AU1556002A - Pesticide formulations containing alkoxylated amine neutralized aromatic sulfonic acid surfactants - Google Patents

Description

AUSTRALIA

PATENTS ACT 1990 DIVISIONAL APPLICATION NAME OF APPLICANT: Syngenta Participations AG ADDRESS FOR SERVICE: DAVIES COLLISON CAVE Patent Attorneys 1 Little Collins Street Melbourne, 3000.

INVENTION TITLE: "Pesticide formulations containing alkoxylated amine neutralized aromatic sulfonic acid surfactants" The following statement is a full description of this invention, including the best method of performing it known to us: A-v.> PESTICIDE FORMULATIONS CONTAINING ALKOXYLATED AMINE NEUTRALIZED AROMATIC SULFONIC ACID

SURFACTANTS

FIELD OF THE INVENTION This application is a divisional of Australian Patent Application No. 53735/99, the entire contents of which are incorporated herein by reference.

The present invention relates to surfactants useful in life science and industrial formulations. More particularly, the invention relates to surfactants of alkoxylated amine neutralized by aromatic sulfonic acid and pesticide formulations containing the same.

BACKGROUND OF THE INVENTION Alkylphenol ethoxylates (APEs) are a class of common industrial surfactants which are widely used in pesticide formulations. However, formulations containing APEs do not always provide the most desirable combination of design specifications, e.g. product 999** 0 efficacy, working parameters and cost. Traditional non-APE surfactant systems have not been readily adaptable substitutes for APE surfactants. For example, depending on the formulation requirements, calcium dodecylbenzesulfonate used in conjunction with fatty acid ethoxylates has proven to be an unacceptable APE substitute because of poor performance within one or more design parameters such as emulsion stability, acute toxicity, temporal and thermal stability, chemical and physical stability; solution, suspension *0o or dilution dynamics, and viscosity and suspension stabilization. Phosphate esters, which are non-APE surfactants found in many types of formulations, suffer from long term stability °0 •problems due to undesirable transesterification and saponification reactions involving the mono-ester, di-ester, and free acid components of the surfactant mixture. The inability of industry to adapt existing technology to improve upon characteristics of surfactant systems containing APEs has prompted the development of entirely new line non-APE surfactant substitutes. The additional challenge faced by the scientific community has been to develop new non-APE substitutes which can be easily made from readily available and cost effective raw materials. Accordingly, there continues to be a need for other non-APE surfactant substitutes.

SUMMARY OF THE INVENTION It has now been found that alkoxylated amine neutralized aromatic sulfonic acids are suitable as non-APE surfactant substitutes. The surfactants of the instant invention may be ~~ri in the form of a surfactant salt compound, or composition containing one or more the surfactant compounds or salts. In one embodiment of the invention, the compositions containing the instant non-APE surfactants do not contain or are substantially free of alkylphenol ethoxylates (APEs). The surfactants of the instant invention are obtained from combining the appropriate aromatic sulfonic acid with the appropriate alkoxylated amine.

DETAILED DESCRIPTION OF THE INVENTION One aspect of the invention is the salt compound of formula n A n

(I)

wherein A"n is the conjugate bas3 of the acid H-A, wherein H-A is an aromatic sulfonic acid; and (H-B) is the conjugate acid of the base B, wherein B is an alkoxylated amine, and n is the number of sulfonate anion groups or sulfonic acid groups on the conjugate base or acid respectively and with the proviso that HA and A"n may not contain a phenolic moiety. A "phenolic moiety" is defined as any phenyl ring containing at least one -OH group or any group developed by replacing the hydrogen of the -OH group with another organic or metal radical. The invention disclosed herein also includes a surfactant composition comprising a salt compound of formula The invention also includes a pesticide formulation comprising at least one pesticide and a salt compound of formula A preferred aspect of the invention is the salt compound having the formula

A

n wherein A n is the anion of the formula: (R)q (SO 3) so S(SO3)S or (R)r (SO 3 wherein each R is independently selected from the group consisting of C1-C24 alkyl, and C7- C24 alkylaryl, m is a number from 0 to 5, n is a number from 1 to 3, p is a number from 0 to 3, q is a number from 0 to 3, and r is a number from 0 to 4, s is a number from 1 to 3, and is the cation of the formula: At -Z4 -A LS .A i i- t n H\ (RsO)-

H

N

R

4 (RsO) H wherein R 4 is selected from the group consisting of hydrogen, C1-C24 alkyl and C 2

-C

24 alkenyl-CH 2 each R 5 independently is straight or branched chain C2-C4 alkylene, and x is a number from 1 to 50 and y is a number from 0 to 50, preferrably x y is number from 2 to inclusive. A more preferred embodiment of the salt compound of formula (H-B)+A wherein A is the anion of the formula: R2 o -0 or and C1-C24 alkyl and (H-B) is the cation of the formula: H (CH2CH20)x

-H

R0 wherein R4 is d e fined above (preferably n-octadecyl, n-hexadecyl and cis-9-octadecenyl); and x y is a number from about 7 to 9 (preferably Another more preferred embodiment of the invention is the salt compound wherein A is an anion having the formula:

*R

RH HH

S

4

S-

wherein R, is n-docecyl group.

S The invention also is the compound or salt produced from the process of neutralizing an aromatic sulfonic acid of formula HA with an alkoxylated amine of formula B. The ammoniumsulfonate salt compounds or the product from the process of combining an aromatic sulfonic acid with an alkoxylated amine (to the extent there is a difference) are both features of the instantly disclosed invention. The scope of the invention disclosed herein should not be construed to be limited by any particular chemical theory relating to the -4complexation, equilibration, reaction or acid-base chemistry of the components used to make the surfactants or other ingredients used to make other ultimately useful formulations pesticide formulations). In this regard, another aspect of the invention is the surfactant composition comprising one or more aromatic sulfonic acids and one or more alkoxylated amines wherein the constituent components may or may not have interacted chemically so as to result in a change in form of the components. The invention encompasses the static composition of the appropriate components admixed together as well as the chemically integrated surfactant composition comprising at least one aromatic sulfonic acid and at least one alkoxylated amine. "Static composition" denotes the composition composed of components wherein the components have not substantially changed by virtue of their l combination with other composition components. "Chemically integrated composition" means a composition that results from the natural equilibration, complexation, dissociation or other chemical transformation if any that may occur after combination of the components and prior to ultimate use of the surfactant in a pesticide formulation. Therefore, the "chemically integrated composition" of the instant invention by definition encompasses the situation where there is a "static composition" as well as any resultant composition occurring at any point in time betvween initial creation and ultimate use in the field of products containing the surfactant. In other words, the disclosed invention 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 sulfonic acid and the alkoxylated amine base to the extent it is composed of products other than ammoniumsulfonate salt compounds. Such a composition may contain chemically unaltered starting materials as well as other reaction products or by-products from reaction, equilibration, dissociation or complexation of the components in the composition.

The invention also includes the process for obtaining a surfactant which is useful as an APE substitute. In addition to the surfactant product or the product-by-process, the process of obtaining or making any of the surfactants is herein disclosed as part of the Sinvention. The invention also includes the method of using the surfactant salt compounds of formula and compositions thereof as APE substitutes.

The alkoxylated amines and the aromatic sulfonic acids used to make the surfactants of the invention are preferably those compounds that are readily available and inexpensive. However, cost of materials is only one factor in selecting the alkoxylated amines and the aromatic acids used as starting materials. After performing a routine costr E~a benefit analysis and in view of other design parameters it may become apparent that more expensive and less readily available starting materials may be preferred.

The aromatic sulfonic acids used in the instant invention may have one or more sulfonic acid groups and one or more groups attached to the aromatic moiety therein. The aromatic sulfonic acids may generally be defined by formulae II or III:

(SO

3

H)

p

(R)

m (SO H) (SO3H)s (11) o r (II) or (Ill) wherein each R, m, n, p, q, r and s are defined as above.

:'*The preferred starting materials for making the surfactants of the instant invention are the compounds defined by formula Ila or Ilia: R2 O o S--OH S-OH II II 0 (lla) or R3 (Ilia) wherein R 1

R

2 and R 3 are defined as above.

The preferred alkoxylated amines useful for making the surfactants of the instant invention are one or more of the compounds defined by formula IV: /(RsO)x-H

R

4

N

S. (R50)y-H 5 y

(IV)

wherein R 4 x and y are defined as above. A preferred feature of the invention is where the alkoxylated amines are one or more of the ethoxylated amines of formula V:

S(CH

2

CH

2 O)x -H

R

4

N

(CH2CH2O) H (V) wherein R 4 x and y are defined as above. Additional preferred aspects of the invention are where R 4 is selected from the group consisting of n-octadecyl, n-hexadecyl and cis-9octadecenyl, and x y is a number from 5-10. Another preferred aspect of the invention is where the average x y is a number from about 7 to 9 (more preferably 8).

Another aspect of the invention is the composition comprising the formulation of the surfactants disclosed above in formulations that contain one or more other active ingredients. A preferred embodiment of the invention is a pesticide formulation which contains the presently disclosed non-APE containing surfactants. However, the invention is not limited to pesticide formulations. Other useful formulations that may contain the instantly disclosed non-APE containing surfactants include shampoo formulations, detergent formulations generally and soap formulations used in the mining industry. The surfactants presently disclosed are considered to have general applicability as APE oooo substitutes, and therefore would be expected to be useful in many other known 9.

formulations. The invention encompasses any formulation obtained by otherwise *substituting the instantly disclosed surfactants for APEs as well as other surfactants. The instantly disclosed invention also encompasses any formulation obtained by supplementing compositions containing APEs with the instantly claimed surfactants. Generally, any formulation that conventionally makes use of surfactant additives would be subject to modification by substitution or supplementation with one or more of the surfactants of the instant invention. Although the compounds and compositions are referred to as "surfactants" in the instant application, it is expected that they will also have other ""nonsurfactant properties that may be useful independently of any inherent surfactant properties. Depending on the application of the instant invention, it may result in increased 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 that contain one or more herbicides and one or more safeners (antidote). When applying herbicides, the cultivated plants may also suffer severe damage owing to factors that include the concentration of the herbicide and the mode of application, the cultivated plant itself, the nature of the soil, and the climatic conditions such as exposure. A preferred embodiment of the invention is for example the formulation of the of s-metolachlor and benoxacor, or s-metolachlor, atrazine and benoxacor each in combination with the surfactants of the instant invention.

The surfactants are prepared by mixing the aromatic sulfonic acid of formula II or III with the alkoxylated amine of formula IV while controlling pH. The desired pH is maintained by precisely regulating the ratio of the acid and base components in the composition. For example, the appropriate acid-base ratio and desired pH can be achieved according to the r following procedure: 1) A known weight of the aromatic sulfonic acid is dissolved in a 50/50 solution of isopropanol and water. 2) A tared amount of alkoxylated amine is slowly added to the aromatic sulfonic acid with constant stirring using a magnetic stirrer while pH is monitored by use of a pH meter fitted with a silver chloride electrode. 3) When the desired pH is attained, the amount of required alkoxylated amine is measured. 4) The ratio of aromatic sulfonic 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 pesticide formulations described herein the preferred acid base ratio is approximately 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, therefore the pH is the controlling factor in preparing the compounds, compositions and formulations of the instant invention. The pKa and pKb for the aromatic sulfonic acid and the alkoxylated 'oamine respectively may be varied to some extent by manipulating the type and degree of substitution for the compounds defined by formula II, III and IV. Therefore, the selection of the particular acid or base used will also effect the acid base ratio used to make the surfactants as well as the desired pH. A preferred pH range for the surfactant is a pH from approximately 3-7, a more preferred pH range is from approximately 4 to 6, and an ultimately preferred pH range is from approximately 5-6. It is less desirable to adjust pH after the sulfonic acid and amine base components are mixed by the further addition of oo other acids or bases typically used to raise or lower pH because even minor amounts of additional salts can make a large difference in the observed properties of the product surfactant. It is also less desirable to have additional process steps or to have the added cost associated with purchasing, handling, storage and disposal of additional chemicals.

The emulsion stability of dodecylbenzenesulfonic acid neutralized with and ethoxylated tallow amine is typically greatest when the "average number of ethylene oxide units" (EO) on the tallow amine is 8 8EO). "Average" is defined as the arithmetic mean of a set of real numbers (in this case the number of ethylene oxide units in the ethoxylated amines used to make the surfactant). A preferred feature of the invention is where there is a continuous and symmetrical bell curve population distribution around 8EO. It is also desirable that there be low dispersion preferably within one standard deviation of the mean (average EO). A decrease in emulsification ability is observed when either 7EO or 9EO tallow amine was used to make the surfactant.

AZ A t *O Some commercial suppliers and product names for the ethoxylated amines (i.e.

amine ethoxylates) are: amine Supplier Product Name Average Number of ethoxylate EO Tallow amines Witco Witcamine TAM-XO 2, 4, 4.5, 5, 6, 7, 8, 9, (X average number of EO) 10 and Coco amines Witco Varonic K-2XX 02, 05, 10 and (XX average number of EO) Stephan Toximul TA-X 2, 4, 4.5, 5, 6, 7, 8, 9, (X average number of EO) 10 and Oleyl amine Witco Varonic Q-202 2 SAddresses: Witco Corporation, 5777 Frantz Road, P.O. Box 646, Dublin, Ohio 43017.

Stephan Company, Northfield, Illinois 60093.

One preferred aspect of the invention includes the combination of the surfactant compositions herein with a liquid pesticide compositions so as to obtain an emulsifiable concentrate formulation which can be directly mixed with water or other aqueous solution to give an aqueous pesticide formulation without special mixing procedures.

By "alkylaryl" is meant an aryl group substituted by one or more alkyl groups, wherein the "aryl" may be either a non-heteroaromatic ring system or heteroaromatic ring system.

The following examples illustrate further some of the aspects of the invention but are not intended to limit the its scope. Where not otherwise specified throughout this specification and claims, temperatures are given in degrees centigrade.

EXAMPLE 1 An oil-based suspension concentrate containing solid glyphosate as active ingredient was prepared according to the following formulation: 36.8% by weight solid glyphosate, b 15.0% by weight linear dodecylbenzenesulfonic acid neutralized with tallow amine (8EO), 0.1% by weight dimethyl polysiloxane as an antifoam agent by weight fumed silicate as thickener, and a petroleum hydrocarbon solvent to make up 100%.

.Z..LVX. Other glyphosate salts may also be used in the invention, such as glyphosateisopropylammonium, glyphosate-sesquisodium, or glyphosate-trimesium.

EXAMPLE 2 An aqueous suspension concentrate containing solid atrazine as active ingredient was prepared according to the following formulation: 43.5% by weight atrazine, by weight linear dodecylbenzenesulfonic acid neutralized with tallow amine (8EO), 1.15% by weight polyoxypropylene polyoxyethylene block copolymer, 0.10% by weight silicone antifoam, 0.15% by weight xanthan gum as thickener, 0.10% by weight preservative formaldehyde, and water to make up 100%.

A pregel is prepared by mixing thickener and water under high shear conditions. A slurry is prepared using the atrazine, the linear dodecylbenzenesulfonic acid neutralized with tallow amine (8EO) and water. The slurry is ground to reduce particle size of atrazine.

The pregel and remaining formulants are added and mixed until material is uniform.

EXAMPLE 3 An aqueous suspension concentrate containing solid atrazine as active ingredient was prepared in a manner analogous to that of Example 2 according to the following formulation: 43.5% by weight atrazine technical, 2.0% by weight branched dodecylbenzenesulfonic acid neutralized with coco amine 1.15% by weight polyoxypropylene polyoxyethylene block copolymer, 0.10% by weight silicone antifoam agent, 0.15% by weight xanthan gum as thickener, 0.10% by weight preservative formaldehyde, and water to make up 100%.

Viscosity of material 130cps (Viscosity by Rotational (Brookfield) viscometer, o ASTM Method D2196) EXAMPLE 4 An aqueous suspension concentrate containing solid atrazine as active ingredient was prepared in a manner analogous to that of Example 2 according to the following formulation: 43.5% by weight atrazine, by weight linear dodecylbenzenesulfonic acid neutralized with coco amine 1.15% by weight polyoxypropylene polyoxyethylene block copolymer, 0.10% by weight silicone antifoam agent, 0.15% by weight xanthan gum as thickener, 0.10% by weight preservative formaldehyde, and water to make up 100%.

Viscosity of material 125cps (Viscosity by Rotational (Brookfield) viscometer, ASTM Method D2196) EXAMPLE An aqueous suspension concentrate containing solid atrazine as active ingredient was prepared in a manner analogous to that of Example 2 according to the following formulation: 43.5% by weight atrazine technical, by weight linear dodecylbenzenesulfonic acid neutralized with tallow amine (9EO), 1.15% by weight polyoxypropylene polyoxyethylene block copolymer, 0.10% by weight silicone antifoam agent, 0.15% by weight xanthan gum as thickener, 0.10% by weight preservative such as formaldehyde and water to make up 100%.

Viscosity of material 324cps (Viscosity by Rotational (Brookfield) viscometer, ASTM Method D2196) Additionally, one or more nonionic surfactant components may be used in the crop o protection formulations. Nonionic surfactants are preferably polyglycol ether derivatives of aliphatic alcohols. The nonionic surfactants for example may be ethylenoxy/propylenoxy block polymers, castor oil ethoxylate and tristyarylphenol ethoxylate.

The crop protection compositions may be formulated in a form suitable for the intended application. Types of formulations include for example a flowable (FL) flowable concentrate for seed treatment wettable powder wettable dispersible granules (WDG), oil miscible flowable concentrate suspension concentrate emulsifiable concentrate liquid water in oil emulsions granules (GR) water dispersible powder for slurry treatment (WS) and dry flowable (DF).

Some additional preferred embodiments of the instant invention are contained in Tables 1 and 2 below.

777777777 11 a. a.

a a. a a Table 1: Crop protection formulations containing surfactant, specified nonionic components and one or more active technical components.

Aromatic Ethoxylated amine sulfonic acid o (CHCHO), -H Nonionic Active Active Active 11 R 4

-N

o11 2

C

2 component Technical Technical Techni I cal 1 4(x+y) T, T 2

T

3 1C12 0 16-18 8 Buloxy EO/PO block melolachlor' polymer 2 012 0 1214 3 Butoxy EO/PO block metolachlor* polymer 3 012 0 1618 4.5, 5, 6, 7,8, EO/PO block polymer atrazine or 9 4 012 0 16-18 4.5, 5, 6, 7, 8, nonylphenol EO/PO atrazine or 9 block polymer 5 0 12. branched 0 1214 10 1 EO/PO block polymer alrazine 6 0 12, branched 01214 15 EO/PO block polymer atrazine 7 012 0 1618 4.5, 5, 6, 7, 8, EO/PO block polymer atrazine or 9 8 012 01618 4.5, 5,6,7,8, Castor oil ethoxylale atrazine metolachlor' or 9 9 012 0 1618 4 5, 5, Buloxy EO/PO block alrazine metolachlor* or 9 polymer 10 012 01618 8 Castor oil ethoxylale Ilumetralin 11 012 0 1618 8 Castor oil ethoxylate oxasulfuron 12 012 0 1618 8 tristyrylphenol ethoxylate propiconazole 13 012 016-18 8 Butoxy EO/PO block metribuzin metolachlor* polymer 14 C12 0 1214 3 Butoxy EO/PQ block metribuzin metolachlor* polymer 012 0 16-18 8 Butoxy EO/PO block flumetsularn metolachlor' polymer 16 012 C01214 3 Butoxy EO/PO block tlumetsulam metolachlor* polymer 17 012 01618 4.5, 5, 6, 7,8, Castor oil ethoxylate flumetsulam metolachlor' atrazine or 9 4b 4 12- 0 00 18 0 12 0 16.18 4.5, 5, 6, 7, 8, Butoxy EO/PO block flumetsulamn metolachlor' atrazine or 9 polymer 19 0 12 0 16.18 8 Butoxy EO/PO block mefenoxam polymer 012 012.14 3 Butoxy EOIPO block metenoxam polymer 21 012 0 16.18 8 Butoxt/ EO/PO block metaaxy polymer 22 012 0 12.14 3 Buloxy EO/PO block metalaxy polymer 23 020.22 0 16.18 4.5, 5, 6, 7, 8, Butoxy EO/PO block diazinon or 9 polymer 24 0 12 0 16.18 4.5, 5, 6, 7, 8, Butoxy EOIPO block diazinon or 9 polymer 012 0 16.18 4.5, 5, 6, 7, 8, Butoxy EO/PO block dicamba or 9 polymer 26 012 0 16.18 4.5, 5, 6, 7, 8, Castor oil ethoxylate dicamba or 9 27 012 016.18 4.5, 5, 6, 7, 8, Buloxy EO/PO block COMPOUND or 9 polymer A 28 012 016.18 4.5, 5, 6, 7, 8, Castor oil ethoxylate COMPOUND or 9 A 29 012 0 16.18 4.5, 5, 6, 7, 8, Butoxy EO/PO block glyphosale or or 9 polymer salts 0 12 016.18 8 Butoxy EO/PO block glyphosate polymer isopropylammo niumn 31 012 0 16.18 8 Butoxy EO/PO block glyphosate polymer sesquisocliumn 32 012 0 16.18 8 Butoxy EO/PO block glyphosate polymer trimesiumn 33 012 0 16.18 4.5, 5, 6, 7, 8, Butoxy EO/PO block fluthiacetor 9 polymer or castor oil methyl ethoxylate 34 012 016.18 45, 6, 7, 8, Butoxy EO/PO block glyphosate or Iluthiacetor 9 polymer or C 13 salts methyl branched alcohol 012 0 16.18 8 Butoxy EO/PO block glyphosate fluthiacetpolymer isopropytamnmo methyl niumn 36 012 0 16-18 8 Butoxy EO/PO block glyphosate fluthiacet- Ipolymer sesquisodium methyll 016-18 Butoxy EO/PO block polymer glyphosate tluthiacettnmsu methy I -13of *to* 0 a.

6:060* 38 012 0 1618 7, 8, Buloxy EO/PO block flumicloracor 9 polymer penlyl 39 0 12 0 16 -18 4 5,5, 6. 7, 8. Butoxy EO/PO block glyphosale or Ilumicloracor 9 polymer salts pentyl 0 12 0 1618 8 Buloxy EO/PO block glypriosale Ilumicloracpolymer isopropytammo penty nlum 41 012 0 1618 8 Butoxy EO/PO block glyphosate flumicloracpolymer sesquisodium pentyt 42 012 0 1618 8 Buloxy EOIPO block glyphosate flumicloracpolymer trimesiumn pentyl 43 012 01618 4.5, 5. 6, 7. 8, Butoxy EO/PO block glufosinale or or 9 polymer sailts 44 012 0 1618 8 Butoxy EO/PO block glufosinale polymer 012 0 1618 8 Butoxy EO/PO block glulosinate polymer ammonium 46 012 01618 4.5, 5, 6, 7, 8, Butoxy EO/PO block glufosinate or fluthiacetor 9 polymer salts methyl 47 0 12 0 1618 8 Butoxy EO/PO block glufosinale fluthiacetpolymer methyl 48 012 0 1618 8 Butoxy EO/PO block glut osinate fluthiacetpolymer ammonium methyl 49 012 0 1618 4.5, 5, 6, 7, 8, Butoxy EO/PO block glufosinate or flumicloracor 9 polymer salts pentyl 012 01618 8 Butoxy EO/PO block glufosinale flumicloracpolymer pentyl 51 012 0 1618 8 Buloxy EO/PO block glufosinate flumicloracpolymer ammonium pentyi 52 012 0 1618 8 Butoxy EO/PO block glyphosate atrazine polymer 53 012 01618 8 Buloxy EO/PO block glyphosate metolachlor* atrazine polymer 54C12 0 16-18 8 Butoxy EO/PO block glyphosate salt atrazine polymer 012 0 1618 8 Butoxy EO/PO block glyphosate salt metolachtor* atrazine L polymer includes the racemic mixtures or s-metolachor R, is linear unless otherwise indicated x y =EO (average #I ethylene oxide units) -14- Table 2. Crop protection formulations: Surfactant used: (defined in terms of starting materials)

SS-OH

0

C

8 22 R. N (CHCHO), -H '(CH2CH,0), -H R4= C 7 19 x y 2E0 to 15E0 Active technical ingredients used and formulation type:

C

ACTIVE ACTIVE ACTIVE FORMULATION TECHNICAL TECHNICAL TECHNICAL TYPE At Tn FL, WPTWGO Atrazine FmeslmFL, WP, WDG, OF Atrazine lMetulao FL, OF, WDGO AtrazineFlmsu Metolachlor SC, OF, WDG Ametryn OF, EC, WP, L, WDG Oh lorothalon il FL, WDG, WP Chlorothalonil Metalaxyl EC, WDG, WP, OF Cyprodinil EC, WP, OF, WOO Cyromazine WP, L Diazinon EW, W, EC, WDG Dicamba OR, L Dicamba Prosulfuron WDG Difenoconazole WP, EC, WS, FS Difenoconazole Metalaxyl WP, EC, WS, FS Diofenolan EC, WP Fenoxycarb WP, WDG, EC Fenoxycarb Pymetrozine 1WP, WDG, EC -t 77 -77 Fludioxinil L, FS, WDG, WP Fludioxinil Metalaxyl L, FS, WOG, WP Fludioxinil Propiconazole L, FS, WOG, WP Flu metrali EC, WDG, WP Flumetralin Oxasulfuron EC, WOG, WP Flumetsula m EC, WDG, WP, OF Flumetsulam Metolachior EC, WDG, WP, OF Fluometu ron L, DF, WP Fluth iacet-m ethyl EC,WDG, WP, OF Fluthiacet-methyl Glyphosate EC,WDG, WP Fluth iacet-m ethyl Oxasulfuron EC,WDG, WPD Isazofos EC, GR Mancozeb SC, FL, WOG, WP Mancozeb Metalaxyl SC, FL, WDG, WP Mefenoxam EC, WPD, GR, FL, L Metalaxyl EC, GR, L, WP Methidlathion EC, WP Metolachlor EC, DF, GR Metolachior Metribuzin WDG, OF, EC Metolachior Simazine WOG, OF, SC s-Metolachlor EC, OF, GR s-Metolachlor Metribuzin WOG, OF, EC s-Metolachlor Simazine WDG, OF, SC Metribuzin EC, OF, WOG, OF Norflurazon OF, GR P rimisu Ifu ron WDG, WP Primisulfuron Prosulfuron WOG, WP Profenofos EC Prometon EC, FL, OF, WP Prometryn WP, L, OF Propiconazole EC, WIP Pymetrozin e WOG, WP A9c4~ 442~~2 2 -16- Simazine WP, WDG, L, GR Triforine WP, EC Trinexapac-ethyl EC, WDG, COMPOUND A WDG, OF, EC, SC COMPOUND B WDG, WP COMPOUND C WDG, WP, EC COMPOUND D EC, WP, WDG EO average number of ethylene oxide units Code Description of formulation code DF dry flowable EC emulsifiable concentrate EW water in oil emulsions FL flowable FS flowable concentrate for seed treatment GR granules L liquid OF oil miscible flowable concentrate SC suspension concentrate WDG wettable dispersible granules WP wettable powder WS water dispersible powder for slurry treatment 11

I

-17- Table 3: Compound designations The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

-o

Claims (22)

1. A salt compound of the formula A"' wherein A"n is: (SO3)p m (so (SO3)S or r (SO 3 )s wherein each R is independently selected from the group consisting of Ci-C24 alkyl and C7-C24 alkylaryl, m is a number from 0 to 5, n is a number from 1 to 3, p is a number from 0 to 3, q is a number from 0 to 3, and r is a number from 0 to 4, s is a number from 1 to 3, e wherein (H-B) is the cation of the formula: H ,(RsO)x -H R4 (R 5 O)y-H wherein R 4 is selected from the group consisting of hydrogen, C1-C24 alkyl and C2-C24 alkenyl-CH 2 each R 5 independently is a straight chain or branched C2-C4 alkylene, x is a number from 1-50 and y is a number from 0 to

2. A salt compound according to claim 1, having the formula (H-B)'A wherein A is: R2 o or o II I/i O S-O R3 0 wherein R 1 R 2 and R 3 are independently selected from the group consisting of hydrogen and C1-C24 alkyl; 11: 1 t, i -19- wherein is the cation of the formula: H (CH 2 CH20), -H NX R 4 (CH 2 CH20), -H wherein x y is a number from about 7 to 9, and R 4 is defined above

3. A salt compound according to claim 2, wherein A is an anion having the formula: R 0 Ss-o 0 wherein R, is defined above.

4. A salt compound according to claim 3, wherein R, is a n-docecyl group.

5. A salt compound according to claim 4, wherein R 4 is selected from the group consisting of n-octadecyl, n-hexadecyl and cis-9-octadecenyl; and x y is equal to 8.

6. A product obtained by the process of neutralizing at least one aromatic sulfonic acid of formulae II or Ill: (SO 3 H) p /(SO H)s (SO 3H)s "3 (II) or s (Il) wherein each R is independently selected from the group consisting of hydrogen, CI-C24 alkyl and C7-024 alkylaryl, m is a number from 0 to 5, n is a number from 1 to 3, p is a number from 0 to 3, q is a number from 0 to 3, and r is a number from 0 to 4, s is a number from 1 to 3, with at least one alkoxylated amine base of formula IV: /(R 5 0)x-H R 4 N (RO) -H S(IV) wherein R 4 is selected from the group consisting of hydrogen, C-C24 alkyl and C2-C24 alkenyl-CH 2 each R 5 independently is a straight chain or branched C2-C4 alkylene, and the average x y is a number from 2 to 50 inclusive. .7

7. A product according to claim 6, where said at least one aromatic sulfonic acid is a compound defined by formula Ila or Illa: R S OH S-OH II II 0 (lla) or R3 (llb) wherein R 1 R 2 and R 3 are independently selected from the group consisting of hydrogen and C1-C24 alkyl; and said at least one ethoxylated amine base represented by the formula V: oR (CH 2 CHO) -H R 4 N (CH 2 CH 2 0) -H wherein R 4 is C01-24 alkyl and the average x y is a number from about 7 to 9.

8. A product according to claim 6, wherein the product surfactant has a pH of 3 to 7.

9. A product according to claim 6, wherein the product surfactant has a pH of 4 to 6. A product according to claim 6, wherein the product surfactant has a pH of 5 to 6.

11. A surfactant composition comprising a salt of: at least one aromatic sulfonic acid compound represented by the formulae II or III: so"3R) (SO3H)s()1 (SO3H)s (SO 3 H)s (II) or r (Il) wherein each R is independently selected from the group consisting of C1-C24 alkyl and C7-C24 alkylaryl, m is a number from 0 to 5, n is a number from 1 to 3, p is a number from 0 to 3, q is a number from 0 to 3, and r is a number from 0 to 4, s is a number from 1 to 3, and at least one alkoxylated amine base represented by the formula IV: ii ri -21 /(RO)x-H R 4 N (R O)y H (IV) wherein R 4 is selected from the group consisting of hydrogen, Ci-C 24 alkyl and C2-C24 alkenyl-CH 2 each R 5 independently is a straight or branched chain C2-C. alkylene, and the average x y is a number from 2 to 50 inclusive.

12. A surfactant composition according to claim 11 wherein: is at least one aromatic sulfonic acid compound represented by the formulae Ila or Illa: R O S-OH S II 0 R2 RS- OH R3 0 (lla) or (Ilia) wherein Ri, R 2 and R 3 are independently selected from the group consisting of hydrogen and Ci-C24 alkyl; and is at least one ethoxylated amine base represented by the formula V: (CH 2 CH 2 -H R 4 N (CH 2 CH 2 0) -H (V) wherein R 4 is C1-024 alkyl and x y is a number from about 7 to 9.

13. A composition of claim 11, wherein the product surfactant has a pH of 3 to 7.

14. A composition of claim 11, wherein the product surfactant has a pH of 4 to 6. A composition of claim 11, wherein the product surfactant has a pH of 5 to 6.

16. A chemically integrated surfactant composition comprising at least one aromatic sulfonic acid compound represented by formula II or III: Lln. i J31~ -r rY~*, -22 i (SO 3 H)p 3H (SO 3 H)s (SO 3 H) or r (III) wherein each R is independently selected from the group consisting of C1-C24 alkyl and C7-024 alkylaryl, m is a number from 0 to 5, n is a number from 1 to 3, p is a number from 0 to 3, q is a number from 0 to 3, and r is a number from 0 to 4, s is a number from 1 to 3, and at least one alkoxylated amine base represented by the formula IV: (RsO)x-H R 4 N (RsO)y-- H (IV) S* wherein R 4 is selected from the group consisting of hydrogen, C1-C24 alkyl and C2-C24 alkenyl-CH 2 each R 5 independently is a straight or branched chain C2-04 alkylene, and the average x y is a number from 2 to 50 inclusive, or the chemical interaction products thereof.

17. A chemically integrated surfactant composition according to claim 16 where the aromatic sulfonic acid compound is defined by the formula Ila or Ilia: R2 0 ni OH II S-OH S-OH O R3 S(II) or R3 0 (III) wherein R 2 and R 3 are independently selected from the group consisting of hydrogen and C1-C24 alkyl; and at least one ethoxylated amine base represented by the formula V: R4N (CH 2 CH 2 -H (CH 2 CH20), -H (V) wherein R 4 is C1-C24 alkyl and x y is a number from about 7 to 9.

18. A composition of claim 16, wherein the product surfactant has a pH of 3 to 7. -23

19. A composition of claim 16, wherein the product surfactant has a pH of 4 to 6. A eomposition of claim 16, wherein the product surfactant has a pH of 5 to 6.

21. A pesticide formulation comprising at least one pesticide and at least one aromatic sulfonic acid neutralized with at least one ethoxylated amine wherein said aromatic sulfonic acid is represented by the formulae (II) or (III): (SO 3 H) p (R)m (SO 3 H)s r (SO 3 H)s o wherein each R is independently selected from the group consisting of C 1 -C 24 alkyl and C7-024 alkylaryl, m is a number from 0 to 5, n is a number from 1 to 3, p is a number from 0 to 3, q is a number from 0 to 3, and r is a number from 0 to 4, s is a number from 1 to 3, and the said alkoxylated amine is represented by the formula IV: /(R 5 0)x-H R 4 N (R O) H y (IV) wherein R 4 is selected from the group consisting of hydrogen, C-C24 alkyl and C2-C24 alkenyl-CH 2 each Rs independently is a straight or branched chain C2-C4 alkylene, and the average x y is a number from 2 to 50 inclusive.

22. A pesticide formulation according to claim 21 wherein said aromatic sulfonic acid is represented by the formulae Ila or Illa: S R2 R0 0 O S-OH S-OH II II or R3 O (II) or R3 0 (III) wherein R 1 R 2 and R 3 are independently selected from the group consisting of hydrogen and CI-C24 alkyl; and the said ethoxylated amine is represented by the formula V: 4.Zi .XZ 24> 2.4< 1 -24- -H R 4 N (CH 2 CH 2 H wherein R 4 is alkyl and x y is a number from about 7 to 9.

23. A pesticide formulation of claim 21 wherein the at least one pesticide is selected from the group consisting of mefenoxam, s-metolachlor, flumetsulam, fluthiacet-methyl, atrazine and glyphosate.

24. A method of protecting crops comprising the step of applying to the locus of the crops in need of protection an agriculturally effective amount of the formulation of claim 21. A method of protecting crops comprising the step of applying to the locus of the crops in need of protection an agriculturally effective amount of the formulation of claim 22.

26. A method of using the salt compounds of claim 1 as an APE substitute which comprises substituting an APE surfactant system in a formulation with the salt compounds having the formula A n DATED this 11th day of February, 2002 Syngenta Participations AG By DAVIES COLLISON CAVE Patent Attorneys for the Applicants li .L 4*.4