Compositions for crop protection

Abstract

A composition is provided that includes a caprolactam-derived solvent and a crop protection active ingredient. An emulsifiable concentrate is also provided that includes a caprolactam-derived solvent, an organic co-solvent, an emulsifier, and a crop protection active ingredient.

Description

FIELD

[0001] The present invention relates to compositions for crop defense. In particular, compositions comprising a caprolactam-derived solvent selected from the group consisting of N-methylcaprolactam, N-ethylcaprolactam, N-butylcaprolactam and mixtures thereof, and a crop protective active ingredient dissolved in the caprolactam-derived solvent, wherein said crop protective active ingredient is tebuconazole.BACKGROUND

[0002] Some important crop protective active ingredients, or pesticides including herbicides, insecticides, and fungicides, are soluble in organic solvents, but are not soluble in water. Some important crop protective active ingredients are soluble in water, but are sensitive to water and tend to decompose over time. Such pesticides may be applied to crops in the form of an emulsion of small droplets of organic solvents that are finely dispersed in water. The droplets of organic solvents contain the pesticides.

[0003] The emulsion containing the pesticide is often formed at the time of use by combining an emulsifiable concentrate (EC) with water. In addition to the pesticide and one or more organic solvents, the EC may include an emulsifier so that the emulsion forms quickly and readily when the EC is added to water. In some cases, the nature of the solvents used in the EC results in the pesticide being suspended in the solvents, rather than dissolved in the solvents. Pesticides that are suspended in the EC, rather than dissolved in the EC, may eventually fall out of suspension, for example, in storage or transportation, particularly under low temperature conditions. The pesticides that fall out of suspension may clog application equipment nozzles and prevent the proper application of the pesticides to the crops or to the fields in which the crops are to be planted.

[0004] Thus, it is beneficial that the one or more solvents in the EC are able to readily dissolve the pesticides, especially at higher pesticide concentrations desirable in the EC. In some cases, the one or more solvents include N-methyl-2-pyrrolidone (NMP) or isophorone. NMP and isophorone are excellent solvents for many of the most difficult to dissolve pesticides. However, NMP has been found to be a reproductive toxin and isophorone is a suspected carcinogen. US2009 / 062120A1 discloses compositions comprising: a caprolactam-derived solvent comprising inter alia N-methylcaprolactam and N-ethylcaprolactam as part of a caprolactam Markush formula and a crop protective active ingredient which can be selected from herbicides, insecticides or fungicides dissolved in the caprolactam-derived solvent. Example 1 discloses a composition comprising tebuconazole and acetylcaprolactam. CN103420914A discloses the use of N-butylcaprolactam as a pesticide penetration promoter in pesticidal compositions. WO2005 / 092953A1 discloses the use of N-methylcaprolactam as solvent or co-solvent in agrochemical compositions comprising as active ingredient an insecticide, a fungicide or an herbicide. US6255350B1 discloses compositions comprising: a caprolactam-derived solvent and a crop protective active ingredient which is an herbicide; the composition is in the form of an anhydrous miniemulsion concentrate with an amount from 0.05 to 25% w / w of the crop protecting agent. CN108378051A discloses a composition comprising an herbicide such as penoxsulam, a penetration enhancer which is N-butylcaprolactam and emulsifiers. What are needed are solvents that readily dissolve pesticides and are neither reproductive toxins nor suspected carcinogens.SUMMARY

[0005] The present invention provides a composition including a crop protective active ingredient and a caprolactam-derived solvent that mitigates or eliminates disadvantages associated with traditional solvents. The composition may be useful applying the crop protective active ingredient to crops or to fields in which crops are to be planted. The invention relates to a composition comprising a caprolactam-derived solvent selected from the group consisting of N-methylcaprolactam, N-ethylcaprolactam, N-butylcaprolactam and mixtures thereof, and a crop protective active ingredient dissolved in the caprolactam-derived solvent, wherein said crop protective active ingredient is tebuconazole.

[0006] The caprolactam-derived solvent is selected from the group consisting of N-methylcaprolactam, N-ethylcaprolactam, N-butylcaprolactam and mixtures thereof. The concentration of the caprolactam-derived solvent may be from 5 weight percent to 50 weight percent of the composition.

[0007] The crop protective active ingredient is tebuconazole. The concentration of the crop protective active ingredient may be from 5 weight percent to 75 weight percent of the composition.

[0008] The composition may further include an emulsifier. The emulsifier may include at least one selected from the group of ethoxylated glycerin / fatty acid esters, glycerol monooleate, glycerol dioleate, PEG alkoxylated block polymers, alkoxylated alcohols, alkoxylated alkylphenols, alkoxylated amines, alkoxylated amides, alkoxylated fatty esters, alkoxylated oils, fatty esters, alkoxylated fatty acids, sorbitan derivatives, alkylaryl sulfonates, alkylaryl sulfonic acids, carboxylated alcohol ethoxylates, alkylphenol ethoxylates, carboxylic acids, olefin sulfonates, phosphate esters, and quaternary surfactants. The concentration of the emulsifier may be from 5 weight percent to 15 weight percent of the composition.

[0009] The composition may further include a co-solvent. The co-solvent may include at least one selected from the group of C 9 -C 12 hydrocarbon solvents, aliphatic paraffinic oils, aromatic solvents, C 9 -C 12 aromatic solvents, chlorinated hydrocarbons, alcohols, ketones, ethers, vegetable oils, methylated vegetable oils, petroleum oils, and sugar esters of fatty acids. The concentration of the co-solvent may be from 15 weight percent to 70 weight percent of the composition.

[0010] In another form thereof, the present disclosure provides an emulsifiable concentrate including the mentioned caprolactam-derived solvent, the mentioned crop protective active ingredient dissolved in the caprolactam-derived solvent, an organic co-solvent, and an emulsifier.

[0011] The concentration of the crop protective active ingredient may be from 5 weight percent to 75 weight percent of the emulsifiable concentrate. The concentration crop protective active ingredient may be from 20 weight percent to 30 weight percent of the emulsifiable concentrate.

[0012] The above mentioned features of the invention, and the manner of attaining them, will become more apparent and the invention itself will be better understood by reference to the following description of the invention.DETAILED DESCRIPTION

[0013] Compositions and concentrates of the disclosure employ caprolactam-derived solvents. The invention relates to a composition comprising a caprolactam-derived solvent selected from the group consisting of N-methylcaprolactam, N-ethylcaprolactam, N-butylcaprolactam and mixtures thereof, and a crop protective active ingredient dissolved in the caprolactam-derived solvent, wherein said crop protective active ingredient is tebuconazole, to replace traditional solvents, such as NMP or isophorone, for example. The caprolactam-derived solvents can replace NMP or isophorone in an emulsifiable concentrate containing crop protective active ingredients. The basis of the caprolactam-derived solvents, caprolactam, has not been found to be, and is not expected to be, either a reproductive toxin or a carcinogen. In particular, N-methylcaprolactam is not considered to be either a reproductive toxin or a carcinogen. Thus, the caprolactam-derived solvents, namely N-methylcaprolactam, N-ethylcaprolactam, and N-butylcaprolactam, are significantly safer solvents than NMP and isophorone.

[0014] In addition, as shown in the example below, the caprolactam-derived solvents, namely N-methylcaprolactam, N-ethylcaprolactam, and N-butylcaprolactam, appear to be as effective as NMP and other commonly used solvents, such as methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate and N-butyl-2-pyrrolidone, in dissolving crop protective active ingredients. As is known in the art, Hansen Solubility Parameters can be used to predict the effectiveness of a solvent. With respect to the dissolution of the crop protective active ingredients, one skilled in the art would expect the polarity and hydrogen bonding Hansen Solubility Parameters to be strongly predictive of the effectiveness of a solvent, with generally higher values corresponding to more effective solvents.

[0015] A comparison of the Hansen Solubility Parameters for the caprolactam-derived solvents and the some commonly used solvents is shown in Table 1 below. Surprisingly, as shown in Table 1, the polarity and hydrogen bonding Hansen Solubility Parameters for the caprolactam-derived solvents are significantly lower than those for the commonly used solvents. Thus, one skilled in the art would not expect the caprolactam-derived solvents to be as effective as NMP and other commonly used solvents. Table 1 Hansen Solubility Parameters Solvent Dispersion Polarity Hydrogen Bonding N-methylcaprolactam 17.97.6 5.7 N-ethylcaprolactam 17.76.7 5.2 N-butylcaprolactam 17.54.8 4.6 N-methyl-2-pyrrolidone18.012.37.2N,N-dimethyladipamide methyl ester17.29.79.3methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate15.810.79.2

[0016] Without wishing to be bound by any theory, it is believed that because the caprolactam-derived solvents used, namely N-methylcaprolactam, N-ethylcaprolactam and N-butylcaprolactam, are polar solvents, they are able to dissolve crop protective active ingredients that include polar groups (e.g. amines, halogens, oxygen containing groups). It is further believed that because the caprolactam-derived solvents are aprotic, they will not tend to cause the crop protective active ingredients to decompose over time. The caprolactam-derived solvent may be a mixture of two or more of N-methylcaprolactam, N-ethylcaprolactam and N-butylcaprolactam.

[0017] The concentration of the caprolactam-derived solvent as a weight percentage of the composition may be as low as 5 wt. %, 8 wt. %, 10 wt. %, 11 wt. %, 14 wt. %, or 17 wt. %, or as high as 26 wt. %, 30 wt. %, 32 wt. %, 38 wt. %, 44 wt. %, or 50 wt. %, or within any range defined between any two of the foregoing values, such as 5 wt. % to 50 wt. %, 8 wt. % to 44 wt. %, 10 wt. % to 30 wt. %, 11 wt. % to 38 wt. %, 14 wt. % to 32 wt. %, or 17 wt. % to 26 wt. %, for example.

[0018] The crop protective active ingredient is tebuconazole.

[0019] The concentration of the crop protective active ingredient as a weight percentage of the composition may be as low as 5 weight percent (wt. %), 8 wt. %, 11 wt. %, 14 wt. %, 17 wt. %, or 20 wt. %, or as high as 30 wt. %, 40 wt. %, 50 wt. %, 60 wt. %, 70 wt. % or 75 wt. %, or within any range defined between any two of the foregoing values, such as 5 wt. % to 75 wt. %, 8 wt. % to 70 wt. %, 11 wt. % to 60 wt. %, 14 wt. % to 50 wt. %, 17 wt. % to 40 wt. %, or 20 wt. % to 30 wt. %, for example.

[0020] The composition may further include an organic co-solvent. The organic co-solvent may include an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or any combination thereof. Such solvents can be less expensive than the caprolactam-derived solvents and thus lower the overall cost of the composition. The organic co-solvent may include C 9 -C 12 hydrocarbon solvents, aliphatic paraffinic oils such as kerosene or refined paraffins, aromatic solvents such as xylene, C 9 -C 12 aromatic solvents, chlorinated hydrocarbons such as chlorobenzene, alcohols such as butanol and benzyl alcohol, ketones such as cyclohexanone, and ethers such as diethylene glycol and diethoxol. The organic co-solvent may include vegetable oils, methylated vegetable oils, petroleum oils, and sugar esters of fatty acids. The organic co-solvent may include any combination of the foregoing co-solvents.

[0021] The concentration of the organic co-solvent as a weight percentage of the composition may be as low as 15 wt. %, 22 wt. %, 29 wt. %, 36 wt. %, 40 wt. %, or 43 wt. %, or as high as 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, or 70 wt. or within any range defined between any two of the foregoing values, such as 15 wt. % to 70 wt. %, 22 wt. % to 65 wt. %, 20 wt. % to 60 wt. %, 36 wt. % to 55 wt. %, 40 wt. % to 50 wt. %, or 43 wt. % to 50 wt. %, for example.

[0022] The composition can further include an emulsifier. The emulsifier may include ethoxylated glycerin / fatty acid esters such as ethoxylated glyceryl fatty acid esters (e.g., PEG 20 glyceryl laurate, PEG 20 glyceryl oleate, PEG 20 glyceryl oleoricinoleate, and PEG 20 glyceryl stearate), sorbitan esters and ethoxylated sorbitan esters (e.g., sorbitan monolaurate and sorbitan trioleate), glycerol monooleate, glycerol dioleate, PEG alkoxylated block polymers, alkoxylated alcohols, alkoxylated alkylphenols, alkoxylated amines, alkoxylated amides, alkoxylated fatty esters, alkoxylated oils, fatty esters, alkoxylated fatty acids, alkylaryl sulfonates, alkylaryl sulfonic acids, carboxylated alcohol ethoxylates, alkylphenol ethoxylates, carboxylic acids, olefin sulfonates, phosphate esters, quaternary surfactants, and combinations thereof.

[0023] The concentration of the emulsifier as a weight percentage of the composition may be as low as 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, or 9 wt. %, or as high as 11 wt. %, 12 wt. %, 13 wt. %, 14 wt. %, or 15 wt. %, or within any range defined between any two of the foregoing values, such as 5 wt. % to 15 wt. %, 6 wt. % to 14 wt. %, 7 wt. % to 13 wt. %, 8 wt. % to 12 wt. %, 9 wt. % to 11 wt. %, or 8 wt. % to 10 wt. %, for example.

[0024] An emulsifiable concentrate (EC) includes a caprolactam-derived solvent selected from the group consisting of N-methylcaprolactam, N-ethylcaprolactam, N-butylcaprolactam and mixtures thereof, a crop protective active ingredient which is tebuconazole, an organic co-solvent and an emulsifier. The EC may be formed by mixing together the components.

[0025] The concentration of the crop protective active ingredient as a weight percentage of the emulsifiable concentrate may be as low as 5 weight percent (wt. %), 8 wt. %, 11 wt. %, 14 wt. %, 17 wt. %, or 20 wt. %, or as high as 30 wt. %, 40 wt. %, 50 wt. %, 60 wt. %, 70 wt. % or 75 wt. %, or within any range defined between any two of the foregoing values, such as 5 wt. % to 75 wt. %, 8 wt. % to 70 wt. %, 11 wt. % to 60 wt. %, 14 wt. % to 50 wt. %, 17 wt. % to 40 wt. %, or 20 wt. % to 30 wt. %, for example.

[0026] The concentration of the caprolactam-derived solvent, which is selected from the group consisting of N-methylcaprolactam, N-ethylcaprolactam, N-butylcaprolactam and mixtures thereof, as a weight percentage of the emulsifiable concentrate may be as low as 5 wt. %, 8 wt. %, 10 wt. %, 11 wt. %, 14 wt. %, or 17 wt. %, or as high as 26 wt. %, 30 wt. %, 32 wt. %, 38 wt. %, 44 wt. %, or 50 wt. %, or within any range defined between any two of the foregoing values, such as 5 wt. % to 50 wt. %, 8 wt. % to 44 wt. %, 10 wt. % to 30 wt. %, 11 wt. % to 38 wt. %, 14 wt. % to 32 wt. %, or 17 wt. % to 26 wt. %, for example.

[0027] The concentration of the emulsifier as a weight percentage of the emulsifiable concentrate may be as low as 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, or 9 wt. %, or as high as 11 wt. %, 12 wt. %, 13 wt. %, 14 wt. %, or 15 wt. %, or within any range defined between any two of the foregoing values, such as 5 wt. % to 15 wt. %, 6 wt. % to 14 wt. %, 7 wt. % to 13 wt. %, 8 wt. % to 12 wt. %, 9 wt. % to 11 wt. %, or 8 wt. % to 10 wt. %, for example.

[0028] The concentration of the organic co-solvent as a weight percentage of the emulsifiable concentrate may be as low as 15 wt. %, 22 wt. %, 29 wt. %, 36 wt. %, 40 wt. %, or 43 wt. %, or as high as 50 wt. %, 55 wt. %, 60 wt. %, 65 wt. %, or 70 wt. or within any range defined between any two of the foregoing values, such as 15 wt. % to 70 wt. %, 22 wt. % to 65 wt. %, 20 wt. % to 60 wt. %, 36 wt. % to 55 wt. %, 40 wt. % to 50 wt. %, or 43 wt. % to 50 wt. %, for example.

[0029] The EC can be provided to a use location, such as a farm, and diluted on-site with water to a desired application concentration (otherwise known as a tank mixture). Upon dilution with water, the emulsifier in the EC quickly and readily forms an emulsion of organic droplets finely dispersed in the tank mixture. The organic droplets include the caprolactam-derived solvent, the co-solvent, and the crop protective active ingredient.

[0030] The organic droplets are not miscible with the water, so that the crop protective active ingredient stays in solution within the organic droplets. This can provide for an even concentration of the crop protective active ingredient in the tank mixture. Once the tank mixture is prepared, the diluted EC is applied to the crops or to the fields in which the crops are to be planted. The diluted EC can be applied by, for example, spraying or dribbling on to the fields or injecting into the soil. Lines and nozzles used to apply the diluted EC are less likely to clog because the crop protective active ingredient stays in solution within the organic droplets.EXAMPLESComparative Example 1 - Herbicide Comparative Solubility

[0031] The solubility of the herbicide saflufenacil was determined for thirteen solvents. Three of the solvents were caprolactam-derived solvents in accordance with this disclosure. The remaining ten were comparative solvents. The solubility of saflufenacil was evaluated for each solvent by preparing four, 2 ml vials containing 20 wt. %, 30 wt. %, 40 wt. % and 50 wt. % of saflufenacil. To prepare the 20 wt. % vial, 0.040 g of saflufenacil was added to 0.160 ml of solvent. To prepare the 30 wt. % vial, 0.060 g of saflufenacil was added to 0.140 ml of solvent. To prepare the 40 wt. % vial, 0.80 g of saflufenacil was added to 0.120 ml of solvent. To prepare the 50 wt. % vial, 0.100 g of saflufenacil was added to 0.100 ml of solvent. The vials were capped and swirled at room temperature until no change in solubility was observed.

[0032] The results are shown in Table 2 below. Table 2 shows the maximum weight percentage of saflufenacil dissolved in each solvent, as described above. Solvents 1-3 are in accordance with the present disclosure. Solvents 4-13 are comparative solvents. As shown in Table 2, the N-methylcaprolactam performed nearly as well as NMP, and better than any other comparative solvent. Table 2 Saflufenacil 1 N-methylcaprolactam 40% 2 N-ethylcaprolactam 30% 3 N-butylcaprolactam 20% 4N-methyl-2-pyrrolidone50%5N-butyl-2-pyrrolidone30%6N,N-dimethyldecanamide30%7N,N-dimethyladipamide methyl ester< 20%8methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate20%9cyclohexanone< 20%10cyclohexyl methyl ether< 20%11cyclohexyl acetate< 20%12cyclohexyl butyrate< 20%13N-(2-cyanoethyl)caprolactam< 20% Comparative Example 2 - Insecticide Comparative Solubility

[0033] Test samples including the insecticide bifenthrin were prepared as described above for Example 1 for saflufenacil. The results are shown in Table 3 below. Table 3 shows the maximum weight percentage of bifenthrin dissolved in each solvent, as described above. As in Table 1 above, solvents 1-3 are in accordance with the present disclosure and solvents 4-13 are comparative solvents. As shown in Table 3, the N-ethylcaprolactam performed as well as NMP. Table 3 Bifenthrin 1 N-methylcaprolactam 40% 2 N-ethylcaprolactam 50% 3 N-butylcaprolactam 40% 4N-methyl-2-pyrrolidone50%5N-butyl-2-pyrrolidone50%6N,N-dimethyldecanamide30%7N,N-dimethyladipamide methyl ester30%8methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate30%9cyclohexanone50%10cyclohexyl methyl ether50%11cyclohexyl acetate40%12cyclohexyl butyrate40%13N-(2-cyanoethyl)caprolactam< 20% Example 3 - Fungicide Comparative Solubility

[0034] Test samples including the fungicide tebuconazole were prepared as described above for Example 1 for saflufenacil. The results are shown in Table 4 below. Table 4 shows the maximum weight percentage of tebuconazole dissolved in each solvent, as described above. As in Table 1 above, solvents 1-3 are in accordance with the present disclosure and solvents 4-13 are comparative solvents. As shown in Table 4, the N-methylcaprolactam and the N-ethylcaprolactam performed as well as NMP. Table 4 Tebuconazole 1 N-methylcaprolactam 50% 2 N-ethylcaprolactam 50% 3 N-butylcaprolactam 40% 4N-methyl-2-pyrrolidone50%5N-butyl-2-pyrrolidone40%6N,N-dimethyldecanamide30%7N,N-dimethyladipamide methyl ester30%8methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate30%9cyclohexanone40%10cyclohexyl methyl ether20%11cyclohexyl acetate20%12cyclohexyl butyrate< 20%13N-(2-cyanoethyl)caprolactam< 20%

Claims

1. A composition comprising a caprolactam-derived solvent selected from the group consisting of N-methylcaprolactam, N-ethylcaprolactam, N-butylcaprolactam and mixtures thereof, and a crop protective active ingredient dissolved in the caprolactam-derived solvent, wherein said crop protective active ingredient is tebuconazole.

2. The composition of claim 2, wherein a concentration of the caprolactam-derived solvent is from 5 weight percent to 50 weight percent of the composition.

3. The composition of any of claims 1 or 2, wherein a concentration of the crop protective active ingredient is from 5 weight percent to 75 weight percent of the composition.

4. The composition of any of claims 1-3, further including an emulsifier.

5. The composition of claim 4, wherein the emulsifier includes at least one selected from the group of ethoxylated glycerin / fatty acid esters, glycerol monooleate, glycerol dioleate, PEG alkoxylated block polymers, alkoxylated alcohols, alkoxylated alkylphenols, alkoxylated amines, alkoxylated amides, alkoxylated fatty esters, alkoxylated oils, fatty esters, alkoxylated fatty acids, alkylaryl sulfonates, alkylaryl sulfonic acids, carboxylated alcohol ethoxylates, alkylphenol ethoxylates, carboxylic acids, olefin sulfonates, phosphate esters, and quaternary surfactants.

6. The composition of either of claim 4 or 5, wherein a concentration of the emulsifier is from 5 weight percent to 15 weight percent of the composition.

7. The composition of any of claims 1-6, further including a co-solvent.

8. The composition of claim 7, wherein the co-solvent includes at least one selected from the group of C9-C12 hydrocarbon solvents, aliphatic paraffinic oils, aromatic solvents, C9-C12 aromatic solvents, chlorinated hydrocarbons, alcohols, ketones, ethers, vegetable oils, methylated vegetable oils, petroleum oils, and sugar esters of fatty acids.

9. The composition of either of claims 7 or 8, wherein a concentration of the co-solvent is from 15 weight percent to 70 weight percent of the composition.