MXPA01005970A - Pesticide formulations containing alkoxylated tristyrylphenol hemi-sulfate ester neutralized alkoxylated amine surfactants - Google Patents

Abstract

The present invention relates to a surfactant for general use in agricultural compositions, including, but not limited to herbicidal, fungicidal and insecticidal formulations comprised of two components:an alkoxylated tristyrylphenol acid neutralized to the desired pH or properties with an appropriate amount of alkoxylated alkyl amine.

Description

PESTICIDE FORMULATIONS CONTAINING NEUTRALIZED ALCOHOLATED AMINO TENSIONERS WITH ESTER OF TRIESTIRYLPHENOL HEMISULPHATE ALCOXILATED FIELD OF THE INVENTION The present invention relates to a surfactant system for general use in agricultural compositions, including, but not limited to, herbicidal, fungicidal, and insecticidal formulations comprised of two components: an alkoxylated tristyrylphenol hemisulfate ester neutralized to pH desired with an appropriate amount of an alkoxylated alkylamine.

BACKGROUND OF THE INVENTION Alkylphenol ethoxylates (APE) and their anionic derivatives are surfactants that are well known in the industry, and historically, have been widely used by agricultural chemical producers. However, formulations containing alkylphenol ethoxylates do not Ref: 129932 always provide the most desirable combination of design specifications, for example product effectiveness, work parameters, and cost. Traditional surfactant systems which are not alkylphenol ethoxylate have not been readily adaptable substitutes for alkylphenol ethoxylate surfactants. For example, calcium dodecylbenzenesulfonic acid used in conjunction with alkoxylated amines has not been as robust as alkylphenol ethoxylates and their derivatives, due to unacceptable performance in one or more key performance areas, such as emulsion stability, toxicity acute, temporary and thermal stability, chemical and physical stability; solution dynamics, suspension, or dilution; stress tolerance due to shear stress; viscosity; or lack of compatibility with mixing partners. Phosphate esters of alcohol ethoxylates, which are surfactants without alkylphenol ethoxylates, found in many industrial uses, have long-term stability problems due to hydrolytically driven transesterification and saponification reactions involving the monoester, diester, and free acid components of the surfactant mixture. Sulfated surfactants in flowable formulations are normally susceptible to hydrolytic decomposition, particularly when the formulations are stored under hot storage conditions in summer. Acingly, there has been a need for an alternative surfactant system that can be easily made from readily available and cost effective raw material, and that is robust to the chemical and physical conditions that could be encountered by the product formulated in its life span BRIEF DESCRIPTION OF THE INVENTION Surprisingly, it has now been discovered that certain aromatic acids, such as the alkoxylated tristyrylphenol hemisulfate esters, which have been neutralized with alkoxylated amines, are suitable as alternative ionic surfactants for general use in agricultural products. Even when the ethoxylated tristyrylphenol hemisulfate esters fall into the general classification of the alkylphenol ethoxylates, the tristyrylphenol group is structurally very different from the known or conventional alkylphenol ethoxylate surfactants. The surfactants of the present invention may be in the form of a surfactant compound, or a composition containing one or more surfactant compounds or salts. In one embodiment of the invention, the compositions containing the present surfactant compounds do not contain or are substantially free of known or conventional alkylphenol ethoxylates. The surfactants of the present invention are obtained from the combination of the appropriate alkoxylated tristyrylphenol hemisulfate ester with the appropriate alkoxylated amine. The steric configuration of the tristyrylphenol group protects the surfactant from the hydrolytic dissociation normally observed in other known anionic sulfate ester surfactant systems.

DETAILED DESCRIPTION OF THE INVENTION One aspect of the invention relates to the compounds of the formula (1): (H-B) + A ~ (1) wherein A- is the conjugated base of H-A acid, wherein H-A is an alkoxylated tristyrylphenol hemisulfate ester; and (H-B) + is the conjugate acid of base B, wherein B is an alkoxylated amine. A preferred aspect of the invention are compounds having the formula (H-B) + A ~, wherein A is the anion of the formula: wherein each R1 is independently an alkylene of 2 to 4 straight or branched chain carbon atoms, n is a number from 1 to 50 inclusive, and wherein (H-B) + is the cation of the formula: wherein R2 is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and alkenyl of 2 to 24 carbon atoms -CH2-, each R3 is independently an alkylene of 2 to 4 carbon atoms of straight or branched string, x is a number from 1 to 50 inclusive, and y is a number from 0 to 50 inclusive. "Independently" in the context of the definition of R3 means that R3 can be independently selected in all aspects. Accordingly, the substituents - (R30) x-H and - (R30)? -H as a whole, can be composed of different R3 groups and each of the substituents themselves can also be composed of different R3 groups. A more preferred embodiment of the invention are the compounds of formula (1), wherein A "is: wherein n is from about 4 to 25 (preferably from 4 to 16, especially 8); and where (H-B) + is the cation of the formula: wherein R2 is selected from the group consisting of normal octadecyl, normal hexadecyl, and cis-9-octadecenyl, and x + y is a number from about 2 to 15 (preferably from 4 to 9). A feature of the invention is where x + y is 5.

The invention also relates to the salt compound produced from the process of neutralizing an alkoxylated tristyrylphenol hemisulfate ester of the formula (2) below (also referred to as HA), with an alkoxylated amine of the formula (3) plus forward (also referred to herein as B). Ammonium sulfate compounds, or the product of the process of combining an aromatic acid HA with an alkoxylated amine B (to the extent there is difference), are both characteristics of the invention disclosed herein. The scope of the invention disclosed herein should not be construed to be limited by any particular chemical theory related to complex formation, equilibrium, reaction, or acid-base chemistry of the components used to make the surfactants or other ingredients used to make the formulations finally useful, such as pesticide formulations. In this regard, another aspect of the invention is the surfactant composition comprising one or more aromatic acids, and one or more alkoxylated amines, wherein the constituent components may or may not have chemically interacted to result in a change in the form of the components. The invention encompasses the static composition of the appropriate components mixed together, as well as the chemically integrated surfactant composition comprising at least one aromatic acid and at least one alkoxylated amine. "Static composition" denotes the composite composition of the components wherein the components have not substantially changed by virtue of their combination with other components of the composition. "Chemically integrated composition" means a composition resulting from natural equilibrium, complex formation, dissociation, or other chemical transformation, where appropriate, which may occur after the combination of the components, and before the final use of the surfactant in a pesticide formulation. Accordingly, the "chemically integrated composition" of the present invention, by definition, encompasses the situation where there is a "static composition" as well as any resulting composition that occurs at any point of time between the initial creation and the final use in the field of products containing the surfactant. In other words, the invention disclosed is not limited to a static composition of chemically unaltered constituent components. Another aspect of the invention is the surfactant composition produced as a whole from the combination of the aromatic acid HA and the alkoxylated amine base B, to the extent that it consists of different products of ammonium sulfate compounds. This composition may contain chemically unaltered starting materials, as well as other reaction products or by-products of the reaction, equilibrium, dissociation, or complex formation of the components in the composition. The invention also includes the process for obtaining a surfactant that is useful as a substitute for known or conventional alkylphenol ethoxylates. In addition to the surfactant product or the product by the process, the process of obtaining or making any of the surfactants is disclosed herein as part of the invention. The invention also includes the method of using the surfactant compounds of the formula (1), and compositions thereof, as substitutes for known or conventional alkylphenol ethoxylates.

The alkoxylated amines B and the aromatic acids HA used to make the surfactants of the invention are preferably those compounds that are readily available and are inexpensive. However, the cost of the materials is only one factor in the selection of the specific alkoxylated amines B and the aromatic acids HA used as starting materials. After performing a routine cost-benefit analysis, and in view of other design parameters, it can be seen that more expensive and less readily available starting materials may be preferred. The aromatic acids used in the present invention can be defined in general by the formula (2) (2) wherein each R 1 is independently a straight or branched chain 2 to 4 carbon alkylene, and n is a number from 1 to 50 inclusive. Preferred starting materials for making the surfactants of the present invention are one or more of the compounds defined by the formula (2a): where n is as defined above. Preferred alkoxylated amines useful for making the surfactants of the present invention are one or more of the compounds defined by the formula (3): wherein R2 is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and alkenyl of 2 to 24 carbon atoms-CH2-, each R3 is independently an alkylene of 2 to 4 carbon atoms of straight or branched string, x is a number from 1 to 50 inclusive, and y is a number from 0 to 50 inclusive. A preferred feature of the invention is wherein the alkoxylated amines are one or more of the ethoxylated amines of the formula (3a) / Í C H > C H * 0) > ~ H Ft N \ (CB2CH20) and - H (5) wherein R, x, ey are defined above, preferably wherein R2 is alkyl of 1 to 24 carbon atoms, and the average of x + y is a number of about 2 to 15. Additional preferred aspects of the invention are wherein R is selected from the group consisting of normal octadecyl, normal hexadecyl, and cis-9-octadecenyl, and x + y is a number from 4 to 9. A feature of the invention is where the average value of x + and is 5. Another aspect of the invention is the composition comprising the formulation of the surfactants disclosed above, in formulations containing one or more different active ingredients. A preferred embodiment of the invention is a pesticidal formulation containing the surfactants disclosed herein. However, the invention is not limited to pesticidal formulations. Other useful formulations which may contain the surfactants disclosed herein include shampoo formulations, general detergent formulations, and soap formulations used in the mining industry. The surfactants disclosed herein are considered to have general applicability as alternatives to conventional alkylphenol ethoxylates, and therefore, would be expected to be useful in many other known formulations. The invention encompasses any formulation obtained by the substitution in another way of the surfactants disclosed herein as alternatives to the alkylphenol ethoxylate surfactants, as well as other surfactants. The invention disclosed herein also encompasses any formulation obtained by supplementing the known or conventional alkylphenol ethoxylate containing compositions with the surfactants claimed herein. In general, any formulation that makes use of a surfactant additive would be subject to modification by substitution or complementation with one or more of the surfactants of the present invention. Although the compounds and compositions are referred to as "surfactants" in the present application, it is expected that they will also have other non-surfactant properties that may be useful regardless of any inherent surfactant properties. Depending on the application of the present invention, may result in greater bioefficacy and / or reduced toxicity and irritation. Another aspect of the invention is the composition comprising the formulation of the surfactants disclosed above, in formulations containing one or more herbicides, and one or more protectants (antidotes). When herbicides are applied, the cultivated plants can also suffer severe damage due to factors including the concentration of the herbicide and the mode of application, the cultivated plant itself, the nature of the soil, and climatic conditions, such as exposure. A preferred embodiment of the invention is, for example, the formulation of S-metolachlor and benoxacor, or S-metolachlor, atrazine and benoxacor, each in combination with the surfactants of the present invention. The surfactants are prepared by mixing at least one aromatic acid of the formula (2) with at least one alkoxylated amine of the formula (3), with pH control. The desired pH is maintained by precisely regulating the proportion of the acid and base components in the composition. For example, the appropriate acid-base ratio and the desired pH can be achieved according to the following procedure: 1) A known weight of the aromatic acid is dissolved in a 50/50 solution of isopropanol and water. 2) A steep amount of alkoxylated amine is slowly added to the aromatic acid with constant stirring, using a magnetic stirrer, while monitoring the pH by using a pH meter adapted with a silver chloride electrode. 3) When the desired pH is obtained, the amount of alkoxylated amine required is measured. 4) The proportion of aromatic acid: alkoxylated amine (acid: base) is determined, and the surfactant is prepared by mixing the appropriate amounts of the two components with stirring. For many of the pesticidal formulations described herein, the preferred ratio of acid: base is about 35:65 (weight ratio). The acidity or basicity of the constituent components may vary, depending on the supplier of the materials or the particular batch, and therefore, the pH is the control factor in the preparation of the compounds, compositions, and formulations of the present invention. The pKa and the pKb for the aromatic acid and the alkoxylated amine, respectively, can be varied to some degree, by manipulating the type and degree of substitution for the compounds defined by the formulas (2) and (3). Accordingly, the selection of the particular acid or base used will also affect the proportion of acid: base used to make the surfactants, as well as the desired pH. A preferred pH scale for the surfactant is a pH of about 3 to 9, a more preferred pH scale is about 3 to 8.5, and a finally preferred pH scale is about 5 to 8. It is less desirable to adjust the pH after the components of aromatic acid and amine base are mixed, by the addition of other acids or bases normally used to raise or lower the pH, due to the fact that even smaller amounts of additional salts can make a big difference in the observed properties of the surfactant product. It is also less desirable to have additional process steps, or to have the added cost associated with the purchase, handling, storage, and disposal of the additional chemicals. The stability of the ethoxylated aromatic acid emulsion, such as the ethoxylated tristyrylphenol hemisulfate ester of the formula (2a), neutralized with an ethoxylated tallow amine of the formula (3a), is usually greater when the average number of units of Ethylene oxide (EO) on the aromatic acid is from 4 to 25 (ie from 4 to 25 EO), and when the EO on the tallow amine is from 4 to 9 EO. "Average" is defined as the arithmetic average of a set of real numbers (in this case, the number of units of ethylene oxide in the ethoxylated aromatic acids or in the ethoxylated amines used to make the surfactant). Another feature of the invention is where there is a continuous and symmetric bell curve population distribution around the EO. It may also be desirable for there to be a low dispersion of preference within one standard deviation (s) from the average (average EO). The tristyrylphenol alkoxylates and the amine alkoxylates can be prepared using chemistry procedures well known in the art. For example, tristyrylphenol ethoxylate can be prepared by treating tristyrylphenol with a base (eg, sodium hydroxide), followed by the addition of the desired equivalents of ethylene oxide. Tristyrylphenol is commercially available, can be prepared by known methods, or can be prepared in another manner using conventional chemistry knowledge.

Table 1: Examples of some suppliers and names of commercial products for the ethoxylated amines (ie, amine ethoxylates).

* Directions: See Table 3.

Another preferred feature of the present invention is the combination of the present compounds of the formula (1) with a nonionic co-surfactant. The non-ionic co-surfactants are those compounds known in the art for formulating surfactant systems. Nonionic co-surfactants include polyglycol ethers, polyglycol ether derivatives of aliphatic alcohols, cycloaliphatic alcohols, phenols, or saturated or unsaturated fatty acids. These derivatives, for example, can contain from 3 to 120 glycol ether groups, and from 8 to 30 carbon atoms in the hydrocarbon fraction. Preferred co-surfactants include, for example, tristyrylphenol ethoxylates (2 to 50 EO, more preferably 16 to 35 EO). Nonionic co-surfactants include block copolymers of ethylene oxide-propylene oxide (EO-PO), and block copolymer derivatives of EO-PO of aliphatic alcohols, cycloaliphatic alcohols, or phenols (for example block copolymers). EO-PO of butoxi). A preferred aspect of the invention includes the combination of the surfactant compositions herein with liquid pesticidal compositions, to obtain a concentrated emulsifiable formulation that can be mixed directly with water or other aqueous solutions, to give an aqueous pesticidal formulation without special mixing procedures . The following examples further illustrate some of the specific features of the invention, but are not intended to limit its scope. Where not otherwise specified throughout this specification and claims, temperatures are given in degrees centigrade.

Table 2: Examples of components that can be used to formulate the compositions of the present invention.

Table 3: Names and addresses of suppliers of materials . A preferred feature of the invention includes combining the previously described surfactant system with a non-ionic co-surfactant and a liquid active ingredient to obtain a concentrated emulsifiable formulation that can be easily diluted with water or other liquid carriers that do not require special procedures of handling or mixing. Here is an example of this formulation: EXAMPLE 1 An oil-based suspension concentrate containing liquid metolachlor was prepared as an active ingredient, in accordance with. the following formulation: 80.0 weight percent of metolachlor, 3.0 weight percent ester thrystyrylphenol ethoxylate ester (8EO) neutralized with tallow amine (5EO), 3.0 weight percent triestylphenylphenol ethoxylate (20EO), 14.0 percent by weight of aromatic hydrocarbon solvent. The above ingredients were formulated as follows: Triestylphenylphenol (8E0) ethoxylate hemisulfate ester neutralized with tallow amine (5E0) and tristyrylphenol ethoxylate (20EO), are charged to a vessel containing the aromatic hydrocarbon solvent, and mixed. Then the technical metolachlor is added and mixed until it is uniform. It is understood that the surfactant system of the present invention would be equally acceptable for, but not limited to, both water-based and oil-based formulations. Another preferred aspect of the invention includes the combination of the surfactant system of the present invention with a solid active ingredient. An example of this formulation is as follows: EXAMPLE 2 An aqueous suspension concentrate containing solid atrazine was prepared as an active ingredient according to the following formulation: 43.5 weight percent atrazine, 2.0 weight percent of tridecyl alcohol ethoxylate (6EO), 1. O per cent by weight. weight of EO-PO block copolymer, 2.0 weight percent of tri-ethyrylphenol ethoxylate (8EO) hemisulfate ester neutralized with tallow amine (8EO), 5.0 weight percent of ethylene glycol, and water to fill up to 1Q0 percent. The above ingredients were formulated as follows: The atrazine technique is gradually added to a vessel containing the tridecyl alcohol ethoxylate (6EO), the EO-PO block copolymer, the tri-styrylphenol ethoxylate hemisulfate ester (8EO) neutralized with tallow amine (8EO), ethylene glycol, and most of the water. The paste is mixed until uniform, and then ground to the appropriate particle size. The remaining water is added to meet the test specifications.

Another preferred aspect of the invention includes the combination of the surfactant system of this invention with a combination of solid and liquid active ingredients. An example of this formulation is as follows: Example 3 An aqueous suspension concentrate containing solid atrazine and liquid metolachlor is prepared as the two active ingredients, according to the following formulation: 26.1 weight percent s-metolachlor, 33.7 weight percent atrazine, 1.31 weight percent weight of benoxacor, 0.4 percent in that of EO-PO block copolymer, 0.67 weight percent of tridecyl alcohol (6EO), 3.15 weight percent of tri-ethyrylphenol ethoxylate ester (8EO) ester neutralized with amine of tallow (5EO), 1.5 weight percent of tristyrylphenol ethoxylate (35EO), 0.7 weight percent of antifoaming agent, 0.03 weight percent of thickening agent, such as xanthan gum, 0.03 percent in that of agent biostatic, 1.6 percent by weight of ethylene glycol, and water to fill up to 100 percent. The above ingredients were formulated as follows: Technical atrazine is slowly added to a • * container containing the EO-PO block copolymer, some of the tridecyl alcohol (6E0), the biostatic agent, the antifoaming agent, most of the water, and most of the ethylene glycol. The contents of the container are mixed until uniform, and then milled to the appropriate particle size. The thickening agent is added as a paste with the remaining tridecyl alcohol, and mixed until a uniform and stable final viscosity is reached. The test is adjust by adding water. The s-metolachlor and the benoxacor are charged in a second heated vessel, and are stirred until the benoxacor dissolves and the solution becomes uniform. The solution co The hemisulfate ester of tristyrylphenol ethoxylate (8EO) neutralized with tallow amine (5EO), tristyrylphenol ethoxylate (35EO), the remainder of ethylene glycol, and a small amount of water, and stirred until uniform. The contents of both containers are then mixed together in a simultaneous manner, and the final composition for the test is prepared.

Again it is understood that this formulation would be acceptable for, but not limited to, formulations based on water and oil. As indicated above, additionally one or more nonionic surfactant components may be used in conjunction with the surfactant composition previously described. Preferred co-surfactants are polyglycol ethers of aliphatic alcoh In particular, nonionic surfactants can include, but are not limited to, castor oil ethoxylates, tristyrylphenol ethoxylates, ethylene oxide / propylene oxide block copolymers, and / or ethylene oxide / oxide block copolymers. of propylene of aliphatic alcoh The crop protection compositions that are part of the invention disclosed herein, can be formulated in a form suitable for the intended application. The types of formulations include, for example, a flowable concentrate (FL) for seed treatment (FS), a wettable powder (WP), wettable dispersible granules (WDG), a flowable and miscible concentrate (OF), a suspension concentrate (SC), an emulsifiable concentrate (EC), liquid (L), water-in-oil (EW) emulsions, granules (GR), water dispersible powder for pulp treatment (WS), and dry flowable (DF). Some additional preferred embodiments of the present invention are contained in the following Tables 9 and 5.

Table: Crop protection formulations containing surfactant, specified non-ionic components, and one or more active technical components.

Ri = C2-4 alkylene R4 = C7-I9 n = 4 to 16 x + y = 2EO to 15EO Active technical ingredients used and type of formulation: Metolachlor Metribuzine WDG, OF, EC Metolachlor Simazine WDG, OF, SC s-Metoiaclor EC, DF, GR s-Metolaclo. Metribuzine WDG, OF, EC s-Metolaclcr S ima z ma WDG, OF, SC Me t r ibuz ma EC, DF, WDG, OF Norflurazon DF, GR Primisulfuron WDG, WP Primisulfuron Prosulfuron WDG, WP Profenofos EC Prometon EC, FL, OF, WP Prometrina WP, L, OF Propiconazole EC, WP Fimet rozma WDG, WP If azine WP, WDG, L, GR Tr. : onna WP, EC Tr i nexapac- EC, WDG, ethyl. COMPOSED TO WDG, OF, EC, SC COMPOSITE B WDG, WP > EU. WDG, WP, EC COMPOSITE D EC, WP, WDG EO = average number of ethylene oxide units.

Code Description of the formulation code DF Dry flowable EC Emulsifiable concentrate EW Water-in-oil emulsions FL Fluible FS Flowable concentrate for seed treatment GR Granules L Liquid OF Concentrate flowable miscible in SC oil Concentrate in suspension WDG Dispersible wettable granules WP Wettable powder WS Water dispersible powder for paste treatment Table 6: Structures for Compounds A to D: In summary, it is seen that this invention provides new compounds useful as surfactants, which are alternatives to known or conventional surfactant systems. In particular, the surfactant compounds of the present invention are useful for formulating agrochemical compositions. Variations in proportions, procedures, and materials can be made without departing from the scope of the invention as defined by the following claims.

It is noted that in relation to this date, the best known method for the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.

Claims (27)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A compound according to formula (H-B) "A" characterized in that A "is: wherein each R1 is independently an alkylene of 2 to 4 straight or branched chain carbon atoms, n is a number from 1 to 50 inclusive, wherein (H-B) + is the cation of the formula: wherein R is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and alkenyl of 2 to 24 carbon atoms-CH2-, each R3 is independently an alkylene of 2 to 4 carbon atoms of straight or branched string, x is a number from 1 to 50 inclusive, and y is a number from 0 to 50 inclusive.
2. 2. A compound according to claim 1, characterized in that A ~ is: or and where (H-B) + is the cation of the formula: where x + y is a number from approximately 4 to 9.
3. 3. A compound according to claim 2, characterized in that n is from 4 to 16.
4. 4. A compound according to claim 3, characterized in that n is 8.
5. 5. A compound according to claim 4, characterized in that R2 is selected from the group consisting of normal octadecyl, normal hexadecyl, and cis-9-octadecenyl; and x + y is equal to 5.
6. 6. A product that can be obtained by the process of neutralizing at least one aromatic acid of the formula (2): characterized in that each R1 is independently an alkylene of 2 to 4 straight or branched chain carbon atoms, n is a number from 1 to 50 inclusive, with at least one alkoxylated amine base of the formula (3): wherein R is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and alkenyl of 2 to 24 carbon atoms-CH2-, each R3 is independently an alkylene of 2 to 4 carbon atoms of straight or branched string, x is a number from 1 to 50 inclusive, and y is a number from 0 to 50 inclusive.
7. 7. A product according to claim 6, characterized in that at least one aromatic acid is a compound defined by the formula (2a): and wherein at least one base of ethoxylated amine is a compound defined by formula (3a): (CH2CH20), H R. N wherein R2 is alkyl of 1 to 24 carbon atoms, and the average of x + y is a number of about 4 to 9.
8. 8. A product according to claim 6, characterized in that the surfactant product has a pH of about 3 to 9.
9. 9. A product according to claim 6, characterized in that the surfactant product has a pH of about 3 to 8.5.
10. 10. A product according to claim 6, characterized in that the surfactant product has a pH of 5 to 8.
11. 11. A surfactant composition characterized in that it comprises a salt of: (k) and at least one aromatic acid which is a compound of the formula (2): wherein each R1 is independently an alkylene of 2 to 4 straight or branched chain carbon atoms, n is a number from 1 to 50 inclusive; and (b) at least one alkoxylated amine base of the formula (3): wherein R is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and alkenyl of 2 to 24 carbon atoms-CH2-, each R3 is independently an alkylene of 2 to 4 carbon atoms of straight or branched string, x is a number from 1 to 50 inclusive, and y is a number from 0 to 50 inclusive.
12. 12. A surfactant composition according to claim 11, characterized in that: (a) is at least one aromatic acid compound of the formula (2a): (b) is at least one ethoxylated amine base of the formula (3a): (CHjCH.}., H / R, N (CHJCHJO (ja) wherein R2 is alkyl of 1 to 24 carbon atoms, and the average of x + y is a number of about 4 to 9.
13. 13. A composition according to claim 11, characterized in that the surfactant product has a pH of about 3 to 9.
14. 14. A composition according to claim 11, characterized in that the surfactant product has a pH of about 3 to 8.5.
15. 15. A composition according to claim 11, characterized in that the surfactant product has a pH of 5 to 8.
16. 16. A chemically integrated surfactant composition characterized in that it comprises at least one aromatic acid compound of the formula (2). wherein each R1 is independently an alkylene of 2 to 4 straight or branched chain carbon atoms, n is a number from 1 to 50 inclusive, and at least one alkoxylated amine base of the formula (3): wherein R2 is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and alkenyl of 2 to 24 carbon atoms-CH2-, each R3 is independently an alkylene of 2 to 4 carbon atoms of straight or branched chain, x is a number from 1 to 50 inclusive, and e is a number from 0 to 50 inclusive, or the chemical interaction products thereof.
17. 17. A chemically integrated surfactant composition according to claim 16, characterized in that the aromatic acid is at least one compound of the formula (2a): (2a) and at least one base of ethoxylated amine which is a compound defined by formula (3a): - (CH2CH20) x H R- N \ (CH .22CwH, .220,) ¥ H (3a) wherein R2 is alkyl of 1 to 24 carbon atoms, and the average of x + y is a number of about 4 to 9.
18. 18. A composition according to claim 16, characterized in that the surfactant product has a pH of about 3 to 9.
19. 19. A composition according to claim 16, characterized in that the surfactant product has a pH of about 3 to 8.5.
20. 20. A composition according to claim 16, characterized in that the surfactant product has a pH of 5 to 8.
21. 21. A pesticidal formulation comprising at least one pesticide and at least one aromatic acid neutralized with at least one ethoxylated amine, characterized in that the aromatic acid is of the formula (2): wherein each R 1 is independently a straight or branched chain 2 to 4 carbon alkylene, n is a number from 1 to 50 inclusive, and the alkoxylated amine of the formula (3): wherein R2 is selected from the group consisting of hydrogen, alkyl of 1 to 24 carbon atoms, and alkenyl of 2 to 24 carbon atoms-CH2-, each R3 is independently an alkylene of 2 to 4 carbon atoms of straight or branched string, x is a number from 1 to 50 inclusive, and y is a number from 0 to 50 inclusive.
22. 22. A pesticidal formulation according to claim 21, characterized in that the aromatic acid is of the formula (2a): (2a) and the ethoxylated amine is of the formula (3a) (CHGH20 / .. H R. N (CH2CH2O -H (3a) wherein R is alkyl of 1 to 24 carbon atoms, and the average of x + y is a number of about 4 to 9.
23. 23. A pesticidal formulation according to claim 21, characterized in that the pesticide is atrazine or glyphosate.
24. 24. A method for protecting crops, characterized in that it comprises the step of applying to the place of the crops in need of protection, an agriculturally effective amount of the formulation according to claim 21.
25. 25. A method for protecting crops, characterized in that it comprises the step of applying to the place of the crops in need of protection, an agriculturally effective amount of the formulation according to claim 22.
26. 26. A method for using the compound according to claim 1 in the form of an alternative surfactant, characterized in that it comprises replacing a known alkylphenol ethoxylate surfactant system in a formulation with the compounds having the formula (H-B) + A ~.
27. 27. A compound according to formula (1): (HB) + A "(1) characterized in that A" is the conjugate base of the HA acid, wherein HA is an alkoxylated tristyrylphenol hemisulfate ester / and (HB) + is the conjugate acid of base B, wherein B is an alkoxylated amine.