Compatibility Agents for Herbicidal Formulations Comprising 2,4- (Dichlorophenoxy) Acetic Acid Salts

FIELD OF THE INVENTION 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

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 art should realize that although 2,4-D is mentioned it should be understood that it also applies generally to the entire phenoxy herbicide family. 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.

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

SUBSTITUTE SFDEET (RLTLE 26)

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. 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.

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

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-amine cations and a method to minimize the formation of nozzle plugging particles in such a system.

DETAILED DESCRIPTION OF THE INVENTION

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.

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. 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. o phenoxyacetic herbicides

4-CPA 2.4-D

3.4-DA MCPA MCPA-thioethyl o phenoxybutyric herbicides 4-CPB

2.4-DB 3.4-DB MCPB o pheπoxypropionic herbicides clopfop

4-CPP dichlorprop dichlorprop-P 3,4-DP fenoprop mecoprop mecoprop-P o aryloxypheπoxypropionic herbicides chlorazifop clodinafop clofop cyhalofop diclofop fenoxaprop fenoxaprop-P fenthiaprop fluazifop fluazifop-P haloxyfop haloxyfop-P isoxapyrifop metamifop propaquizafop quizalofop quizalofop-P tfifop

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.

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-amine 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.

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, aikoxylated (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. The aikoxylated quaternary surfactants usefully employed in the context of the present invention can be represented by the following general formula:

wherein Rl 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 QH ₂ 1 where i is 2 to 4; B is C _j lt _j 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 C2H4, f = 0, g = 0, m + n is 2 to 20, R2 is methyl group, p = 1 , and X is chloride.

The alkyl quaternary surfactants useful in the invention are represented by the formula:

wherein Rl 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 CH ₂ , where i is 2 to 4; B is C _j H ₂ J 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 f = 0, g = 0, R2 is methyl group, R3 is a methyl group, R4 is a methyl group, p = 1, and X is chloride.

The following alkoxylated amines are useful:

III wherein Rl is a straight or branched chain, saturated or unsaturated alkyl group having from 8 to 22 carbon atoms; A is C,H ₂ i 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 H4, 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.

The following alkoxylated amidoamines are useful:

wherein Rl is a straight or branched chain, saturated or unsaturated alkyl group having from 7 to 21 carbon atoms; A is CjH _2J where i is 2 to 4; m is 1 to 30, and n is 1 to 30. The particularly useful Rl is from tall oil, coconut oil, soya oil, com, or tallow. The following amidoamines are useful: O CH3 Il I

R1-C-N-CH2-CH2-CH2-N-CH3

V where Rl a straight or branched chain, saturated or unsaturated alkyl group having from 7 to 21 carbon atoms. 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,

wherein Rl is a straight or branched chain, saturated or unsaturated alky] group having from 7 to 21 carbon atoms; A is QH _∑ j 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 Rl is from tall oil, coconut oil, soya oil, com, or tallow.

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,

wherein Rl is a straight or branched chain, saturated or unsaturated alkylene group having from 8 to 22 carbon atoms; A is Ciføi where i is 2 to 4; m is 1 to 30, and n is 1 to 30.

The following alkyl alcohol alkoxylates are useful,

wherein Rl is a straight or branched chain, saturated or unsaturated alkyl group having from 6 to 14 carbon atoms; A is QH ₂ ,- where i is 2 to 4; and v is 2 to 10 when Rl is linear and 9 - 20 when Rl is branched.

The following polyethylene sorbitans are useful:

Il O

IX where R is C8 to C22, n + m + w is about 10 to 30, preferably 20.

The tristyrylphenol ethoxylate with 8 - 30 moles of ethylene oxide and its phosphate or salts thereof are useful. The following EO/PO block and random copolymers are useful,

wherein Rl is H, or C4 to ClO linear or branched alkyl, A' is C2 or C3, x is 30 to 300, EO:PO > 40:60 (weight ratio). When Rl = H, they are preferably EO-PO-EO copolymer with a molecular weight > ~4000. When Rl is C4 to ClO, their molecular weight is preferably > ~ 1500.

The alkyl olefin sulfonate useful in the claimed invention includes alkyl chain length between C8 and Cl 8 and preferably C8 — 12 olefin sulfonate and salts thereof.

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.

Castor oil EO-PO alkoxylate (total 25 to 50 EO + PO units) can also be usefully employed in the context of the present invention .

C8-16 linear or branched alkyl polyglycoside with 1 - 5, preferably 1 - 2, glucose units are also useful. Alkylethersulfate amine salts are useful, and the alkyl chain length is preferably

C6 to C 12 with 1 to 5 EO groups. The preferred amine is dimethylamidopropylamine (DMAPA), triethanol amine (TEA), diethanolamine (DEA), monoethanolamine (MEA), butylamine, cocoamiπe, diethylene triamine (DETA), and isopropylamine.

The useful alkylnaphthalene sulfonate (formaldehyde polymer) salt has an alkyl group C8 - C 18 and the C8 - C 12 sodium salt is preferred.

Polyethylene sorbitol tallate of the following formula are also useftil:

C-O-(C-C-O) ₁₇₁ -R

I R-(O-C-C) _n -O-C

C-O-(C-C-O) _x -R

R-iO-C-C) _y -O-C

where R is H or a group with the structure: I

O=C-Rl here Rl 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 O to 20 independently with a provision of n+m+p+q+χ+y greater than or equal to 6.

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.

Where Rl, 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 O to 40; p is 1 - 7 independent of a, b, c, d, e, f, and g.

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.

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.

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 & capric glycerol ester, C8-10 glycosides, 2-ethylhexyl glycoside, C9-C1 1 glycoside, iso Cl 3 + 4EO phosphate ester (acid), propyl glycosides, isopropyl alcohol, C8-10 + 4 EO phosphate ester (acid), alkyl ether citrate, sodium xylene sulfonate, phenol ethoxylate2-propylheptanol-5EO, sodium dodecylbenzene sulfonate, 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 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-lOEO, nonylphenol- 3OEO, C 10- 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, C 10- 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, Cl 1 alcohol ethoxylate (5EO), ClO-12 alcohol ethoxylate (7EO), EO-PO-EO Block copolymer (70% EO) MW 6600, C 10- 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 ClO-12 alcohol ethoxylate (5EO), ethoxylated (20EO) sorbitol ester, 2-Ethylhexanol + 13PO + 2OEO, 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-lOEO, cocoamine- 5EO, tallowamine-6EO, cocodimethylamidopropylamine, tallowamine- 1 OEO, sodium lauryl olefin sulfonate, tall oil fatty acid amidoamine-lOEO, 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 + tπethanolamine + 1OEO, cocoamuie-2EO, tπstyrylphenol + 15EO, cocoamine-2EO methylchloπde, C4 with average of 61EO and 55PO, coco duoamine- 3EO, and mixtures and combinations thereof.

In the herbicidal formulations of the invention, the ratio of said amine salt of a 5 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 10 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 15 weight

The invention will now be illustrated by the following non-limiting examples Example 1.

In example 1, the electrolyte tolerance of 6 chemicals with and without the

1 1

SUBSTITUTE SHEET (RLiLE 26)

presence of 2,4-D amine was evaluated in ammonium sulfate system

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

Example #4 showed that cocoamme-2EO, like #1 castor oil ethoxylate- 1 OEO, has little compatibility in water or AMS solution Those skilled in the art would expect cocoamιne-2EO, like castor oil ethoxylate- 1 OEO 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.

Examples #5 and #6 showed that both cocoamine-2EO methylchloπde 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 methylchlonde 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

In this example, the appearance of alO g solution of (2.5 wt% ai 2,4-D DMA + tested chemical) was evaluated after adding 40% AMS

13

SUBS πTU 1 h Sl-IEh I (Rl ILE 26)

14

SUBSTI IUTr SlIl El (RULF 26)

Example 3

In this example, the phase diagram of 28% N fertilizer, Ethoquad C/12, and 2,4-D DMA was constructed.

10 20 30 40 SO 60 70 80 90 100 B

°λB ->

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.

90% 28% N 90% 28% N 1% 2,4-D DMA 1% 2,-4D DMA 9% DI water 5.5% DI water 3.5% Coco-2EO quat

Example 4

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-lOEO into sample (0:0) dissolved most crystals (sample (0:100)). However, adding 0.069 g 1 : 1 cocoamine- 2EO : tallowamine-lOEO 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-lOEO in preventing 2,4-D electrolyte precipitate formation.

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.

Coco-2 0 100 45 50 55 60 0

Tallow-10 0 0 55 50 45 40 100

Example 5. 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%).

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. It is understood that the method also applies to in-can concentrated formulations and tank side mixed applications.