Abstract:
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.

Description:
[0001]    “This is a continuation of International Application No. PCT/EP99/05628, filed Mar. 8, 199, the contents of which are incorporated herein by reference” 
         FIELD OF THE INVENTION  
         [0002]    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  
         [0003]    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 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 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 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  
         [0004]    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 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  
       [0005]    One aspect of the invention is the salt compound of formula (I):  
         [(H—B + ] n A n−   (1)  
         [0006]    wherein A n−  is the conjugate base 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 (I). The invention also includes a pesticide formulation comprising at least one pesticide and a salt compound of formula (I).  
         [0007]    A preferred aspect of the invention is the salt compound having the formula [(H—B) + ] n  A n−  wherein A n−  is the anion of the formula:  
                         
 
         [0008]    wherein each R is independently selected from the group consisting of C 1 -C 24  alkyl, and C 7 -C 24  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 (H—B) +  is the cation of the formula:  
                         
 
         [0009]    wherein R 4  is selected from the group consisting of hydrogen, C 1 -C 24  alkyl and C 2 -C 24  alkenyl-CH 2 -, each R 5  independently is straight or branched chain C 2 -C 4  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 50 inclusive. A more preferred embodiment of the salt compound of formula (H—B) + A −  wherein A −  is the anion of the formula:  
                         
 
         [0010]    wherein R 1 , R 2 , and R 3  are independently selected from the group consisting of hydrogen and C 1 -C 24  alkyl and (H—B) +  is the cation of the formula:  
                         
 
         [0011]    wherein R 4  is defined above (preferably n-octadecyl, n-hexadecyl and cis-9-octadecenyl); and x+y is a number from about 7 to 9 (preferably 8). Another more preferred embodiment of the invention is the salt compound wherein A is an anion having the formula:  
                         
 
         [0012]    wherein R 1  is n-docecyl group.  
         [0013]    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 complexation, equilibration, reaction or acid-base chemistry of the components used to make the surfactants or other ingredients used to make other ultimately useful formulations (e.g. 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 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 between 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.  
         [0014]    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.  
         [0015]    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 invention. The invention also includes the method of using the surfactant salt compounds of formula (I) and compositions thereof as APE substitutes.  
         [0016]    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 cost-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.  
         [0017]    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:  
                         
 
         [0018]    wherein each R, m, n, p, q, r and s are defined as above.  
         [0019]    The preferred starting materials for making the surfactants of the instant invention are the compounds defined by formula IIa or IIIa:  
                         
 
         [0020]    wherein R 1 , R 2 , and R 3  are defined as above.  
         [0021]    The preferred alkoxylated amines useful for making the surfactants of the instant invention are one or more of the compounds defined by formula IV:  
                         
 
         [0022]    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:  
                         
 
         [0023]    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-9-octadecenyl, 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).  
         [0024]    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 substitutes, and therefore would be expected to be useful in many other known 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.  
         [0025]    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.  
         [0026]    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 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 pK a  and pK b  for the aromatic sulfonic acid and the alkoxylated amine 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 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.  
         [0027]    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 (i.e. 8 EO). “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 8 EO. It is also desirable that there be low dispersion preferably within one standard deviation (σ) of the mean (average EO). A decrease in emulsification ability is observed when either 7 EO or 9 EO tallow amine was used to make the surfactant.  
         [0028]    Some commercial suppliers and product names for the ethoxylated amines (i.e. amine ethoxylates) are:  
                                                                                                
 
         [0029]    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.  
         [0030]    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.  
         [0031]    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  
       [0032]    An oil-based suspension concentrate containing solid glyphosate as active ingredient was prepared according to the following formulation:  
         [0033]    36.8% by weight solid glyphosate,  
         [0034]    15.0% by weight linear dodecylbenzenesulfonic acid neutralized with tallow amine (8 EO),  
         [0035]    0.1% by weight dimethyl polysiloxane as an antifoam agent  
         [0036]    1.0% by weight fumed silicate as thickener, and a petroleum hydrocarbon solvent to make up 100%.  
         [0037]    Other glyphosate salts may also be used in the invention, such as glyphosate-isopropylammonium, glyphosate-sesquisodium, or glyphosate-trimesium.  
       EXAMPLE 2  
       [0038]    An aqueous suspension concentrate containing solid atrazine as active ingredient was prepared according to the following formulation:  
         [0039]    43.5% by weight atrazine,  
         [0040]    2.0% by weight linear dodecylbenzenesulfonic acid neutralized with tallow amine (8 EO),  
         [0041]    1.15% by weight polyoxypropylene polyoxyethylene block copolymer,  
         [0042]    0.10% by weight silicone antifoam,  
         [0043]    0.15% by weight xanthan gum as thickener,  
         [0044]    0.10% by weight preservative formaldehyde, and water to make up 100%.  
         [0045]    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 (8 EO) 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  
       [0046]    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:  
         [0047]    43.5% by weight atrazine technical,  
         [0048]    2.0% by weight branched dodecylbenzenesulfonic acid neutralized with coco amine (10 EO),  
         [0049]    1.15% by weight polyoxypropylene polyoxyethylene block copolymer,  
         [0050]    0.10% by weight silicone antifoam agent,  
         [0051]    0.15% by weight xanthan gum as thickener,  
         [0052]    0.10% by weight preservative formaldehyde, and water to make up 100%.  
         [0053]    Viscosity of material=130 cps (Viscosity by Rotational (Brookfield) viscometer, ASTM Method D2196)  
       EXAMPLE 4  
       [0054]    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:  
         [0055]    43.5% by weight atrazine,  
         [0056]    2.0% by weight linear dodecylbenzenesulfonic acid neutralized with coco amine (15 EO),  
         [0057]    1.15% by weight polyoxypropylene polyoxyethylene block copolymer,  
         [0058]    0.10% by weight silicone antifoam agent,  
         [0059]    0.15% by weight xanthan gum as thickener,  
         [0060]    0.10% by weight preservative formaldehyde, and water to make up 100%.  
         [0061]    Viscosity of material=125 cps (Viscosity by Rotational (Brookfield) viscometer, ASTM Method D2196)  
       EXAMPLE 5  
       [0062]    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:  
         [0063]    43.5% by weight atrazine technical,  
         [0064]    2.0% by weight linear dodecylbenzenesulfonic acid neutralized with tallow amine (9 EO),  
         [0065]    1.15% by weight polyoxypropylene polyoxyethylene block copolymer,  
         [0066]    0.10% by weight silicone antifoam agent,  
         [0067]    0.15% by weight xanthan gum as thickener,  
         [0068]    0.10% by weight preservative such as formaldehyde and water to make up 100%.  
         [0069]    Viscosity of material=324 cps (Viscosity by Rotational (Brookfield) viscometer, ASTM Method D2196)  
         [0070]    Additionally, one or more nonionic surfactant components may be used in the crop 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.  
         [0071]    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 (FS), wettable powder (WP), wettable dispersible granules (WDG), oil miscible flowable concentrate (OF), suspension concentrate (SC), emulsifiable concentrate (EC), liquid (L), water in oil emulsions (EW), granules (GR) water dispersible powder for slurry treatment (WS) and dry flowable (DF).  
         [0072]    Some additional preferred embodiments of the instant invention are contained in Tables 1 and 2 below.  
                                                                               TABLE 1                           Crop protection formulations containing surfactant, specified nonionic       components and one or more active technical components.                                                                                                            Nonionic component   Active Technical T 1     Active Technical T 2     Active Technical T 3                           1   C 12     C 16-18     8   Butoxy EO/PO block   metolachlor*                               polymer        2   C 12     C 12-14     3   Butoxy EO/PO block   metolachlor*                       polymer        3   C 12     C 16-18     4.5, 5, 6, 7, 8,   EO/PO block polymer   atrazine                   or 9        4   C 12     C 16-18     4.5, 5, 6, 7, 8,   nonylphenol EO/PO   atrazine                   or 9   block polymer        5   C 12,branched     C 12-14     10    EO/PO block polymer   atrazine        6   C 12,branched     C 12-14     15    EO/PO block polymer   atrazine        7   C 12     C 16-18     4.5, 5, 6, 7, 8,   EO/PO block polymer   atrazine                   or 9        8   C 12     C 16-18     4.5, 5, 6, 7, 8,   Castor oil ethoxylate   atrazine   metolachlor                   or 9           *        9   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   atrazine   metolachlor                   or 9   polymer       *       10   C 12     C 16-18     8   Castor oil ethoxylate   flumetralin       11   C 12     C 16-18     8   Castor oil ethoxylate   oxasulfuron       12   C 12     C 16-18     8   tristyrylphenol   propiconazole                       ethoxylate       13   C 12     C 16-18     8   Butoxy EO/PO block   metribuzin   metolachlor                       polymer       *       14   C 12     C 12-14     3   Butoxy EO/PO block   metribuzin   metolachior                       polymer       *       15   C 12     C 16-18     8   Butoxy EO/PO block   flumetsulam   metolachlor                       polymer       *       16   C 12     C 12-14     3   Butoxy EO/PO block   flumetsulam   metolachlor                       polymer       *       17   C 12     C 16-18     4.5, 5, 6, 7, 8,   Castor oil ethoxylate   flumetsulam   metolachlor   atrazine                   or 9           *       18   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   flumetsulam   metolachlor   atrazine                   or 9   polymer       *       19   C 12     C 16-18     8   Butoxy EO/PO block   mefenoxam                       polymer       20   C 12     C 12-14     3   Butoxy EO/PO block   mefenoxam                       polymer       21   C 12     C 16-18     8   Butoxy EO/PO block   metalaxyl                       polymer       22   C 12     C 12-14     3   Butoxy EO/PO block   metalaxyl                       polymer       23   C 20-22     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   diazinon                   or 9   polymer       24   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   diazinon                   or 9   polymer       25   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   dicamba                   or 9   polymer       26   C 12     C 16-18     4.5, 5, 6, 7, 8,   Castor oil ethoxylate   dicamba                   or 9       27   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   COMPOUND                   or 9   polymer   A       28   C 12     C 16-18     4.5, 5, 6, 7, 8,   Castor oil ethoxylate   COMPOUND                   or 9       A       29   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   glyphosate or                   or 9   polymer   salts       30   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate                       polymer   isopropylamm                           onium       31   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate                       polymer   sesquisodium       32   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate                       polymer   trimesium       33   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   fluthiacet-                   or 9   polymer or castor oil   methyl                       ethoxylate       34   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   glyphosate or   fluthiacet-                   or 9   polymer or C13   salts   methyl                       branched alcohol       35   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   fluthiacet-                       polymer   isopropylamm   methyl                           onium       36   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   fluthiacet-                       polymer   sesquisodium   methyl       37   C 12     C 16-18     8   Butoxy EC/PO block   glyphosate   fluthiacet-                       polymer   trimesium   methyl       38   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   flumiclorac-                   or 9   polymer   pentyl       39   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   glyphosate or   flumiclorac-                   or 9   polymer   salts   pentyl       40   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   flumiclorac-                       polymer   isopropylamm   pentyl                           onium       41   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   flumiclorac-                       polymer   sesquisodium   pentyl       42   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   flumiclorac-                       polymer   trimesium   pentyl       43   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   glufosinate or                   or 9   polymer   salts       44   C 12     C 16-18     8   Butoxy EO/PO block   glufosinate                       polymer       45   C 12     C 16-18     8   Butoxy EO/PO block   glufosinate                       polymer   ammonium       46   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   glufosinate or   fluthiacet-                   or 9   polymer   salts   methyl       47   C 12     C 16-18     8   Butoxy EO/PO block   glufosinate   fluthiacet-                       polymer       methyl       48   C 12     C 16-18     8   Butoxy EO/PO block   glufosinate   fluthiacet-                       polymer   ammonium   methyl       49   C 12     C 16-18     4.5, 5, 6, 7, 8,   Butoxy EO/PO block   glufosinate or   flumiclorac-                   or 9   polymer   salts   pentyl       50   C 12     C 16-18     8   Butoxy EO/PO block   glufosinate   flumiclorac-                       polymer       pentyl       51   C 12     C 16-18     8   Butoxy EO/PO block   glufosinate   flumiclorac-                       polymer   ammonium   pentyl       52   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   atrazine                       polymer       53   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   metolachlor   atrazine                       polymer       *       54   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   atrazine                       polymer   salt       55   C 12     C 16-18     8   Butoxy EO/PO block   glyphosate   metolachlor   atrazine                       polymer   salt   *                                          
 
         [0073]    [0073]                                                 TABLE 2                       Crop protection formulations:                   Surfactant used: (defined in terms of starting materials)                                                         Active technical ingredients used and formulation type:            ACTIVE   ACTIVE   ACTIVE           TECHNICAL   TECHNICAL   TECHNICAL   FORMULATION       T 1     T 2     T 3     TYPE               Atrazine           FL, WP, WDG, OF       Atrazine   Flumetsulam       FL, WP, WDG, OF       Atrazine   Metolachlor       SC, OF, WDG       Atrazine   Flumetsulam   Metolachlor   SC, OF, WDG       Ametryn           OF, EC, WP, L, WDG       Chlorothalonil           FL, WDG, WP       Chlorothalonil   Metalaxyl       EC, WDG, WP, OF       Cyprodinil           EC, WP, OF, WDG       Cyromazine           WP, L       Diazinon           EW, W, EC, WDG       Dicamba           GR, L       Dicamba   Prosulfuron       WDG       Difenoconazole           WP, EC, WS, FS       Difenoconazole   Metalaxyl       WP, EC, WS, FS       Diofenolan           EC, WP       Fenoxycarb           WP, WDG, EC       Fenoxycarb   Pymetrozine       WP, WDG, EC       Fludioxinil           L, FS, WDG, WP       Fludioxinil   Metalaxyl       L, FS, WDG, WP       Fludioxinil   Propiconazole       L, FS, WDG, WP       Flumetralin           EC, WDG, WP       Flumetralin   Oxasulfuron       EC, WDG, WP       Flumetsulam           EC, WDG, WP, OF       Flumetsulam   Metolachlor       EC, WDG, WP, OF       Fluometuron           L, DF, WP       Fluthiacet-           EC, WDG, WP, OF       methyl       Fluthiacet-   Glyphosate       EC, WDG, WP       methyl       Fluthiacet-   Oxasulfuron       EC, WDG, WP       methyl       Isazofos           EC, GR       Mancozeb           SC, FL, WDG, WP       Mancozeb   Metalaxyl       SC, FL, WDG, WP       Mefenoxam           EC, WP, GR, FL, L       Metalaxyl           EC, GR, L, WP       Methidathion           EC, WP       Metolachlor           EC, DF, GR       Metolachlor   Metribuzin       WDG, OF, EC       Metolachlor   Simazine       WDG, OF, SC       s-Metolachlor           EC, DF, GR       s-Metolachlor   Metribuzin       WDG, OF, EC       s-Metolachlor   Simazine       WDG, OF, SC       Metribuzin           EC, DF, WDG, OF       Norflurazon           DF, GR       Primisulfuron           WDG, WP       Primisulfuron   Prosulfuron       WDG, WP       Profenofos           EC       Prometon           EC, FL, OF, WP       Prometryn           WP, L, OF       Propiconazole           EC, WP       Pymetrozine           WDG, WP       Simazine           WP, WDG, L, GR       Triforine           WP, EC       Trinexapac-           EC, WDG,       ethyl       COMPOUND           WDG, OF, EC, SC       A       COMPOUND           WDG, WP       B       COMPOUND           WDG, WP, EC       C       COMPOUND           EC, WP, WDG       D                    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            
         [0074]    [0074]                         TABLE 3                           Compound designations            CGA Number   Structure                           COMPOUND A                                             COMPOUND B                                             COMPOUND C                                             COMPOUND D