Abstract:
The present invention generally relates to a method for minimizing the formation of insoluble salts of phenoxy herbicides. The method comprises (1) mixing a compatibility agent, amine salts of phenoxy acid herbicides, and a chemical containing non-amine cations in a aqueous system to form a stable and non-nozzle plugging solution; and (2) application of said stable and non-nozzle plugging solution onto target plants.

Description:
FIELD OF THE INVENTION 
       [0001]    The present invention generally relates to a method for minimizing the formation of insoluble salts of phenoxy herbicides. The method comprises (1) mixing a compatibility agent, amine salts of phenoxy acid herbicides, and a chemical containing non-amine cations in an aqueous system to form a stable and non-nozzle plugging solution; and (2) the method of applying the stable and non-nozzle plugging solution onto a plant. 
       BACKGROUND OF THE INVENTION 
       [0002]    Phenoxy herbicides, especially 2,4-D, is well known in the art as an effective herbicide for the control broad leaf weeds. From this point on, we will use 2,4-D as the example but those skilled in the an should realize that although 2,4-D is mentioned it should be understood that it also applies generally to the entire phenoxy herbicide family. 
         [0003]    It is a common practice for farmers to add 2,4-D amine herbicide to a concentrated liquid fertilizer (such a 28% N) and to spray it without further dilution with water. 2,4-D amine herbicide is also widely used together with other herbicides and diluted fertilizers such as ammonium sulfate (AMS) to enhance the bioefficacy and to achieve a broader weed control spectrum. However, 2,4-D acid and its non-amine salts have very low solubility in water. Because of this, the most commonly used 2,4-D herbicide is 2,4-D amine salts. Although hydrophobic 2,4-D esters are available, 2,4-D formulated and applied as a water-soluble salt has the added advantages of not requiring an emulsifier and/or an organic solvent. 
         [0004]    It is a common practice for farmers to mix various products in a spray tank for convenience and economy reasons. For example, farmers may mix together a 2,4-D product and a fertilizer product. However, when a 2,4-D amine product is mixed with another product that contains non-amine cations, such as ammonium, sodium, potassium, and multivalent ions, a precipitate can form in the spray tank resulting in the blockage of the spray nozzle. Even if farmers intentionally try to avoid mixing 2,4-D with incompatible components, it may not be possible to avoid having both 2,4-D anion and non-amine cations in the same spray tank because ammonium, K, Na, Ca, and Mg may come from, for example, fertilizers, other herbicide formulations, micronutrients, or hard water, thereby causing unwanted precipitate. Farmers have been trying to solve this precipitate problem by adding traditional compatibility agents or hydrotropes such as phosphate esters, glycols, or alcohol without satisfactory result. 
         [0005]    Accordingly, it is desirable to develop a method for minimizing the formation of nozzle plugging precipitate in a vessel containing a 2,4-D herbicide and non-amine cations. 
         [0006]    It is, therefore, an objective of the present invention to provide a method for minimizing the formation of nozzle plugging precipitate in a vessel containing a 2,4-D herbicide and non-amine cations by using a suitable compatibility agent. It is a further and preferred objective to provide a method of using a surfactant which not only functions as a compatibility agent for precipitation crystal-free spray application but also as an adjuvant for improved efficacy. 
       SUMMARY OF THE INVENTION 
       [0007]    The present invention relates to herbicide formulations free from nozzle plugging particles comprising 2,4-D anion and a compatibility agent in the presence of non-anine cations and a method to minimize the formation of nozzle plugging particles in such a system. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0008]    Some chemicals have been found to apparently improve the solubility of another in water. Such a chemical is sometimes called a hydrotrope and it is defined as the ability of some agents to increase the solvent power of water towards other molecules. The phenomenon refers mainly to the increased solubility of ethoxylated products in water due to the addition of a hydrotrope. The other phenomenon of hydrotropy, commonly employed in shampoo and cleaner formulations, refers to the reduced viscosity of the product by using hydrotropes to prevent a liquid crystalline formation in the micellar system. This effect of hydrotropy differs from the solubilization properties of surfactants which results in a third hydrophobic material being enclosed in a microstructure such as micelle or microemulsion, the whole thing being dispersed in water. The chemical which increases the solubility of a hydrophobic material is called a solubilizer or coupling agent and it is generally referred to as a surfactant. 
         [0009]    Many chemicals have been called fertilizer compatibility agents. Examples of common fertilizer compatibility agents include phosphate esters, alkylpolyglycosides, nonionic nonylphenol ethoxylates, and the like. Specifically, they prevent the diluted pesticide emulsion from separating out in the presence of fertilizer and another herbicide. 
         [0010]    It is an objective of the present invention to increase the aqueous solubility of non-amine salts of phenoxy acid herbicides. Examples of phenoxy acid herbicides referred to in the present invention include, but are not limited to the following.
       phenoxyacetic herbicides   4-CPA   2,4-D   3,4-DA   MCPA   MCPA-thioethyl   phenoxybutyric herbicides   4-CPB   2,4-DB   3,4-DB   MCPB   phenoxypropionic herbicides   cloprop   4-CPP   dichlorprop
           dichlorprop-P   
           3,4-DP   fenoprop   mecoprop
           mecoprop-P   
           aryloxyphenoxypropionic herbicides   chlorazifop   clodinafop   clofop   cyhalofop   diclofop   fenoxaprop
           fenoxaprop-P   
           fenthiaprop   fluazifop
           fluazifop-P   
           haloxyfop
           haloxyfop-P   
           isoxapyrifop   metamifop   propaquizafop   quizalofop
           quizalofop-P   
           trifop
 
Although it is believed that the present invention is useful for all of the phenoxy herbicides known to the skilled artisan, including those mentioned above, the present inventors will focus this description on 2,4 D acid and its salts because it is by far the phenoxy herbicide having the widest application and use.
       
 
         [0050]    Increasing the solubility of the 2,4-D non-amine salts differs from increasing the solubility of an ethoxylated product through a hydrotropy effect. It also differs from increasing the solubility of an oily product through a solubilization effect. The reason is that a 2,4-D non-amine salt is a salt and is neither an ethoxylated chemical nor an oily, hydrophobic chemical. Additionally, because of its nature, it is not possible to predict which chemical would be useful for increasing the solubility of 2,4-D non-amine salts based on conventional knowledge. In fact, some of the observations made by the present inventors were totally against conventional wisdom. More specifically, the present inventors found that the so called well known “hydrotropes” and “compatibility agents”, which may be good for other applications, were not suitable for increasing the solubility of 2,4-D non-amino salt. In this regard, phosphate esters, short chain alkyl glycosides, glycols, nonylphenol ethoxylate, isopropyl alcohol, octanol, sodium xylene sulfonate, ethoxylated (2EO) cocoamide oxides, sodium dioctyl sulfosuccinate, butyl cellosolve acetate, amphoteric surfactants, and methyl 2-pyrrolidinone were found to be ineffective. 
         [0051]    In accordance with the present invention it is highly desirable to increase the compatibility between a 2,4-D product and another product containing non-amine cations such as co-herbicides, fertilizers, micronutrients, hard water and the like. In this respect, it has been found that only certain chemicals were effective as the compatibility agents to minimize a precipitate formation in the spray tank when a 2,4-D product is mixed with a non-amine cation containing product. The non-limiting examples of such chemicals are: quaternary amines, alkoxylated (quaternary) amines, amidoamines, ethoxylated esteramines, alkyl alcohol alkoxylates, ethoxylated sorbitans and sorbitol esters, tristyrylphenol ethoxylates, EO-PO block and random copolymers, alkyl olefin sulfonates, carboxylated nonionic alcohols, alkylamide ethoxylates, alkylethersulfate amine salts, sodium alkylnaphthalene sulfonates (formaldehyde polymer) and combinations thereof. 
         [0052]    The alkoxylated quaternary surfactants usefully employed in the context of the present invention can be represented by the following general formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein R1 is a straight or branched chain, saturated or unsaturated alkyl group having from 8 to 22 carbon atoms; R2 is a straight or branched chain, saturated or unsaturated alkyl group having from 1 to 4 carbon atoms; and A is C i H 2i  where i is 2 to 4; B is C j H 2j  where j is 2 to 6; and X −  is a compatible anion such as methyl sulfate or chloride, f is zero to 10; m and n is an integer of from 1-30 with the proviso that m+n is at least 2, p is 1 to 7 and g can be any number from zero to 6 for each p and independent of p, and q is 1 to 7 with a provision that p may be greater than q. In one embodiment, the A is C 2 H 4 , f=0, and g=0. In another embodiment, the A is C 2 H 4 , f=0, g 0, m+n is 2 to 20, R2 is methyl group, p=1, and X is chloride. 
         [0053]    The alkyl quaternary surfactants useful in the invention are represented by the formula: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein R1 is a straight or branched chain, saturated or unsaturated alkyl group having from 8 to 22 carbon atoms. R2, R3, and R4 is independently a straight or branched chain, saturated or unsaturated alkyl group having from 1 to 4 carbon atoms. A is C i H 2i  where i is 2 to 4; B is C j H 2j  where j is 2 to 6; and X −  is a compatible anion such as methyl sulfate or chloride. f is zero to 10; p is 1 to 7 and g can be any number from zero to 6 for each p and independent of p, and q is 1 to 7 with a provision that p may be greater than q. In one embodiment, the A is C 2 H 4 , f=0, and g=0. In another embodiment, the A is C 2 H 4 , f=0, g=0, R2 is methyl group, R3 is a methyl group, R4 is a methyl group, p=1, and X is chloride. 
         [0054]    The following alkoxylated amines are useful: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein R1 is a straight or branched chain, saturated or unsaturated alkyl group having from 8 to 22 carbon atoms; A is C i H 2i  where i is 2 to 4; and B is C j H 2j  where j is 2 to 6. f is zero to 10; m and n is an integer of from 0-30 with the proviso that m+n is at least 1, p is 1 to 7 and g can be any number from zero to 6 for each p and independent of p. In one embodiment, A is C 2 H 4 , f=0, and g=0. In another embodiment, the A is C 2 H 4 , f=0, g=0, m+n is 1 to 20, p=1. 
         [0055]    The following alkoxylated amidoamines are useful: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein R1 is a straight or branched chain, saturated or unsaturated alkyl group having from 7 to 21 carbon atoms; A is C i H 2i  where i is 2 to 4; m is 1 to 30, and n is 1 to 30. The particularly useful R1 is from tall oil, coconut oil, soya oil, corn, or tallow. 
         [0056]    The following amidoamines are useful: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    where R1 a straight or branched chain, saturated or unsaturated alkyl group having from 7 to 21 carbon atoms. 
         [0057]    The reaction products of fatty acid with polyamines followed by alkoxylation, alkoxylated amido polyamines, are useful. Example of a preferred reaction product has the following structure, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    wherein R1 is a straight or branched chain, saturated or unsaturated alkyl group having from 7 to 21 carbon atoms; A is C i H 2i  where i is 2 to 4; n, m, p, and q all is 1 to 20 independently; x and y is 0 to 5 independently with a provision of x+y greater than or equal to 1. The particularly useful R1 is from tall oil, coconut oil, soya oil, corn, or tallow. 
         [0058]    The reaction products of fatty acid and triethanolamine and its alkoxylated products are useful. The preferred species is the monoester which can be represented by the following structure, 
         [0000]    
       
                 
         
             
             
         
       
     
         [0059]    wherein R1 is a straight or branched chain, saturated or unsaturated alkylene group having from 8 to 22 carbon atoms; A is C i H 2i  where i is 2 to 4; m is 1 to 30, and n is 1 to 30. 
         [0060]    The following alkyl alcohol alkoxylates are useful, 
         [0000]      R1OA) V H  VIII 
         [0000]    wherein R1 is a straight or branched chain, saturated or unsaturated alkyl group having from 6 to 14 carbon atoms; A is C i H 2i  where i is 2 to 4; and v is 2 to 10 when R1 is linear and 9-20 when R1 is branched. 
         [0061]    The following polyethylene sorbitans are useful: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    where R is C8 to C22, n+m+w is about 10 to 30, preferably 20. 
         [0062]    The tristyrylphenol ethoxylate with 8-30 moles of ethylene oxide and its phosphate or salts thereof are useful. 
         [0063]    The following EO/PO block and random copolymers are useful, 
         [0000]      R1OA′) x H  X 
         [0064]    wherein R1 is H, or C4 to C10 linear or branched alkyl, A′ is C2 or C3, x is 30 to 300, EO:PO&gt;40:60 (weight ratio). When R1=H, they are preferably EO-PO-EO copolymer with a molecular weight &gt;˜4000. When R1 is C4 to C10, their molecular weight is preferably &gt;˜1500. 
         [0065]    The alkyl olefin sulfonate useful in the claimed invention includes alkyl chain length between C8 and C18 and preferably C8-12 olefin sulfonate and salts thereof. 
         [0066]    The carboxylated alkylphenol ethoxylate is useful. Preferably it is a carboxylated octylphenol or nonylphenol with 5 to 15 EO. A non-limiting example is the reaction product of nonylphenol ethoxylate (9EO) and sodium monochloroacetate. 
         [0067]    Castor oil EO-PO alkoxylate (total 25 to 50 EO+PO units) can also be usefully employed in the context of the present invention . 
         [0068]    C8-16 linear or branched alkyl polyglycoside with 1-5, preferably 1-2, glucose units are also useful. 
         [0069]    Alkylethersulfate amine salts are useful, and the alkyl chain length is preferably C6 to C12 with 1 to 5 EO groups. The preferred amine is dimethylamidopropylamine (DMAPA), triethanol amine (TEA), diethanolamine (DEA), monoethanolamine (MEA), butylamine, cocoamine, diethylene triamine (DETA), and isopropylamine. 
         [0070]    The useful alkylnaphthalene sulfonate (formaldehyde polymer) salt has an alkyl group C8-C18 and the C8-C12 sodium salt is preferred. 
         [0071]    Polyethylene sorbitol tallate of the following formula are also useful: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    where R is H or a group with the structure: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    here R1 is a straight or branched chain, saturated or unsaturated alkyl group having from 7 to 21 carbon atoms; n, m, p, q, x and y is 0 to 20 independently with a provision of n+m+p+q+x+y greater than or equal to 6. 
         [0072]    The short amines with the following structure are also useful but they are not the preferred because they are not surfactants and they do not provide other benefits to the herbicides. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0073]    Where R1, R2, R3, R4, R5 and R6 are each independently a straight or branched alkenyl group with 1 to 6 carbon atoms; a, b, c, d, e, f, and g are each independently a number from 0 to 40; p is 1-7 independent of a, b, c, d, e, f, and g. 
         [0074]    Inorganic bases, such as hydroxides of sodium, potassium, and ammonium can also be used but they are not the preferred because they are not surfactants and they do not provide other benefits to the herbicides. It should also be noted that if glyphosate is present in the herbicidal formulations, the inorganic base is excluded. 
         [0075]    As is well known to those skilled in the art, efficacy of many herbicides including 2,4-D is strongly related to the system pH. Typically low pH favors good efficacy. Therefore, it shall be pointed out that using inorganic hydroxides or the short amines, depending on the degree of substitution or its equivalent to minimize the 2,4-D precipitate formation, the system pH could be raised to a value too high to give satisfactory efficacy. 
         [0076]    Specific examples of compatibility agents employable in the context of the present invention include, but are not limited to cocoamine-2EO oxide, sodium lauryl sulfate, ethoxylated (6EO), caprylic &amp; capric glycerol ester, C8-10 glycosides, 2-ethylhexyl glycoside, C9-C11 glycoside, iso C13+4EO phosphate ester (acid), propyl glycosides, isopropyl alcohol, C8-10+4 EO phosphate ester (acid), alkyl ether citrate, sodium xylene sulfonate, phenol ethoxylate 2-propylheptanol-5EO, sodium dodecylbenzene sulfonate, to butyl cellosolve acetate (C4-O—C—C—OOCC), hexylglycosides, 2-ethylhexanol+35PO+32EO, Na cocoamphocarboxy glycinate, oleylamphopolycarboxyglycinate, EO-PO-EO Block copolymer (40% EO) MW 2900, castor oil ethoxylate-20EO, octyliminodipropionate, EO-PO-EO block copolymer MW 3200, triethyl ammonium phosphate, EO-PO-EO block copolymer (30% EO) MW 1850, EO-PO-EO Block is copolymer (50% EO) MW 1900, methyl-2-pyrrolidinone, EO-PO-EO Block copolymer (40% EO) MW 2200, nonylphenol-12EO, 2-propylheptanol-8EO, trideceth-8, trideceth-6, nonylphenol-9EO, castor oil ethoxylate-55EO, soya acid ethoxylate-10EO, nonylphenol-30EO, C10-12 alcohol ethoxylate (9EO), EO-PO-EO block copolymer (40% EO) MW 5900, C6-10 isopropylamine alcohol ether sulfate, trideceth-10, trideceth-12, sodium alkylnaphthalene sulfonate, formaldehyde polymer, C10-12 alcohol ethoxylate (12EO), polyoxyethylene sorbitol tallate, Di (propylene glycol) methyl ether, lauryldimethyl betaine, cocamide DEA, bottom amines, EO-PO-EO Block copolymer (70% EO) MW 12600, C11 alcohol ethoxylate (5EO), C10-12 alcohol ethoxylate (7EO), EO-PO-EO Block copolymer (70% EO) MW 6600, C10-12 alcohol ethoxylate (7EO), EO-PO-EO Block copolymer (80% EO) MW 13000, EO-PO-EO Block copolymer (80% EO) MW 8400, C8-10 glycosides C10-12 alcohol ethoxylate (SEQ), ethoxylated (20EO) sorbitol ester, 2-Ethylhexanol+13PO+20EO, tristyrylphenol+16EO, EO-PO-EO Block copolymer (50% EO) MW 6500, tallowamine-14EO, tallowamine-2EO, Nonylphenol-9EO carboxylate, C4 with average of 52EO and 46PO, cocoamine-10-EO, cocoamine-5EO, tallowamine-6EO, cocodimethylamidopropylamine, tallowamine-10EO, sodium lauryl olefin sulfonate, tall oil fatty acid amidoamine-10EO, castor oil ethoxylate-36EO, tallowamine-15EO methylchloride, Iso C13 etheramine-5EO, EO-PO-EO Block copolymer (50% EO) MW 4600, sodium lauryl olefin sulfonate, cocotrimethyl chloride, tallow acid+triethanolamine+10EO, cocoamine-2EO, tristyrylphenol+15EO, cocoamine-2EO methylchloride, C4 with average of 61EO and 55PO, coco duoamine-3EO, and mixtures and combinations thereof. 
         [0077]    In the herbicidal formulations of the invention, the ratio of said amine salt of a phenoxy acid herbicide, and said compatibility agent is generally between 20:1 to 1:2; in another embodiment, between 10:1 to 1:1.5; and in yet another embodiment 5:1 to 1:1. The concentration of amine salt of the phenoxy acid herbicide is generally between 0.1 to 40% by weight ai based on the weight of the formulation, in another embodiment 1 to 30% by weight and in still another embodiment 2 to 20% by weight. 
         [0078]    In one embodiment of the invention, the phenoxy acid herbicide is 2,4-D, and the ratio of 2,4-D amine salt to the compatability agent is between 10:1 to 1:1.5; in another embodiment 5:1 to 1:1. The concentration of 2,4-D amine salt in such formulations is generally between 0.1 to 40% by weight ai based on the weight of the formulation, in another embodiment 1 to 30% by weight and in still another embodiment 2 to 20% by weight. 
         [0079]    The invention will now be illustrated by the following non-limiting examples. 
       Example 1 
       [0080]      
         [0000]    
       
         
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                   
                 Solubility of 
                 Added 40% AMS wt 
                 Added 40% AMS wt into 
               
               
                   
                   
                 Solubility of tested 
                 testes 
                 into 10 g 0.13% 
                 10 g (2.5% 2,4-D + 
               
               
                   
                   
                 chemical in DI 
                 chemical in 
                 tested chemical in DI 
                 0.13% tested chemical in 
               
               
                 Example # 
                 Tested Chemical 
                 Water 
                 40% AMS 
                 water 
                 DI water) 
               
               
                   
               
             
             
               
                 1 
                 Castor oil ethoxylate- 
                 &lt;0.007% 
                 &lt;0.007% 
                 All hazy 
                 All hazy 
               
               
                   
                 10EO 
               
               
                 2 
                 Castor oil ethoxylate- 
                   &gt;20% 
                 &lt;0.036% 
                 0 g clear, 3.57 clear, 
                 0 g clear, 1.73 clear, 2.14 
               
               
                   
                 36EO 
                   
                   
                 3.74 hazy 
                 hazy 
               
               
                 3 
                 Castor oil ethoxylate- 
                   &gt;20% 
                 0.036% to 
                 0 g clear, 3.63 clear, 
                 0 g clear, 0.48 clear, 0.55 
               
               
                   
                 55EO 
                   
                 0.08% 
                 3.74 hazy 
                 hazy 
               
               
                 4 
                 Cocoamine-2EO 
                 &lt;0.016% 
                 &lt;0.016% 
                 All hazy 
                 0 g clear, 2.1 g clear, 2.26 g 
               
               
                   
                   
                   
                   
                   
                 hazy 
               
               
                 5 
                 Cocoamine-2EO 
                 All clear 
                 All clear 
                 All clear 
                 0 g clear, 2.21 g clear, 
               
               
                   
                 methylchloride 
                   
                   
                   
                 2.51 g hazy 
               
               
                 6 
                 Hexyl glycoside 
                 All clear 
                 All clear 
                 All clear 
                 0 g clear, 0.18 g clear, 
               
               
                   
                   
                   
                   
                   
                 0.36 g hazy 
               
               
                   
               
             
          
         
       
     
         [0081]    In example 1, the electrolyte tolerance of 6 chemicals with and without the presence of 2,4-D amine was evaluated in ammonium sulfate system. 
         [0082]    Examples #1, 2 and 3 show that the presence of the 2,4-D amine totally upsets the solubility trend of castor oil ethoxylate in the AMS solution. Judging from the solubility of castor oil ethoxylates in water and AMS solution, it is not possible to predict that 36EO castor oil ethoxylate would tolerate 3 times more AMS electrolyte than 55EO castor oil ethoxylate in 2.5% 2,4-D DMA solution without actually doing the experiment. 
         [0083]    Example #4 showed that cocoamine-2EO, like # 1 castor oil ethoxylate-10EO, has little compatibility in water or AMS solution. Those skilled in the art would expect cocoamine-2EO, like castor oil ethoxylate-10EO in #1, to have poor compatibility in 2,4-D amine and AMS solution. However, cocoamine-2EO, unlike castor oil ethoxylate-10EO, has very good compatibility in 2,4-D amine and AMS solution. 
         [0084]    Examples #5 and #6 showed that both cocoamine-2EO methylchloride and hexyl glycoside have excellent solubility in water and electrolyte tolerance (mutually soluble in 40% AMS solution). Those skilled in the art would expect both to have similar compatibility in 2,4-D amine and AMS system. However, cocoamine-2EO methylchloride is a very good compatibility agent while hexyl glycoside, which is a well known compatibility agent for other applications, is a poor compatibility agent in 2,4-D amine and AMS system. 
       Example 2 
       [0085]    In this example, the appearance of a 10 g solution of (2.5 wt % ai 2,4-D DMA+tested chemical) was evaluated after adding 40% AMS 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                   
               
               
                   
                   
                   
                   
                 Weight of 
                   
               
               
                   
                   
                   
                   
                 (grams) 
                 40% AMS 
               
               
                   
                   
                 wt % a.i. 
                 Addition 
                 System was 
                 System was 
               
               
                   
                 Trade Name of 
                 of tested 
                 0 gram 
                 clear after 
                 cloud after 
               
               
                 Tested Chemical 
                 tested chemical 
                 chemical 
                 Appearance 
                 adding 
                 adding 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 None (i.e., 2.5% 2,4-D 
                 None 
                 0.00% 
                 Clear 
                 0.217 
                 0.267 
               
               
                 DMA) 
               
               
                 Nonylphenol-4EO 
                 Ethylan NP-40 
                 0.13% 
                 cloudy 
                 cloudy 
                 0 
               
               
                 PO-EO-PO block 
                 Pluronic 25 R4 
                 0.13% 
                 cloudy 
                 cloudy 
                 0 
               
               
                 copolymer (MW 3600 
               
               
                 40% EO 
               
               
                 Trideceth-4 
                 Ethylan TD-40 
                 0.13% 
                 cloudy 
                 cloudy 
                 0 
               
               
                 Castor oil ethoxylate 
                 Emulpon CO-100 
                 0.13% 
                 Haze 
                 Haze 
                 0 
               
               
                 (10EO) 
               
               
                 Nonylphenol-6EO 
                 Ethylan NP-60 
                 0.13% 
                 Hazy 
                 Hazy 
                 0 
               
               
                 Castor oil ethoxylate 
                 Emulpon CO-50 
                 0.13% 
                 very 
                 very cloudy 
                 0 
               
               
                 (5EO) 
                   
                   
                 cloudy 
               
               
                 Sodium dioctyl 
                 Lankropol 4500 
                 0.13% 
                 very 
                 very cloudy 
                 0 
               
               
                 sulfonsuccinate 
                   
                   
                 cloudy 
               
               
                 Tall oil fatty acid-4EO 
                 Witconol FA-40 
                 0.13% 
                 very 
                 very cloudy 
                 0 
               
               
                   
                   
                   
                 cloudy 
               
               
                 EO-PO-EO Block 
                 Pluronic L31 
                 0.13% 
                 Haze 
                   
                 0.056 
               
               
                 copolymer (10% EO) MW 
               
               
                 1100 
               
               
                 Cocoamine-2EO oxide 
                 Aromox C/12 
                 0.13% 
                 Clear 
                   
                 0.096 
               
               
                 Sodium lauryl sulfate 
                 Witcolate WAC- 
                 0.04% 
                 Clear 
                   
                 0.101 
               
               
                   
                 LA 
               
               
                 Ethoxylated (6EO) 
                 Acconon CC-6 
                 0.13% 
                 Clear 
                   
                 0.163 
               
               
                 caprylic &amp; capric glycerol 
               
               
                 ester 
               
               
                 C8-10 glycosides 
                 Agnique PG 8166 
                 0.13% 
                 Clear 
                   
                 0.217 
               
               
                 2-ethylhexyl glycoside 
                 AG 6202 
                 0.13% 
                 Clear 
                   
                 0.226 
               
               
                 C9-C11 glycoside 
                 Agnique PG 9116 
                 0.13% 
                 Clear 
                   
                 0.272 
               
               
                 Iso C13 + 4EO phosphate 
                   
                 0.13% 
                 Clear 
                   
                 0.324 
               
               
                 ester (acid) 
               
               
                 Propyl glycosides 
                 AG 6203 
                 0.13% 
                 Clear 
                   
                 0.329 
               
               
                 Isopropyl alcohol 
                 IPA 
                 0.13% 
                 Clear 
                   
                 0.461 
               
               
                 C8-10 + 4 EO phosphate 
                   
                 0.13% 
                 Clear 
                   
                 0.488 
               
               
                 ester (acid) 
               
               
                 Alkyl ether citrate 
                 Alkyl ether citrate 
                 0.13% 
                 Clear 
                   
                 0.509 
               
               
                   
                 (AEC-3) 
               
               
                 Sodium xylene sulfonate 
                 Naxonate 4LS 
                 0.13% 
                 Clear 
                   
                 0.524 
               
               
                 Phenol ethoxylate 
                 Agrisol PX401 
                 0.13% 
                 Clear 
                   
                 0.577 
               
               
                 2-propylheptanol-5 EO 
                 Ethylan 1005 
                 0.13% 
                 Clear 
                   
                 0.633 
               
               
                 Sodium dodecylbenzene 
                 Witconate 90 Flake 
                 0.13% 
                 Clear 
                 0.107 
                 0.156 
               
               
                 sulfonate 
               
               
                 Butyl cellosolve Acetate 
                 Dowanol DPM 
                 0.13% 
                 Clear 
                 0.162 
                 0.324 
               
               
                 (C4—O—C—C—OOCC) 
               
               
                 Hexylglycosides 
                 AG 6206 
                 0.13% 
                 Clear 
                 0.179 
                 0.359 
               
               
                 2-Ethylhexanol + 35PO + 
                   
                 0.13% 
                 Clear 
                 0.246 
                 0.396 
               
               
                 32EO 
               
               
                 Na Cocoamphocarboxyglycinate 
                 Ampholak XCO-30 
                 1.25% 
                 Clear 
                 0.25 
                 0.508 
               
               
                 Oleylamphopolycarboxyglycinate 
                 Ampholak XO7/C 
                 0.13% 
                 Clear 
                 0.261 
                 0.459 
               
               
                 EO-PO-EO Block 
                 Pluronic L64 
                 0.13% 
                 clear 
                 0.268 
                 0.31 
               
               
                 copolymer (40% EO) MW 
               
               
                 2900 
               
               
                 Castor oil ethoxylate- 
                 Emulpon CO 200 
                 0.13% 
                 Clear 
                 0.279 
                 0.521 
               
               
                 20EO 
               
               
                 Octyliminodipropionate 
                 Ampholak YJH-40 
                 1.25% 
                 Clear 
                 0.283 
                 0.602 
               
               
                 EO-PO-EO Block 
                 Pluronic L10 
                 0.13% 
                 Clear 
                 0.288 
                 0.328 
               
               
                 copolymer MW 3200 
               
               
                 Triethyl ammonium 
                 Phospholan TEAP 
                 1.25% 
                 Clear 
                 0.303 
                 0.535 
               
               
                 phosphate 
               
               
                 EO-PO-EO Block 
                 Pluronic L43 
                 0.13% 
                 Clear 
                 0.339 
                 0.402 
               
               
                 copolymer (30% EO) MW 
               
               
                 1850 
               
               
                 EO-PO-EO Block 
                 Pluronic L35 
                 0.13% 
                 Clear 
                 0.358 
                 0.44 
               
               
                 copolymer (50% EO) MW 
               
               
                 1900 
               
               
                 Methyl-2-pyrrolidinone 
                 methyl-2- 
                 0.13% 
                 Clear 
                 0.36 
                 0.567 
               
               
                   
                 pyrrolidinone 
               
               
                 EO-PO-EO Block 
                 Pluronic L44 NF 
                 0.13% 
                 Clear 
                 0.389 
                 0.432 
               
               
                 copolymer (40% EO) MW 
               
               
                 2200 
               
               
                 Nonylphenol-12EO 
                 Ethylan NP-120 
                 0.13% 
                 Clear 
                 0.415 
                 0.502 
               
               
                 2-propylheptanol-8EO 
                 Ethylan 1008 
                 0.13% 
                 Clear 
                 0.43 
                 0.526 
               
               
                 Trideceth-8 
                 Ethylan TD-80 
                 0.13% 
                 Clear 
                 0.458 
                 0.684 
               
               
                 Trideceth-6 
                 Ethylan TD-60 
                 0.13% 
                 Clear 
                 0.47 
                 0.717 
               
               
                 Nonylphenol-9EO 
                 Ethylan NP-90 
                 0.13% 
                 Clear 
                 0.473 
                 0.601 
               
               
                 Castor oil ethoxylate- 
                 Emulpon CO 550 
                 0.13% 
                 Clear 
                 0.476 
                 0.554 
               
               
                 55EO 
               
               
                 Soya acid ethoxylate- 
                 Soya acid + 10 EO 
                 0.13% 
                 Clear 
                 0.482 
                 0.756 
               
               
                 10EO 
               
               
                 Nonylphenol-30EO 
                 Ethylan NP-300 
                 0.13% 
                 Clear 
                 0.487 
                 0.584 
               
               
                 C10-12 alcohol ethoxylate 
                 Ethylan SN-90 
                 0.13% 
                 Clear 
                 0.519 
                 0.72 
               
               
                 (9EO) 
               
               
                 EO-PO-EO Block 
                 Pluronic P104 
                 0.13% 
                 Clear 
                 0.521 
                 0.689 
               
               
                 copolymer (40% EO) MW 
               
               
                 5900 
               
               
                 C6-10 isopropylamine 
                 Witcolate 1259 
                 0.13% 
                 Clear 
                 0.528 
                 0.712 
               
               
                 alcohol ether sulfate 
               
               
                 Trideceth-10 
                 Ethylan TD-100 
                 0.13% 
                 Clear 
                 0.557 
                 0.685 
               
               
                 Trideceth-12 
                 Ethylan TD-120 
                 0.13% 
                 Clear 
                 0.581 
                 0.688 
               
               
                 Sodium alkylnaphthalene 
                 Morwet D-425 
                 0.13% 
                 Clear 
                 0.602 
                 1.066 
               
               
                 sulfonate, formaldehyde 
               
               
                 polymer 
               
               
                 C10-12 alcohol ethoxylate 
                 Ethylan SN-120 
                 0.13% 
                 Clear 
                 0.619 
                 0.669 
               
               
                 (12EO) 
               
               
                 Polyoxyethylene Sorbitol 
                 Armotan AL-69-66 
                 0.13% 
                 Clear 
                 0.661 
                 0.71 
               
               
                 Tallate 
               
               
                 Di (propylene glycol) 
                   
                 0.13% 
                 Clear 
                 0.665 
                 0.829 
               
               
                 methyl ether 
               
               
                 Lauryldimethyl betaine 
                 Amphoteen 24 
                 1.25% 
                 Clear 
                 0.693 
                 0.913 
               
               
                 Cocamide DEA 
                 Amadol 128T 
                 0.13% 
                 Clear 
                 0.701 
                 0.987 
               
               
                 Bottom amines 
                 Berolamine 20 
                 0.13% 
                 Clear 
                 0.758 
                 0.839 
               
               
                 EO-PO-EO Block 
                 Pluronic F127 
                 0.13% 
                 Clear 
                 0.805 
                 0.849 
               
               
                 copolymer (70% EO) MW 
               
               
                 12600 
               
               
                 C11 alcohol ethoxylate 
                   
                 0.13% 
                 Clear 
                 0.819 
                 0.918 
               
               
                 (5EO) 
               
               
                 C10-12 alcohol ethoxylate 
                 Ethylan SN-70 
                 0.13% 
                 Clear 
                 0.829 
                 1.033 
               
               
                 (7EO) 
               
               
                 EO-PO-EO Block 
                 Pluronic F77 
                 0.13% 
                 Clear 
                 0.901 
                 1.022 
               
               
                 copolymer (70% EO) MW 
               
               
                 6600 
               
               
                 C10-12 alcohol ethoxylate 
                 Ethylan SN-70 
                 0.13% 
                 Clear 
                 0.903 
                 1.026 
               
               
                 (7EO) 
               
               
                 EO-PO-EO Block 
                 Pluronic F98 
                 0.13% 
                 Clear 
                 0.917 
                 1.014 
               
               
                 copolymer (80% EO) MW 
               
               
                 13000 
               
               
                 EO-PO-EO Block 
                 Pluronic F68 
                 0.13% 
                 Clear 
                 0.939 
                 1.13 
               
               
                 copolymer (80% EO) MW 
               
               
                 8400 
               
               
                 C8-10 glycosides 
                 AG 6210 
                 0.13% 
                 Clear 
                 1 
                 1.212 
               
               
                 C10-12 alcohol ethoxylate 
                 Ethylan SN-50 
                 0.13% 
                 Clear 
                 1.035 
                 1.226 
               
               
                 (5EO) 
               
               
                 Ethoxylated (20EO) 
                 Tween 20 
                 0.13% 
                 Clear 
                 1.037 
                 1.25 
               
               
                 sorbitol ester 
               
               
                 2-Ethylhexanol + 13PO + 
                   
                 0.13% 
                 Clear 
                 1.0719 
                 1.251 
               
               
                 20EO 
               
               
                 Tristyrylphenol + 16EO 
                 Soprophor BSU 
                 0.13% 
                 Clear 
                 1.084 
                 2.235 
               
               
                 EO-PO-EO Block 
                 Pluronic P105 
                 0.13% 
                 Clear 
                 1.251 
                 1.301 
               
               
                 copolymer (50% EO) MW 
               
               
                 6500 
               
               
                 Tallowamine-14EO 
                 Ethomeen T/24 
                 0.13% 
                 Clear 
                 1.273 
                 1.526 
               
               
                 Tallowamine-2EO 
                 Ethomeen T/12 
                 0.13% 
                 Clear 
                 1.31 
                 1.513 
               
               
                 Nonylphenol-9EO 
                 Emcol CNP-110 
                 0.13% 
                 Clear 
                 1.312 
                 1.692 
               
               
                 carboxylate 
               
               
                 C4 with average of 52EO 
                 Polyoxyalkylene 
                 0.13% 
                 Clear 
                 1.325 
                 1.459 
               
               
                 and 46PO 
                 Glycol Butyl Ether 
               
               
                 Cocoamine-10EO 
                 Ethomeen C/20 
                 0.13% 
                 Clear 
                 1.454 
                 1.541 
               
               
                 Cocoamine-5EO 
                 Ethomeen C/15 
                 0.13% 
                 Clear 
                 1.478 
                 1.633 
               
               
                 Tallowamine-6EO 
                 Ethomeen T/16H 
                 0.13% 
                 Clear 
                 1.485 
                 1.751 
               
               
                 Cocodimethylamidopropylamine 
                 Armeen APA C 
                 0.13% 
                 Clear 
                 1.488 
                 1.731 
               
               
                 Tallowamine-10EO 
                 Ethomeen T/20 
                 0.13% 
                 Clear 
                 1.503 
                 1.717 
               
               
                 Sodium lauryl olefin 
                 Witconate AOS-12 
                 0.05% 
                 Clear 
                 1.526 
                 2.121 
               
               
                 sulfonate 
               
               
                 Tall oil fatty acid 
                   
                 0.13% 
                 Clear 
                 1.591 
                 2.243 
               
               
                 amidoamine-10EO 
               
               
                 Castor oil ethoxylate- 
                 Emulpon CO 360 
                 0.13% 
                 Clear 
                 1.726 
                 2.141 
               
               
                 36EO 
               
               
                 Tallowamine-15EO 
                 Ethoquad T/25 
                 0.13% 
                 Clear 
                 1.731 
                 2.014 
               
               
                 methylchloride 
               
               
                 Iso C13 etheramine-5EO 
                   
                 0.13% 
                 Clear 
                 1.732 
                 2.045 
               
               
                 EO-PO-EO Block 
                 Pluronic P85 
                 0.13% 
                 Clear 
                 1.76 
                 2.018 
               
               
                 copolymer (50% EO) MW 
               
               
                 4600 
               
               
                 Sodium lauryl olefin 
                 Witconate AOS-12 
                 0.13% 
                 Clear 
                 1.896 
                 2.546 
               
               
                 sulfonate 
               
               
                 Cocotrimethyl Chloride 
                 Arquad C33 
                 0.13% 
                 Clear 
                 2.038 
                 2.123 
               
               
                 Tallow acid + 
                   
                 0.13% 
                 Clear 
                 2.087 
                 3.049 
               
               
                 triethanolamine + 10EO 
               
               
                 Cocoamine-2EO 
                 Berol 307 
                 0.13% 
                 Clear 
                 2.096 
                 2.264 
               
               
                 Tristyrylphenol + 15EO 
                 TSP (EO) 14.8 Top 
                 0.13% 
                 Clear 
                 2.102 
                 2.509 
               
               
                 Cocoamine-2EO 
                 Ethoquad C/12 
                 0.13% 
                 Clear 
                 2.21 
                 2.511 
               
               
                 methylchloride 
               
               
                 C4 with average of 61EO 
                 Polyoxyalkylene 
                 0.13% 
                 Clear 
                 2.27 
                 2.728 
               
               
                 and 55PO 
                 Glycol Butyl Ether 
               
               
                 Coco duoamine-3EO 
                 Ethoduomeen 
                 0.13% 
                 Clear 
                 3.521 
                 4.058 
               
               
                   
                 CD/13 
               
               
                   
               
             
          
         
       
     
       Example 3 
       [0086]    In this example, the phase diagram of 28% N fertilizer, Ethoquad C/12, and 2,4-D DMA was constructed. 

 
         [0087]    For example, a farmer can add 10% of a pre-mixed (8:2 Ethoquad C/12W-43.7%: 2,4-D DMA-50% ai) to 90% 28% N and obtain a non-nozzle plugging spray solution. However, if 10% pre-mixed (8:2 water: 2,4-D DMA-50% ai) is added to 90% 28% N, a hazy system with coarse particles (2,4-D NH4 salt) will form in a few minutes at room temperature. This clearly showed than cocoamine-2EO methylchloride can prevent or minimize the formation of coarse particles of the 2,4-D ammonium salt as is shown in the following picture. 

 
       Example 4 
       [0088]    In the following picture, sample (0:0) was 3% 2,4-DMA (50%)+90% water (1000 ppm hardness)+7% AMS (40%) and it readily formed crystals at room temperature. Adding 0.069 g cocoamine-2EO into sample (0:0) changed it into a hazy product without crystals (sample (100:0)). Adding 0.069 g tallowamine-10EO into sample (0:0) dissolved most crystals (sample (0:100)). However, adding 0.069 g 1:1 cocoamine-2EO: tallowamine-10EO into sample (0:0) turned it into a clear solution (sample (50:50)). This demonstrated that there is a synergy between cocoamine-2EO and tallowamine-10EO in preventing 2,4-D electrolyte precipitate formation. 
         [0089]    The first sample, (0:0), on the left had no surfactant and it had about 15% crystal at the bottom. The rest of the samples had 0.069 g surfactant post-added to the first sample. Sample (100:0) was a hazy sample with a little oily sediment at bottom. Sample (45:55) was a little hazy with some crystals at the bottom. Sample (50:50) was perfectly clear without any crystals. Sample (55:45) was a little hazy with a few crystal particles at bottom. Sample (60:40) was a little hazy with some crystal at bottom. Sample (0:100) was a little hazy with ˜5% crystal at bottom. 

 
       Example 5 
       [0090]    System appearance after adding various chemicals into “System A” which was 100 g of 3% 2,4-D DMA (50%)+90% water (1000 ppm)+7% Ammonium sulfate (40%). 
         [0000]                                                          Sample composition   Added wt, grams   Appearance   pH                                System A (alone)   0   10% crystals   4.9       Ethoquad C/12 43.7%   0.815   clear   5.2       NH4OH 28-30%   0.079   hazy   8       Dimethylamine 40%   0.091   slightly hazy   7.8       10% NaOH   1.07   clear   6       10% NaOH   1.35   crystals re-appeared   10                    
It can be seen here that adding a significant amount of Ethoquad C/12 into the System A, the pH only changed slightly. However, adding inorganic base into the System A, the pH was not easy to control and it quickly changed to a high pH.
 
         [0091]    It is understood that the method also applies to in-can concentrated formulations and tank side mixed applications.