ALKYL POLYAMINE POLYGLYCEROL SURFACTANTS

Info

Publication number: 20230165244
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: 17/997,577

Abstract

A surfactant has a structure (I)-(VI) and may be used in an agrochemical composition that includes at least one surfactant of this disclosure and an agrochemical. The surfactant may be further defined as alkyl amine polyglycerol or alkyl polyamine polyglycerol, or alkyl polyglycerylamine. 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.

Description

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/EP2021/061049, 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 polyamine polyglycerol surfactants. More specifically, this disclosure relates to surfactants that are particular alkyl polyamine 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 and 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 and 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.

The production of alkylamine ethoxylates, including alkyl polyamine 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, 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 alkylamine ethoxylates requires special design of the reactor requiring a pressured reactor with a gas feeding pipe.

Even though alkylamine ethoxylates are difficult to manufacture, they are one of the most used adjuvants in pesticide compositions. An alkylamine 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 structure:

where R is a hydrocarbon group (i.e., the hydrophobic portion) of various chain lengths and x and y can be various values. It is this molecular structure that creates usefulness as adjuvants in agricultural applications.

SUMMARY OF THE DISCLOSURE

This disclosure provides a surfactant having the structure:

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H, so long as at least one Z is (glycerol)_a; and
wherein each a is independently of from about 1 to about 30, so long as each a is not 1 when Z is glycerol only; or

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H; and
wherein each a is independently of from about 1 to about 30; or

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H;
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; or

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H; 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 R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glyceryl)_aor H;
wherein each a is independently of from about 1 to about 30;
wherein each B⁻is independently optionally present and when present is R¹X⁻, so long as at least one B⁻is present;

wherein each R¹is independently optionally present and when present is a methyl or ethyl group;

wherein each X⁻is independently Cl⁻, Br, CH₃OSO₃⁻, CH₃CH₂OSO₃⁻, or is not present if R¹is not present; and/or

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glyceryl)_aor H;
wherein each a is independently of from about 1 to about 30;
wherein each B⁻is independently optionally present and when present is R¹X⁻, so long as at least one B⁻is present;
wherein each R¹is independently optionally present and when present is a methyl or ethyl group;
wherein each X⁻is independently Cl⁻, Br⁻, CH₃OSO₃⁻, CH₃CH₂OSO₃⁻, or is not present if R¹is not present.

This disclosure also provides an agrochemical composition that includes an agrochemical and the aforementioned surfactant. 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 alkyl polyamine polyglycerol surfactants. For example, the disclosure provides a surfactant having the structure:

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H, so long as at least one Z is (glycerol)_a; and
wherein each a is independently of from about 1 to about 30, so long as each a is not 1 when Z is glycerol only;

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H; and
wherein each a is independently of from about 1 to about 30;

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H; 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 R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glyceryl)_aor H;
wherein each a is independently of from about 1 to about 30;
wherein each B⁻is independently optionally present and when present is R¹X⁻, so long as at least one B⁻is present;
wherein each R¹is independently optionally present and when present is a methyl or ethyl group;
wherein each X⁻is independently Cl⁻, Br, CH₃OSO₃⁻, CH₃CH₂OSO₃⁻, or is not present if R¹is not present; or

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glyceryl)_aor H;
wherein each a is independently of from about 1 to about 30;
wherein each B⁻is independently optionally present and when present is R¹X⁻, so long as at least one B⁻is present;
wherein each R¹is independently optionally present and when present is a methyl or ethyl group;
wherein each X⁻is independently Cl⁻, Br, CH₃OSO₃⁻, CH₃CH₂OSO₃⁻, or is not present if R¹is not present.

For example, in one embodiment, the surfactant has the structure (I) below:

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H, so long as at least one Z is (glycerol)_a; and
wherein each a is independently of from about 1 to about 30, so long as each a is not 1 when Z is glycerol only.
In another embodiment, the surfactant has the structure (II):

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H; and
wherein each a is independently of from about 1 to about 30.
In another embodiment, the surfactant has the structure (III):

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H; 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.

In this structure, and throughout this disclosure, the “arrow” present in the structure between N and O is as is understood by those in the chemical arts to represent electron donation to O from the N, if/when the O is present.

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

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glycerol)_aor H; 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.

In this structure, and throughout this disclosure, the “arrow” present in the structure between N and O is as is understood by those in the chemical arts to represent electron donation to O from the N, if/when the O is present.

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

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glyceryl)_aor H;
wherein each a is independently of from about 1 to about 30;
wherein each B⁻is independently optionally present and when present is R¹X⁻, so long as at least one B⁻is present;
wherein each R¹is independently optionally present and when present is a methyl or ethyl group;
wherein each X⁻is independently Cl⁻, Br⁻, CH₃OSO₃⁻, CH₃CH₂OSO₃⁻, or is not present if R¹is not present. In other words, R¹can be nothing and, if so, then X⁻is nothing.

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

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group;
wherein each m is independently of from about 1 to about 4;
wherein each Z is independently a glyceryl residue (glyceryl)_aor H;
wherein each a is independently of from about 1 to about 30;
wherein each B⁻is independently optionally present and when present is R¹X⁻, so long as at least one B⁻is present;
wherein each R¹is independently optionally present and when present is a methyl or ethyl group;
wherein each X⁻is independently Cl⁻, Br⁻, CH₃OSO₃⁻, CH₃CH₂OSO₃⁻, or is not present if R¹is not present. In other words, R¹can be nothing and, if so, then X⁻is nothing.

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 C₆to C₂₂linear 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-C₁₈group. In another embodiment, each R is independently a C₈-C₁₆group. In another embodiment, each R is independently a C₅-C₁₄group. In another embodiment, each R is independently a C₅-C₁₂group. In another embodiment, each R is independently a C₅-C₁₀group. In another embodiment, each R is independently a C₁₀-C₁₈group. In another embodiment, each R is independently a C₁₀-C₁₆group. In another embodiment, each R is independently a C₁₀-C₁₄group. In another embodiment, each R is independently a C₁₀-C₁₂group. In another embodiment, each R is independently a C₁₂-C₁₈group. In another embodiment, each R is independently a C₁₂-C₁₆group. In another embodiment, each R is independently a C₁₂-C₁₄group. In another embodiment, each R is independently a C₁₄-C₁₈group. In another embodiment, each R is independently a C₁₄-C₁₆group. In another embodiment, each R is independently a C₁₆-C₁₈group.

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 n is independently 0, 1, 2, 3, or 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 various embodiments, each Z is independently a glyceryl residue (glyceryl)_aor 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 so long as each a is not 1. In other embodiments, each a is independently of from about 1 to about 30 without the aforementioned proviso. 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 R¹is independently nothing, e.g. optionally present, and, if present, is a methyl or ethyl group. In one embodiment, one or more R¹groups is a methyl group. In another embodiment, one or more R¹groups is an ethyl group. In a further embodiments, one or more R¹groups is a methyl group and one or more R¹groups is an ethyl group.

As described above, each R¹is 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 R¹is 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 amine polyglycerol or alkyl polyamine polyglycerol, or alkyl 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-C₁₈group. In another embodiment, each R is independently a C₁₀-C₁₈group. 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, R¹is CH₃and X⁻is Cl⁻.

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

wherein each R is independently a C₆to C₂₂linear or branched, saturated or unsaturated hydrocarbon group; and wherein each m is independently of from about 1 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 amine polyglycerols (alkyl polyamine 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 conditions for the oxide reaction of alkyl polyamine polyglycerols is similar to the well-known oxidation reaction conditions of alkyl amine alkoxylates. For example, the oxidation reaction of alkyl polyamine 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 1 polyamine polyglycerols is similar to the well-known quaternization condition of alkyl amine alkoxylates. For example, the quaternization of alkyl polyamine 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 polyamine with glycidol which is an improvement over alkyl amine 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 amine ethoxylates. It is desirable to have alkyl polyamine polyglycerol derivatives that behave similarly to alkyl amine 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, 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 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-A1, 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 methoprene), 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 Example 1. Synthesis of Alkyl Polyamine Polyglycerols

Raw-materials used

Glycidol (Acros):

Duomeen C (R=Coco, C12/14) (Nouryon) N-Coco-1,3-Diaminopropane Duomeen O (R=Oleyl, C18:1) (Nouryon) N-Oleyl-1,3-Diaminopropane Triameen YT (R=Tallow) (Nouryon)

Hydrogen peroxide
Methyl chloride

Abbreviations Used

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

TABLE 1 Synthesis/Compound Examples Description Sample (Alkyl polyamine + approx, # theoretical average glycerol units) 1 Duomeen C-3G 2 Duomeen C-3.5G 3 Duomeen C-6G 4 Duomeen 0-3 G 5 Duomeen 0-6G 6 Duomeen 0-9G 7 Duomeen 0-12G 8 Triameen YT-4G 9 Triameen YT-8G 10 Triameen YT-12G 11 Duomeen C-6G mono N-oxide 12 Duomeen C-6G di N-oxide 13 Duomeen C-3.5G methyl chloride monoquat 14 Duomeen C-3.5G methyl chloride diquat

Synthesis Procedure to Prepare Alkyl Polyamine Polyglycerols

The following procedure was used to create sample #1 (Duomeen C-3G), and similar procedures were used to synthesize the additional samples (2-14, with the relevant alkyl polyamine and glycidol molar ratios adjusted appropriately (as discussed below). As the glycidol purity changed from batch to batch, the actual amount used was adjusted based on the purity of that batch.

Sample #1: Duomeen C-3G

Glycidol (96% purity) (46.25 g after purity correction, 0.6 mol) was added dropwise over a period of 45 minutes to Duomeen C (48.4 g, 0.2 mol) stirred in a round bottom flask under nitrogen atmosphere keeping the temperature of the reaction mixture between 105° to 140° 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 obtained was collected.

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

The process for Sample #1 was repeated using the indicated di- or triamine in the relevant molar ratio with glycidol as shown in Table 1 to prepare samples #2-10. For example, for sample #2, the process used for sample #1 was repeated using molar ratio of 1:3.5 for Duomeen C and glycidol, sample #3 used a molar ratio of 1:6 for Duomeen C and glycidol, and so forth.

Synthesis Procedure to Prepare Alkyl Polyamine Polyglycerol N-Oxides

Sample #11 Duomeen C-6G mono N-oxide

Sample #12 Duomeen C-6G di N-oxide

The following procedure was used to create sample #11 (Duomeen C-6G mono N-oxide), and similar procedure was used to synthesize the di N-oxide sample (#12) using additional excess hydrogen peroxide.

Sample #11 Duomeen C-6G Mono N-Oxide

The round bottom flask containing 194.6 grams of Duomeen C-6G (sample #3 from Table 1) (0.284 moles) was warmed to 55-60° C. and 40.5 grams of water was added to increase its fluidity. Dequest 2010, 0.4 grams was added to this mixture followed by slow addition of 20.7 grams (0.3 moles) of hydrogen peroxide (50 wt % in water) from a metered dropping funnel over a period of about 1 hour. A slight exotherm was observed. The reaction was then heated at 70° C. for two hours, cooled and collected as a yellow, viscous product which was used without any further purification but can optionally be further diluted by adding necessary amount of water or other solvents/diluents.

Synthesis Procedure To Prepare Alkyl polyamine polyglycerol Methyl Chloride Mono and Diquats
Sample #13 Duomeen C-3.5G methyl chloride monoquat
Sample #14 Duomeen C-3.5G methyl chloride diquat

To a 2 L autoclave was charged Duomeen C-3.5G (Sample #2 from Table 1) (374 g, 0.75 moles), sodium bicarbonate (25.7 g), and isopropanol (392 g). The autoclave was sealed, leak checked, and pressurized/depressurized three times with 50 psig nitrogen. The reactor contents were heated to 100° C. and methyl chloride (68 g, 1.36 moles) was added. The reaction was monitored periodically by measuring free amine by titration and when the sample showed 50% conversion, 328 g of the reaction mixture was taken out, filtered and stripped off the isopropanol to give the ‘mono’ quat product (sample #14) as a yellow liquid. The quaternary site selectivity was not determined and the product was used after diluting in water as required.

The diquaternary product (Sample #14) was prepared by adding more methyl chloride as needed to the remaining reaction mixture after periodic monitoring of withdrawn samples and monitoring the pH until it turned acidic. The total amount of methyl chloride added was 106 g (2.12 moles). The reaction was then stopped and worked-up as mentioned for sample #13 to give the diquat product (sample #14) as a viscous yellow liquid which was used after dilution with water as required.

Subsequently, many of the samples 1-14 were evaluated to determine compatibility in high load glyphosate formulations.

TABLE 2a Compatibilities of various surfactants in high load glyphosate formulations K-glyphosate Water, Sample Cloud Sample (48.2% ae), wt. % wt. % Surfactant wt. % point, ° C. 2a.1 82.2 7.8 Duomeen C-3G 10 >80 2a.3 82.2 7.8 Duomeen C-6G 10 >80 2a.4 82.2 7.8 Duomeen 0-3 G 10 >80 2a.5 82.2 7.8 Duomeen 0-6G 10 >80 2a.6 82.2 7.8 Duomeen 0-9G 10 >80 2a.7 82.2 7.8 Duomeen 0-12G 10 >80 2a.8 82.2 7.8 Triameen YT-4G 10 >80 2a.9 82.2 7.8 Triameen YT-8G 10 >80 2a.10 82.2 7.8 Triameen YT-12G 10 >80 2a.11 82.2 7.8 Duomeen C-6G 10 >80 mono N-oxide 2a.12 82.2 6.7 Duomeen C-6G di 11.1 >80 N-oxide 2a.13 82.2 7.8 Duomeen C-3.5G 10 80 methyl chloride diquat

TABLE 2b Compatibilities of various surfactants in IPA glyphosate formulations IPA-glyphosate Water, Sample Cloud Sample (46.7% ae), wt. % wt. % Surfactant wt. % point, ° C. 2b. 1 66.0 24.0 Duomeen C-3.5G 10 >80 methyl chloride monoquat 2b.2 66.0 24.0 Duomeen C-3.5G 10 >80 methyl chloride diquat

TABLE 3 Pesticide Formulation composition containing alkyl polyglyceryl polyamines and derivatives Smpl Wt % of Name of # Name of Pesticide Pesticide surfactant wt % Comment 3.1 Ammonium glufosinate 90 Duomeen C-3G 10 4C - 80C (50% ai) clear 3.2 Ammonium glufosinate 90 Duomeen C-6G 10 4C - 80C (50% ai) clear 3.3 Ammonium glufosinate 90 Duomeen O-3G 10 4C - 80C (50% ai) clear 3.4 Ammonium glufosinate 90 Duomeen 0-6G 10 4C - 80C (50% ai) clear 3.5 Ammonium glufosinate 90 Duomeen 0-9G 10 4C - 80C (50% ai) clear 3.6 Ammonium glufosinate 90 Duomeen O-12G 10 4C - 80C (50% ai) clear 3.7 Ammonium glufosinate 90 Triamine YT-4G 10 4C - 80C (50% ai) clear 3.8 Ammonium glufosinate 90 Triamine YT-8G 10 4C - 80C (50% ai) clear 3.9 Ammonium glufosinate 90 Triamine YT- 10 4C - 80C (50% ai) 12G clear 3.10 Ammonium glufosinate 85 Duomeen C-3.5G 15 2C - 80C (50% ai) methyl chloride clear monoquat 3.11 Ammonium glufosinate 85 Duomeen C-3.5G 15 2C - 80C (50% ai) methyl chloride clear diquat 3.12 Base camp Amine 90 Duomeen C-6G 10 0C - 80C (46.8% 2,4-D DMA) clear 3.13 Base camp Amine 90 Duomeen O-3G 10 OC - 80C (46.8% 2,4-D DMA) clear 3.14 Base camp Amine 90 Duomeen O-12G 10 OC - 80C (46.8% 2,4-D DMA) clear 3.15 Base camp Amine 90 Triamine YT-4G 10 OC - 60C (46.8% 2,4-D DMA) clear, 80C hazy 3.16 Base camp Amine 90 Triamine YT- 10 OC - 80C (46.8% 2,4-D DMA) 12G clear 3.17 Base camp Amine 85 Duomeen C-3.5G 15 2C - 80C (46.8% 2,4-D DMA) methyl chloride clear monoquat 3.18 Base camp Amine 85 Duomeen C-3.5G 15 2C - 80C (46.8% 2,4-D DMA) methyl chloride clear diquat 3.19 Dicamba IPA (40% ae) 90 Duomeen C-6G 10 OC - 80C clear 3.20 Dicamba IPA (40% ae) 90 Duomeen O-3G 10 OC - 80C clear 3.21 Dicamba IPA (40% ae) 90 Duomeen O-12G 10 OC - 80C clear 3.22 Dicamba IPA (40% ae) 90 Triamine YT-4G 10 OC - 80C clear 3.23 Dicamba IPA (40% ae) 90 Triamine YT- 10 0C - 80C 12G clear 3.24 Dicamba-IPA (40% ae) 85 Duomeen C-3.5G 15 2C - 80C methyl chloride clear monoquat 3.25 Dicamba-IPA (40% ae) 85 Duomeen C-3.5G 15 2C - 80C methyl chloride clear diquat 3.26 Dicamba IPA (40% ae) 80 Duomeen C-6G 20 -25C - 80C di N-oxide clear 3.27 Base camp Amine 80 Duomeen C-6G 20 0C - 80C (46.8% 2,4-D DMA) di N-oxide clear 3.28 Ammonium glufosinate 80 Duomeen C-6G 20 OC - 80C (50% ai) di N-oxide clear

The results demonstrate that alkyl polyamine polyglycerols and their N-oxides and quaternary ammonium surfactants 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. 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 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H, so long as at least one Z is (glycerol)a; and

wherein each a is independently of from about 1 to about 30, so long as each a is not 1 when Z is glycerol only;

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 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H; and

wherein each a is independently of from about 1 to about 30;

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 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H; 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 R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;

wherein each m is independently of from about 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H; 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 R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;

wherein each m is independently of from about 1 to about 4;

wherein each Z is independently a glyceryl residue (glyceryl)a or H;

wherein each a is independently of from about 1 to about 30;

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;

wherein each X− is independently Cl−, BR−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present; or

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 1 to about 4;

wherein each Z is independently a glyceryl residue (glyceryl)a or H;

wherein each a is independently of from about 1 to about 30;

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;

wherein each X− is independently Cl−, BR−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

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

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

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

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

6. The surfactant according to claim 1 to 5 wherein each R is independently a C10-C18 group.

7. The surfactant 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 surfactant according to claim 6 wherein m is 1, Z is (glycerol)a, and wherein each a is from about 1 to about 7 when the surfactant has structure (II) to (VI).

9. The surfactant of claim 8 having Structure (V) or Structure (VI) wherein R1 is CH3 and X− is C1−.

10. The surfactant ccording to claim 1 that is the derivative of the reaction product or reaction product of glycidol and at least one amine 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 1 to about 4.

11. 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 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H, so long as at least one Z is (glycerol)a; and

wherein each a is independently of from about 1 to about 30;

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 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H; and

wherein each a is independently of from about 1 to about 30;

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 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H; 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 R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;

wherein each m is independently of from about 1 to about 4;

wherein each Z is independently a glyceryl residue (glycerol)a or H; 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 R is independently a C6 to C22 linear or branched, saturated or unsaturated hydrocarbon group;

wherein each m is independently of from about 1 to about 4;

wherein each Z is independently a glyceryl residue (glyceryl)a or H;

wherein each a is independently of from about 1 to about 30;

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;

wherein each X− is independently Cl−, BR−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present; or

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 1 to about 4;

wherein each Z is independently a glyceryl residue (glyceryl)a or H;

wherein each a is independently of from about 1 to about 30;

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;

wherein each X− is independently Cl−, BR−, CH3OSO3−, CH3CH2OSO3−, or is not present if R1 is not present.

12. The agrochemical composition of claim 11 wherein each a is independently from about 1 to about 20.

13. The agrochemical composition of claim 11 wherein each a is independently from about 1 to about 4.

14. The agrochemical composition of according to claim 11 wherein each glyceryl residue independently comprises a linear portion, a branched portion, and a cyclic portion.

15. The agrochemical composition according to claim 11 wherein each R is independently a C5-C18 group.

16. The agrochemical composition according to claim 11 wherein each R is independently a C10-C18 group.

17. The agrochemical composition according to claim 11 wherein each R is independently a hydrocarbon group derived from an animal source, a vegetable source, a microbial/algae source, and combinations thereof.

18. The surfactant of claim 16 wherein m is 1, Z is (glycerol)a, and wherein each a is from about 1 to about 7.

19. The surfactant of claim 18 that has Structure (V) or Structure (VI) wherein R1 is CH3 and X− is Cl−.

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

21-24. (canceled)