Alkyl amidoamine polyglycerol surfactant

Abstract

The present invention discloses an agricultural chemical composition, which comprises an agricultural chemical and a surfactant having structure (I)-(VI). The surfactant can be described as an alkyl amidoamine glycerol surfactant, an oxide thereof, or a quaternary ammonium compound thereof.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application 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 April 30, 2020, and each of which is expressly incorporated herein by reference in its entirety. Technical Field

[0003] In general, the present disclosure relates to alkyl amidoamine polyglycerol surfactants. More specifically, the present disclosure relates to surfactants specifically alkyl amidoamine polyglycerols, oxides thereof, and quaternary ammonium compounds. Background Art

[0004] Many surfactants are used as adjuvants in pesticide compositions. Adjuvants can be used, for example, as synergists, wetting agents, emulsifiers, spreading agents, deposition aids, drift control agents, water conditioners, crystal inhibitors, suspension aids, thickeners or dispersants that can enhance the biological efficacy of pesticides. The biological efficacy of pesticides can be improved by adding appropriate surfactant adjuvants. For example, it is well known that nitrogen-containing surfactants such as alkylamine alkoxylate surfactants can enhance the biological efficacy of herbicides, fungicides and insecticides. Examples of nitrogen-containing surfactants as synergist adjuvants for herbicides can be found in US4528023 and US5226943. US5226943 also discloses that the activity of fungicide compositions can be improved by incorporating certain nitrogen-containing surfactants. Examples of nitrogen-containing surfactants as synergist adjuvants for insecticides can be found in WO201280099. Examples of nitrogen-containing surfactants as emulsifiers in pesticide emulsions can be found in US5565409 and US8097563. Examples of nitrogen-containing surfactants as thickeners in glyphosate compositions can be found in WO201020599. Examples of nitrogen-containing surfactants as drift control agents in pesticide emulsions can be found in WO2013098220.

[0005] Alkyl amidoamine alkoxylates and their further derivatives are well-known surfactants that can be used in many industries such as agrochemicals, mining, cleaning, etc. In particular, ethoxylated alkyl amidoamines have been disclosed as adjuvants in pesticide formulations (WO199705779, US8828911 and US2010279870)).

[0006] The production of alkyl amidoamine ethoxylates requires a high degree of caution and sophisticated technology. Alkyl amidoamine ethoxylates are prepared by reacting ethylene oxide with 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. Due to its volatility, ethylene oxide is usually handled and transported as a refrigerated liquid to reduce the risk of fire or explosion. This increases transportation and storage costs. Due to the hazardous nature of ethylene oxide, the production of alkyl amidoamine ethoxylates requires special reactor design, requiring a pressurized reactor with a gas feed line.

[0007] Although alkyl amidoamine ethoxylates are difficult to manufacture, they are one of the most commonly used adjuvants in pesticide compositions. The alkyl amidoamine ethoxylate molecule contains a hydrophilic part (tertiary nitrogen with various ethylene oxide units) and a hydrophobic part (hydrocarbon group), for example, as shown in the following general formula:

[0008]

[0009] Where R is a hydrocarbon group (i.e., a hydrophobic portion) with various chain lengths, (AO) x It is a linear or branched C2 to C4 alkoxylate group, x>0, and m is usually 0 to 4. It is this molecular structure that can be used as an adjuvant in agricultural applications.

[0010] To produce alkyl amidoamine derivatives, hydrocarbons with various chain lengths are readily available, but the choice of hydrophilic groups other than ethylene oxide is limited. It would be desirable to have alkyl amidoamine derivatives that have similar properties to alkyl amidoamine ethoxylates but that also have the following properties: (1) are less hazardous when handling the components; (2) allow for easier manufacturing conditions; and (3) have better compatibility in high-load pesticide compositions. Summary of the invention

[0011] The present disclosure provides an agricultural chemical composition comprising an agricultural chemical and at least one surfactant having the following structure:

[0012]

[0013]

[0014] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0015] wherein each m is independently from about 0 to about 4;

[0016] wherein each Z is independently a glyceryl residue (glyceryl) a ((glycerin)a Residue, (glycerol) a ) or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;

[0017] wherein each a is independently from about 1 to about 30;

[0018] wherein each O is independently optional, as long as at least one O is present;

[0019] Each of the B - is independently optional and when present is R 1 X - , as long as there is at least one B - ;

[0020] Each R 1 is independently optional and when present is methyl or ethyl; and

[0021] Each X - Independently Cl - Br - 、CH3OSO3 - 、CH3CH2OSO3 - , or if R 1 If it doesn't exist, it doesn't exist.

[0022] The present disclosure also provides one or more of the above-mentioned surfactants independently of the agrochemical composition. DETAILED DESCRIPTION OF THE INVENTION

[0024] The present disclosure provides an agrochemical composition comprising at least one surfactant as described below. The present disclosure also provides the surfactant itself.

[0025] In various embodiments, the surfactant has the following structure:

[0026]

[0027] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0028] wherein each m is independently from about 0 to about 4;

[0029] wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;and

[0030] wherein each a is independently from about 1 to about 30;

[0031] wherein each O is independently optional, as long as at least one O is present;

[0032] Each of the B - is independently optional and when present is R 1 X - , as long as there is at least one B - ;

[0033] Each R 1 is independently optional and when present is methyl or ethyl; and

[0034] Each X - Independently Cl - Br - 、CH3OSO3 - 、CH3CH2OSO3 - , or if R 1 If it doesn't exist, it doesn't exist.

[0035] In one embodiment, the surfactant has structure (I):

[0036]

[0037] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0038] wherein each m is independently from about 0 to about 4;

[0039] wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;and

[0040] wherein each a is independently from about 1 to about 30.

[0041] In one embodiment, the surfactant has structure (II):

[0042]

[0043] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0044] wherein each m is independently from about 0 to about 4;

[0045] wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;and

[0046] wherein each a is independently from about 1 to about 30.

[0047] In one embodiment, the surfactant has structure (III):

[0048]

[0049] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0050] wherein each m is independently from about 0 to about 4;

[0051] wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;

[0052] wherein each a is independently from about 1 to about 30; and

[0053] wherein each O is independently optional, as long as at least one O is present.

[0054] In one embodiment, the surfactant has structure (IV):

[0055]

[0056] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0057] wherein each m is independently from about 0 to about 4;

[0058] wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;

[0059] wherein each a is independently from about 1 to about 30;

[0060] wherein each O is independently optional, as long as at least one O is present;

[0061] Each of the B - is independently optional and when present is R 1 X - , as long as there is at least one B - ;

[0062] Each R 1 is independently optional and when present is methyl or ethyl; and

[0063] Each X- Independently Cl - Br - 、CH3OSO3 - 、CH3CH2OSO3 - , or if R 1 If it doesn't exist, it doesn't exist.

[0064] In one embodiment, the surfactant has structure (V):

[0065]

[0066] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0067] wherein each m is independently from about 0 to about 4;

[0068] wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;

[0069] wherein each a is independently from about 1 to about 30; and

[0070] wherein each O is independently optional, as long as at least one O is present.

[0071] In one embodiment, the surfactant has structure (VI):

[0072]

[0073] Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups;

[0074] wherein each m is independently from about 0 to about 4;

[0075] wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a ;

[0076] wherein each a is independently from about 1 to about 30;

[0077] wherein each O is independently optional, as long as at least one O is present;

[0078] Each of the B - is independently optional and when present is R 1 X - , as long as there is at least one B - ;

[0079] Each R 1 is independently optional and when present is methyl or ethyl; and

[0080] Each X - Independently Cl - Br - 、CH3OSO3 - 、CH3CH2OSO3 - , or if R 1 If it doesn't exist, it doesn't exist.

[0081] It is expected that any one of the above-mentioned surfactants (I)-(VI) can be combined with any one or more of the above-mentioned surfactants (I)-(VI). Therefore, it is expected that the combination of two or three or more of the above-mentioned surfactants (I)-(VI) is used herein. In addition, each of the above-mentioned surfactants (I)-(VI) can be used as a single surfactant, or as a combination of two or more of each surfactant of the above (I)-(VI) type. In addition, as long as at least one of the above-mentioned surfactants (I)-(VI) is used, any composition or preparation may not contain any one or more of the other above-mentioned surfactants (I)-(VI) or its variant, or may include one or more of the other above-mentioned surfactants (I)-(VI) One or more variants.

[0082] It is contemplated that a surfactant component may be used herein, for example in a formulation or an agrochemical composition, wherein the surfactant component comprises one or more of the above-mentioned surfactants (I)-(VI). For example, the surfactant component may comprise, be, consist essentially of, or consist of one or more of the above-mentioned surfactants (I)-(VI).

[0083] In the foregoing embodiments, each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon radical. For example, each R can 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 numerical values ​​(including integers and decimals) and numerical ranges, including the above-mentioned numerical values ​​and the numerical values ​​between the above-mentioned numerical values, are all clearly considered to be used.

[0084] In one embodiment, one or more R groups are linear hydrocarbon groups.

[0085] In one embodiment, one or more R groups are branched hydrocarbyl groups.

[0086] In one embodiment, one or more R groups are saturated hydrocarbon groups.

[0087] In one embodiment, one or more R groups are unsaturated hydrocarbon groups.

[0088] In one embodiment, each R is independently C8-C 18 In another embodiment, each R is independently C8-C 16 In another embodiment, each R is independently C8-C 14 In another embodiment, each R is independently C8-C 12 In another embodiment, each R is independently C8-C 10 In another embodiment, each R is independently C 10 -C 18 In another embodiment, each R is independently C 10 -C 16 In another embodiment, each R is independently C 10 -C 14 In another embodiment, each R is independently C 10 -C 12 In another embodiment, each R is independently C 12 -C 18 In another embodiment, each R is independently C 12 -C 16 In another embodiment, each R is independently C 12 -C 14 In another embodiment, each R is independently C 14 -C 18 In another embodiment, each R is independently C 14 -C 16 In another embodiment, each R is independently C 16 -C 18 In another embodiment, each R is independently C 10 -C 18 Group.

[0089] In another embodiment, each R is independently a hydrocarbon group derived from an animal source, a plant source, a microorganism / algae source, and combinations thereof. In one embodiment, each R is independently a hydrocarbon group derived from a plant 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 microorganism / algae source.

[0090] In other embodiments, each m is independently 0, 1, 2, 3, or 4, e.g., from about 0 to about 4, from about 0 to about 2, from about 0 to about 1, from about 1 to about 4, from about 1 to about 3, from about 1 to about 2, from about 2 to about 4, from about 2 to about 3, or from about 3 to about 4. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and numerical ranges, including the recited values ​​and values ​​between the recited values, are expressly contemplated for use herein.

[0091] 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 ((glycerin) a Residue, (glyceryl) a ). In various embodiments, each a is independently from about 1 to about 30. For example, in various embodiments, each α 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 numerical values ​​(including integers and decimals) and numerical ranges, inclusive of the recited values ​​and values ​​between the recited values, are expressly contemplated for use herein.

[0092] 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.

[0093] In one embodiment, the polyglyceryl moiety may be linear or branched or cyclic. In another embodiment, the linear polyglyceryl moiety may have the formula:

[0094]

[0095] In yet another embodiment, the branched polyglyceryl moiety may have the formula:

[0096]

[0097] The growth of the polyglyceryl moiety can start from the terminal primary hydroxyl group of the glyceryl residue (generating a linear chain segment), or from the non-terminal secondary hydroxyl group of the glyceryl residue (generating a branched chain segment).

[0098] In other embodiments, each O is independently optional, as long as at least one O is present.

[0099] Furthermore, in various embodiments, each B - is independently optional and when present is R 1 X - , as long as there is at least one B - Therefore, each R 1 is independently nothing, for example optionally present, and if present, is methyl or ethyl. In one embodiment, one or more R 1 In another embodiment, one or more R 1 In a further embodiment, one or more R 1 The group is methyl and one or more R 1 The group is ethyl.

[0100] As mentioned above, each R 1 is independently optional and when present is methyl or ethyl. In addition, each X - Independently Cl - Br - 、CH3OSO3 - or CH3CH2OSO3 - , or if R 1 If it does not exist, it does not exist, as long as at least one R 1 X - As B - In one embodiment, each X - Independently Cl - Br - 、CH3OSO3 - 、CH3CH2OSO3 - In one embodiment, each X- Independently Cl - In another embodiment, each X - Independently for Br - In another embodiment, each X - Independently CH3OSO3 - In another embodiment, each X - independently CH3CH2OSO3 - Alternatively, one or more X - It can be nothing, as long as there is at least one R 1 X - .

[0101] In one embodiment, the surfactant can be further defined as an alkyl amidoamine polyglycerol or an alkyl amidopolyamine polyglycerol or an alkyl amidopolyglyceryl polyamine as described above. Also as described above, in another embodiment, the surfactant can be further defined as an amine oxide. In another embodiment, the surfactant can be further defined as a quaternary ammonium salt or a quaternary ammonium compound.

[0102] 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 from about 1 to about 4. In another embodiment, each glyceryl residue independently includes a linear portion, a branched portion, and a cyclic portion. In another embodiment, each R is independently C8-C 18 In another embodiment, each R is independently C 10 -C 18 In another embodiment, each R is independently a hydrocarbon group derived from animal origin, plant origin, microbial / algae origin, and combinations thereof. In another embodiment, m is 1, and Z is (glyceryl) a , and wherein each a is 1 to 7. In another embodiment, R 1 is CH3 and X - Cl - .

[0103] In various embodiments, the surfactant is a derivative or reaction product of the reaction product of glycidol and at least one amidoamine having the structure:

[0104]

[0105] Where each R is independently C6 to C 22 linear or branched, saturated or unsaturated hydrocarbon group; and wherein each m is independently from about 0 to about 4.

[0106] As is known in the art, for polymers, subscripts are usually not integers and can be fractional values, for example because they are average values. Therefore, in various non-limiting embodiments, it is explicitly expected that all subscript values ​​herein can be average values ​​or can be fractional values ​​including all values ​​and value ranges described herein and therebetween. Alternatively, one or more subscripts can be integer values ​​or can be average values.

[0107] In various embodiments, the conditions for reacting with glycidol to obtain alkylamidoamine polyglycerol are similar to the conditions for reacting alkylamines with glycidol known in the art. Typically, the reaction is carried out at a temperature of about 65° C. to about 165° C., with or without a nitrogen atmosphere. The reaction can be carried out in the absence of a catalyst or in the presence of a base catalyst, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, and the like.

[0108] In other embodiments, the reaction conditions for the oxidation of the alkylamidoamine polyglycerol are similar to the well-known oxidation reaction conditions of alkylamine alkoxylates. For example, the oxidation of the alkylamidoamine polyglycerol with hydrogen peroxide can be carried out at a temperature preferably below 70° C. A solvent such as water, glycol or alcohol is typically used to reduce the viscosity of the product. The reaction can be carried out without any catalyst.

[0109] In other embodiments, the quaternization conditions of the alkyl amidoamine polyglycerol are similar to the well-known quaternization conditions of alkylamine alkoxylates. For example, the quaternization reaction of the alkyl amidoamine polyglycerol with methyl chloride can be carried out in a sealed reactor at a temperature below 110°C. The reaction can be carried out in the absence of a catalyst. Solvents such as water, glycols or alcohols can be used to reduce the viscosity of the product.

[0110] It is contemplated that the surfactants of the present invention are not limited to any particular method of formation and may involve any known suitable reactants and reaction conditions, as will be appreciated by those skilled in the art. In addition to the above reactions, other reactions to form oxides and quaternary ammonium compounds may be utilized. For example, these reactions may be performed as described above or by any mechanism as will be appreciated by those skilled in the art.

[0111] In various embodiments, surfactants are obtainable by reacting an alkyl amidoamine with glycidol, which is an improvement over alkyl amidoamine ethoxylates. Glycidol is a liquid that is classified by various government agencies as less hazardous than ethylene oxide. Thus, the handling of glycidol and the manufacture of the surfactants of the present disclosure are easier than the handling of ethylene oxide and the manufacture of alkyl amidoethoxylates. It would be desirable to have alkyl amidoamine polyglycerol derivatives that perform similarly to alkyl amidoamine ethoxylates in various applications, but that: (1) are less hazardous in handling the components; and (2) allow for easier manufacturing conditions.

[0112] Agrochemical compositions:

[0113] The present disclosure also provides a kind of agrochemical composition, it comprises one or more of the above-mentioned surfactant and agrochemical.In one embodiment, the agrochemical composition is basically composed of one or more of the above-mentioned surfactant and agrochemical.In such an embodiment, the composition may not contain any surfactant that does not belong to the scope of surfactant described herein.

[0114] As used herein, an agrochemical is a chemical used in an agricultural composition. Non-limiting examples of agrochemicals include fertilizers, micronutrients, activator adjuvants or synergists, drift control agents, emulsifiers, deposition aids, water conditioners, wetting agents, dispersants, compatibilizers, suspension aids, pesticides (such as herbicides, fungicides and insecticides) and growth inhibitors.

[0115] In one embodiment, the agrochemical is selected from the group consisting of herbicides, fungicides, insecticides, and combinations thereof. In another embodiment, the herbicide is selected from the group consisting of glyphosate, dicamba, glufosinate, 2,4-D, and combinations thereof.

[0116] In another embodiment, the agrochemical is glyphosate or glufosinate.

[0117] One embodiment of the present disclosure is a herbicide composition comprising one or more 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, Befluanid, and chlorpyrifos. nfluralin), bensulfuron-methyl, bentazone, bifenox, binalafos, bispyribac-sodium, bromacil, bromoxynil, butachlor, butroxidim, cafenstrole, carbetamide, carfentrazone-ethyl, chloridazon, chlorpyrifos chlorimuron-ethyl, chlorobromuron, chlorotoluron, chlorsulfuron, cinidon-ethyl, cinosulfuron, clethodim, clomazone, clopyralid, cloransulam-methyl, cloorsulfuron, cypermethrin, chlorsulfuron-ethyl, chlorsulfuron-methyl, chlorsulfuron-ethyl, chlorsulfuron-methyl, chlorsulfuron-methyl, chlorsulfuron-ethyl ... ), 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, imazethapyr, imazamox mazosulfuron), iodosulfuron, ioxynil, isoproturon, isoxaben, isoxaflutole, lactofen, lenacil, linuron, mefenacet, mesosulfuron-Methyl, mesotrione, metamitron, Metazachlor, methabenzthiazuron on), 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 simazine), S-metolachlor, Sulcotrione, sulfentrazone, Sulfosulfuron, tebuthiuron, Tepraloxydim, Terbuthylazine, terbutryn, thifensulfuron-methyl, thiobencarb, Tralkoxydim, tri-allate, Triasulfuron, tribenuron-methyl, triclopyr, trifloxysulfuron, trifluralin, triflusulfuron-methyl, Tritosulfuron, and mixtures and combinations thereof. Typical herbicides are acetochlor, atrazine, dicamba, glufosinate, paraquat, glyphosate, 2,4-D, and mixtures and combinations thereof. More typical herbicides are 2,4-D, atrazine, dicamba, glyphosate, and glufosinate, and mixtures and combinations thereof. The most typical herbicides are glyphosate and glufosinate. When the herbicide is an acid, it may be used in the acid form, but typical herbicides are selected from amines, lithium, sodium,It should be noted that throughout the specification, when a herbicide is shown as a common name herein without specifying a counterion, both its acid form and salt form are intended.

[0118] Another embodiment of the present disclosure is a fungicide composition comprising one or more 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 blasticidin-S, boscalid, bromuconazole, bupirimate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, copper, cyazofamid, cyflufenamid, cyproconazole, moxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, Diniconazol ole), dinocap, dithianon, dodemorph, dodine, edifenphos, enestrobin, epoxiconazole, etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole,Fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentin chloride, fentin toxicity hydroxide), ferbam, ferimzone, fluazinam, fludioxonil, flumorph, fluopicolide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-Al, fthalide, fuberidazole, furaxyl, furametpyr, guazatine, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, iodocarb, cyproconazole pconazole), iprobenfos (IBP), iprodione, iprovalicarb, isoprothiolane, isotianil, kasugamycin, kresoxim-methyl, laminarin, mancozeb, mandipropamid, maneb, biomaterials, mepanipyrim, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, metiram, metominostrobin, metrafenone, mineral oil, organic oil, myclobutanil, naftifine, nuarimol,octhilinone, ofurace, origin, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, pefurazoate, penconazole, pencycuron, penthiopyrad, phophorous acid 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), salt, silthiobactam silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, teclofthalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofosmethyl, tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph,trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valiphenal, vinclozolin, zineb, ziram and zoxamide, and mixtures and combinations thereof.

[0119] Yet another embodiment of the present disclosure is a pesticide composition comprising the alkyl polyamine polyglycerol surfactant of the present disclosure. Examples of suitable pesticides include, but are not limited to, kerosene or borax, botanicals or natural organic compounds (such as nicotine), pyrethrin, strychnine and rotenone), chlorinated hydrocarbons (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), terpenoids (such as methoprene), and mixtures and combinations thereof.

[0120] One embodiment of the present disclosure is a surfactant composition comprising a 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 selected from water, glycols, liquid alcohol alkoxylates, and combinations thereof. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and numerical ranges, including the above numerical values ​​and the numerical values ​​between the above numerical values, are expressly considered for use herein.

[0121] Yet another embodiment of the present disclosure is a combination comprising any herbicide, fungicide, and insecticide selected from the above classes and further comprising one or more surfactants of the present disclosure.

[0122] The surfactants of the present disclosure can be used as tank mix additives or formulated in in-can compositions. They are suitable for use in solid pesticide compositions, especially liquid pesticide compositions.

[0123] Other additives that may be present in the compositions of the present disclosure are defoamers, diluents, compatibilizers, biocides, thickeners, drift control agents, dyes, fragrances and chelating agents. Due to the high compatibility of surfactants in high-loaded pesticide compositions, the use of compatibilizers may not be required.

[0124] The surfactant of the present disclosure can be used at a concentration of about 0.005% to about 30% in the in-tank pesticide composition, typically about 0.05% to about 20%, and more typically about 0.5% to about 15% by weight. The pesticide concentration is about 5% to about 30%, typically about 10% to about 60%, and more typically about 30% to about 55% (in terms of % weight agrochemicals). In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and numerical ranges, including the above numerical values ​​and the numerical values ​​between the above numerical values, are expressly contemplated for use herein.

[0125] The surfactants of the present disclosure may be used at concentrations of about 0.001% to about 5%, typically about 0.01% to about 2%, and more typically about 0.1% to about 1% (in terms of % by weight surfactant) in tank-mixed pesticide compositions. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and numerical ranges, including the above numerical values ​​and the values ​​between the above numerical values, are expressly contemplated for use herein.

[0126] Also disclosed is a method for treating plants or vegetation with the composition of the present disclosure. The method comprises applying an effective amount of an agricultural composition to a plant (particularly a crop) to kill or control pests. The agricultural composition listed above is contacted with the pests. The agricultural composition can be used in the above form or diluted with water or a suitable diluent.

[0127] Generally, all units described herein are expressed as weight percent (ie, wt %).

[0128] The surfactants of the present disclosure may also be combined with other surfactants such as alkoxylated alkylamines and their quaternary ammonium salts, anionic surfactants such as alkyl or ether sulfates, alkyl or aryl sulfonates, phosphates and ethoxylated phosphates, nonionic surfactants such as alcohol alkoxylates, alkyl (C6-C 18 ) polyglucosides, amphoteric surfactants, quaternary surfactants and silicone surfactants are used together.

[0129] The following non-limiting examples are given to further illustrate and explain the present disclosure. Example

[0130] Raw materials used

[0131]

[0132] Abbreviations used

[0133] "xG" refers to an alkylamidoamine polyglycerol having x moles of glycerol in the molecule.

[0134] Table 1. Synthesis / Compound Examples of Alkylamidoamine Polyglycerol Surfactants

[0135]

[0136] TOFA DETA Amide is commercially available from Nouryon. The other three were prepared as described in the references noted below, each of which is expressly incorporated herein by reference with respect to various non-limiting embodiments:

[0137] Fatty acylaminoamine derivatives: N,N-dimethyl-N-(3-alkylamidopropyl)amine and its salts, TM Muzyczko, S. Shore & J.A. Loboda, Journal of the American Oil Chemists' Society Vol. 45, pp. 720-725 (1968); and

[0138] Stern et al., Method of preparing amidoamine alkoxylates and compositions thereof, US210279870 and US2018289002.

[0139] Synthetic Procedure for Preparing Alkylamido-Amine Polyglycerol Surfactants

[0140] To a stirred solution of TOFA DETA Amide (58.72 g, 0.16 mol) in a round bottom flask was added glycidol (96% purity) (37 g, 0.48 mol, corrected for purity) dropwise over about 2 hours under nitrogen atmosphere, maintaining the temperature of the reaction mixture between 130°C and 155°C. The reaction mixture was stirred at about 120-130°C for another hour until IR analysis indicated a peak at 840 cm -1 There was no longer any epoxide peak attributed to glycidol nearby. The resulting clear light brown viscous liquid product was collected.

[0141] The process for Sample #1 was repeated to prepare Samples #2-9 using the specified alkyl amidoamines and glycidol in the relevant molar ratios as shown in Table 1. For example, for Sample #2, the process for Sample #1 was repeated using TOFA DETA Amide and glycidol in a molar ratio of 1:6, Sample #3 was repeated using TOFA DETA Amide and glycidol in a molar ratio of 1:9, and Sample #4 was repeated using TOFA DETA Amide and glycidol in a molar ratio of 1:12. At the same time, the same procedure as described above for Sample #1 was used to prepare Samples #5 and 6 using Soya DETA Amide and glycidol in the specified molar ratios as shown in Table 1, Sample 7 was prepared using Oleic DETA Amide, and Samples #8 and 9 were prepared using Tallow DETA Amide.

[0142] The product thus obtained may optionally be further diluted by adding the necessary amount of water or other solvents / diluents.

[0143] For the addition of glycidol, various addition temperature ranges of about 60°C to about 160°C can be used. In addition, depending on the scale of the reaction, the addition rate can be about 5 ml per hour to about 3 to 4 days. It is expected that by-products such as polyglycerol will be formed in the final product. The samples described herein and in the following examples can be used without further purification.

[0144] Table 2. Pesticide formulations containing alkylamidoamine polyglycerols

[0145]

[0146]

[0147] *APA-7: Alkyl-amidopropylamine of C7 fatty acid

[0148] The results show that the surfactants of the present disclosure are compatible with various pesticides.

[0149] Although at least one exemplary embodiment has been given in the foregoing detailed description, it should be understood that there are a large number of variations. It should also be understood that the exemplary embodiment or multiple exemplary embodiments are merely examples and are not intended to limit the scope, applicability or configuration in any way. On the contrary, the foregoing detailed description will provide a convenient roadmap for implementing the exemplary embodiment for those skilled in the art. It should be understood that various changes can be made to the function and arrangement of the elements described in the exemplary embodiment without departing from the scope set forth in the appended claims.

Claims

1. An agricultural chemical composition comprising: Pesticides; and At least one surfactant having the structure: (I)； (II); (III); (IV); (V); or (WE); Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups; wherein each m is independently 1 to 4; wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a wherein the glyceryl residue (glyceryl) a Selected from: With formula A linear polyglyceryl moiety; or With formula A branched polyglyceryl moiety; wherein each a is independently 1 to 30; wherein each O is independently optional, as long as at least one O is present; Each of the B - is independently optional and when present is R 1 X - , as long as there is at least one B - ; Each R 1 is independently optional and when present is methyl or ethyl; and Each X - Independently Cl - Br - 、CH3OSO3 - 、CH3CH2OSO3 - , or if R 1 If it doesn't exist, it doesn't exist.

2. The agricultural chemical composition according to claim 1, wherein each a is independently 1 to 20.

3. The agricultural chemical composition according to claim 1, wherein each a is independently 1 to 4.

4. The agricultural chemical composition according to any one of claims 1 to 3, wherein each R is independently C8-C 18 Group.

5. The agricultural chemical composition according to any one of claims 1 to 3, wherein each R is independently C 10 -C 18 Group.

6. The agricultural chemical composition according to any one of claims 1 to 3, wherein each R is independently a hydrocarbon group derived from an animal source, a plant source, a microorganism or an algae source, and a combination thereof. 7 . The agricultural chemical composition according to claim 1 , wherein the surfactant has structure (I) and wherein m is 1 and a is 1 to 15. 8 . The agricultural chemical composition according to claim 1 , wherein the surfactant has structure (II) and wherein m is 1 and a is 1 to 15.

9. The agricultural chemical composition according to any one of claims 1 to 3 and claims 7 to 8, wherein the surfactant is a derivative or reaction product of a reaction product of glycidol and an alkyl amidoamine having the following structure: Where each R is independently C6 to C 22 A linear or branched, saturated or unsaturated hydrocarbon group; and wherein each m is independently 1 to 4.

10. The agrochemical composition according to any one of claims 1 to 3 and claims 7 to 8, wherein the pesticide is selected from the group consisting of herbicides, fungicides, insecticides and combinations thereof. 11 . The agricultural chemical composition according to claim 10 , wherein the herbicide is selected from glyphosate, dicamba, glufosinate, 2,4-D or a combination thereof.

12. The agricultural chemical composition according to claim 11, wherein the herbicide is glyphosate or glufosinate.

13. A method of forming an agrochemical composition according to any one of claims 1 to 12, said method comprising the step of combining said at least one surfactant and said pesticide.

14. A method for treating vegetation, comprising the step of applying the agricultural chemical composition according to any one of claims 1 to 12 to the vegetation.

15. A surfactant having the following structure: (I)； (III); (IV); (V); or (WE); Where each R is independently C6 to C 22 Linear or branched, saturated or unsaturated hydrocarbon groups; wherein each m is independently 1 to 4; wherein each Z is independently a glyceryl residue (glyceryl) a or H, provided that at least one Z is a glyceryl residue (glyceryl) a wherein the glyceryl residue (glyceryl) a Selected from: With formula A linear polyglyceryl moiety; or With formula A branched polyglyceryl moiety; wherein each a is independently 1 to 30; wherein each O is independently optional, as long as at least one O is present; Each of the B - is independently optional and when present is R 1 X - , as long as there is at least one B - ; Each R 1 is independently optional and when present is methyl or ethyl; and Each X - Independently Cl - Br - 、CH3OSO3 - 、CH3CH2OSO3 - , or if R 1 If it doesn't exist, it doesn't exist.

16. The surfactant according to claim 15, wherein each a is independently 1 to 20.

17. The surfactant according to claim 15, wherein each a is independently 1 to 4.

18. A surfactant according to any one of claims 15 to 17, wherein each R is independently C8-C 18 Group.

19. The surfactant according to any one of claims 15 to 17, wherein each R is independently C 10 -C 18 Group.

20. The surfactant according to any one of claims 15 to 17, wherein each R is independently a hydrocarbon group derived from animal origin, plant origin, microbial origin or algae origin, and combinations thereof.

21. The surfactant of claim 15 having structure (I) and wherein m is 1 and a is 1 to 15.

22. The surfactant of claim 15 having structure (II) and wherein m is 1 and a is 1 to 15.

23. A surfactant according to any one of claims 15 to 17 and claims 21 to 22 which is a derivative or reaction product of a reaction product of glycidol with an alkylamidoamine having the structure: Where each R is independently C6 to C 22 A linear or branched, saturated or unsaturated hydrocarbon group; and wherein each m is independently 1 to 4.

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