycerol)a;
wherein each a is independently of from about 1 to about 30;
wherein each O is independently optionally present so long as at least one O is present;
wherein each B− is independently optionally present and when present is R1X−, so long as at least one B− is present;
wherein each R1 is independently optionally present and when present is a methyl or ethyl group; and
wherein each X− is independently Cl−, Br, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

17. The surfactant of claim 16 wherein each a is independently from about 1 to about 20.

18. The surfactant of claim 16 wherein each a is independently from about 1 to about 4.

19. The surfactant according to claim 16 wherein each glyceryl residue independently comprises a linear portion, a branched portion, and a cyclic portion.

20. The surfactant according to claim 16 wherein each R is independently a C8-C18 group.

21-25. (canceled)

Patent History
Publication number: 20230165246
Type: Application
Filed: Apr 28, 2021
Publication Date: Jun 1, 2023
Applicant: NOURYON CHEMICALS INTERNATIONAL B.V. (Amsterdam)
Inventors: Hanamanthsa BEVINAKATTI (Somerset, NJ), Shawn ZHU (Ringoes, NJ), Mojahedul ISLAM (Whitehouse Station, NJ)
Application Number: 17/997,579
Classifications
International Classification: A01N 25/30 (20060101); A01N 57/20 (20060101);