Clethodim composition

Abstract

The invention relates to a stable clethodim composition, which comprises, relative to the total mass of the composition, (a) 1-70% of clethodim; (b) from 0.1% to 10% of an anionic surfactant; (c) 0.1 to 10 percent of a first non-ionic surface active agent, wherein the first non-ionic surface active agent is polyoxyethylene sorbitan fatty acid ester; (d) 0.1 to 10 percent of a second non-ionic surface active agent, wherein the second non-ionic surface active agent is oleic acid polyoxyethylene ester; and (e) 20%-85% of a solvent.

Description

Clethodim Composition Technical Field

[0001] This invention relates to clethodim compositions. Background Technology

[0002] Clethodim is an important cyclohexanedione oxime herbicide with the following structure:

[0003] Due to the presence of double bonds and oxime functional groups in its molecule, clethodim is unstable, and factors such as soil temperature, ambient temperature, water, and light can all promote its degradation. Therefore, maintaining the stability of clethodim technical and formulations during long-term transportation and storage has always been a major concern, with degradation rates typically exceeding 10% after two years.

[0004] Summary of the Invention

[0005] This invention aims to provide a stable clethodim composition that effectively solves the problem of clethodim's easy degradation upon exposure to light and heat. In this composition, three surfactants are used in combination as emulsifiers, including two specific nonionic surfactants, which ensures that the degradation rate of clethodim after heat storage at 54℃±2℃ for 2 weeks is stably controlled within 4%, and the emulsion exhibits excellent stability.

[0006] Specifically, the present invention provides:

[0007] (1) A clethodim composition, comprising, relative to the total mass of the composition:

[0008] (a) 1-70%, preferably 10-60% of clethodim;

[0009] (b) 0.1-10%, preferably 2-8%, of anionic surfactants;

[0010] (c) 0.1-10%, preferably 0.5-5%, of a first nonionic surfactant, wherein the first nonionic surfactant is polyoxyethylene dehydrated sorbitan fatty acid ester;

[0011] (d) 0.1-10%, preferably 1-6%, of a second nonionic surfactant, wherein the second nonionic surfactant is oleic acid polyoxyethylene ester;

[0012] (e) 20-85%, preferably 30-75% solvent.

[0013] (2) According to the composition described in (1) above, the anionic surfactant is a sulfonate type, preferably C 8-20 Alkylbenzene sulfonates or C 8-20 Alkyl sulfonate, more preferably C 10-18 Alkylbenzene sulfonate, more preferably C 12-18Alkylbenzene sulfonates, particularly calcium dodecylbenzene sulfonate or sodium dodecylbenzene sulfonate.

[0014] (3) According to the composition described in (1) or (2) above, wherein the average degree of polymerization of the first nonionic surfactant polyoxyethylene dehydrated sorbitan fatty acid ester is 1 to 200, more preferably 1 to 100, further preferably 1 to 50, and even more preferably 1 to 30.

[0015] (4) The composition according to any one of (1)-(3) above, wherein the first nonionic surfactant polyoxyethylene dehydrated sorbitan fatty acid ester is a Tween series, preferably polyoxyethylene dehydrated sorbitan monooleate.

[0016] (5) The composition according to any one of (1)-(4) above, wherein the average degree of polymerization of the second nonionic surfactant oleic acid polyoxyethylene ester is 1 to 200, more preferably 1 to 100, further preferably 1 to 50, and even more preferably 1 to 30.

[0017] (6) The composition according to any one of (1)-(5) above, wherein the solvent is a solvent oil, preferably 150# solvent oil or 200# solvent oil.

[0018] (7) The composition according to any one of (1)-(6) above, wherein the total content of the anionic surfactant, the first nonionic surfactant and the second nonionic surfactant is not more than 15%, preferably not more than 12%, and more preferably 8-10%.

[0019] (8) The composition according to any one of (1)-(7) above, comprising, relative to the total mass of the composition, 10-60% clethodim and 2-8% C 10-18 Alkylbenzene sulfonate, 0.5-5% of the first nonionic surfactant polyoxyethylene dehydrated sorbitan fatty acid ester, 1-6% of the second nonionic surfactant oleic acid polyoxyethylene ester, and 30-75% of solvent.

[0020] (9) The composition according to any one of (2)-(8) above, wherein C 10-18 Alkylbenzene sulfonate is calcium dodecylbenzene sulfonate. Detailed Implementation

[0021] In this application, unless otherwise specified, "%" refers to the mass percentage content. The percentage content of clethodim is expressed as a percentage on a denominated basis. The term "about" means ±10%, preferably ±5%.

[0022] In this invention, degradation rate is an important indicator for measuring the stability of the clethodim composition. The initial content of the clethodim compound in the composition is denoted as w1. The composition is then placed at 54℃±2℃ for 2 weeks, and the content of the clethodim compound is measured and denoted as w2. The degradation rate is calculated as (w1-w2) / w1×100%. The content of the clethodim compound is determined according to known methods.

[0023] The emulsion stability of the composition was tested according to known methods of CIPAC.

[0024] After being stored at 54℃±2℃ for 2 weeks, the degradation rate of the clethodim compound in the composition of the present invention can be stably controlled within 4%, and the emulsion stability is very good.

[0025] In the compositions of the present invention, the content of clethodim compound is 1-70%, preferably 10-60%.

[0026] In this invention, the anionic surfactant can be of the fatty carboxylic acid ester type, fatty alcohol sulfate type, sulfonate type, or phosphate ester type, preferably of the sulfonate type, and more preferably of C. 8-20 Alkylbenzene sulfonates or C 8-20 Alkyl sulfonate, more preferably C 10-18 Alkylbenzene sulfonates, more preferably C 12-18 Alkylbenzene sulfonates.

[0027] In some specific embodiments, the above-mentioned anionic surfactant is calcium dodecylbenzenesulfonate or sodium dodecylbenzenesulfonate.

[0028] In the composition of the present invention, the content of the above-mentioned anionic surfactant is 0.1-10%, preferably 2-8%.

[0029] In the composition of the present invention, the polyoxyethylene dehydrated sorbitan fatty acid ester used as the first nonionic surfactant is preferably a Tween series, such as Tween 20, Tween 21, Tween 40, Tween 60, Tween 61, Tween 80 (i.e., polyoxyethylene dehydrated sorbitan monooleate), Tween 81, Tween 85, etc. These can be used alone or in combination of any two or more.

[0030] The average degree of polymerization of the polyoxyethylene dehydrated sorbitan fatty acid ester is preferably 1-200, more preferably 1-100, further preferably 1-50, and even more preferably 1-30.

[0031] In the composition of the present invention, the content of the first nonionic surfactant is 0.1-10%, preferably 0.5-5%, and more preferably 0.5-3%.

[0032] In some specific embodiments, the oleic acid polyoxyethylene ester used as the second nonionic surfactant is preferably one or more of oleic acid polyoxyethylene esters A-103, A-105, A-110, and A-115.

[0033] The average degree of polymerization of oleic acid polyoxyethylene ester is preferably 1 to 200, more preferably 1 to 100, further preferably 1 to 50, and even more preferably 1 to 30.

[0034] In the composition of the present invention, the content of the second nonionic surfactant is 0.1-10%, preferably 1-6%.

[0035] The compositions of the present invention contain 20-85%, preferably 30-75%, of a solvent, and specific examples of the solvent include, but are not limited to, solvent oils.

[0036] In some specific embodiments, the solvent is 150# solvent oil or 200# solvent oil.

[0037] Compositions containing the five components as described in (a)-(e) above, compositions consisting essentially of these components, and compositions consisting of these components are all included within the scope of this invention.

[0038] In some specific embodiments, the compositions of the present invention comprise, are substantially composed of, or are composed of: 10-60% clethodim, 2-8% C 10-18 Alkylbenzene sulfonate, 0.5-5% of the first nonionic surfactant polyoxyethylene dehydrated sorbitan fatty acid ester, 1-6% of the second nonionic surfactant oleic acid polyoxyethylene ester, and 30-75% of solvent.

[0039] From a cost perspective, the total content of the anionic surfactant, the first nonionic surfactant, and the second nonionic surfactant in the composition of the present invention is preferably no more than 15%, and more preferably no more than 12%.

[0040] Considering both emulsification effect and cost, the total content of the anionic surfactant, the first nonionic surfactant and the second nonionic surfactant in the composition of the present invention is preferably 8-10%.

[0041] In some more specific embodiments, the compositions of the present invention comprise, are substantially composed of, or are composed of the following components: 10-60% clethodim, 2-8% calcium dodecylbenzenesulfonate, about 0.5-5% of a first nonionic surfactant polyoxyethylene dehydrated sorbitan fatty acid ester, 1-6% of a second nonionic surfactant polyoxyethylene oleate, and about 30-75% solvent oil.

[0042] In some more specific embodiments, the composition of the present invention comprises, is substantially composed of, or is composed of the following components: about 25% clethodim, about 4% calcium dodecylbenzenesulfonate, about 0.8% of a first nonionic surfactant polyoxyethylene dehydrated sorbitan monooleate, about 3.2% of a second nonionic surfactant polyoxyethylene oleate, and the balance being solvent oil.

[0043] The compositions of the present invention can be formulated into pesticide formulations commonly used in pesticides, including but not limited to emulsions and emulsifiable concentrates, by methods known in the art.

[0044] In addition to the above-mentioned components, the composition of this invention may also contain one or more other excipients or adjuvants permitted for use in pesticides. Those skilled in the art can rationally select and use these excipients or adjuvants as needed.

[0045] The compositions of the present invention can be used alone or in combination with other herbicides, insecticides, fungicides, acaricides, plant growth regulators, plant nutrients and other active ingredients or preparations.

[0046] The dosage of the composition of the present invention varies depending on factors such as the target of application, and is usually 1g-10kg composition / ha, preferably 10g-5kg composition / ha, and more preferably 100g-5kg composition / ha.

[0047] Example

[0048] The present invention will be described in more detail below through specific embodiments, but the present invention is not limited to these embodiments. Any modifications or changes that do not depart from the spirit and scope of the present invention fall within the scope of the present invention.

[0049] In the following examples, the clethodim content was detected by HPLC under the following conditions:

[0050] Instrument: Normal-phase high-performance liquid chromatograph

[0051] Detection wavelength: 254nm (variable wavelength ultraviolet detector)

[0052] Flow rate: 1.0 ml / min

[0053] Column temperature: 30℃

[0054] Mobile phase: Cyclohexane: Dichloromethane: Glacial acetic acid = 50:50:0.5 (volume ratio).

[0055] The emulsion stability was tested as follows:

[0056] 1. Preparation of standard hard water: Prepared according to the methods in GB / T 43167-2023 Standard Hard Water for Pesticide Testing, specifically in sections 5.3.4.1.1, 5.3.4.1.2, and 5.3.4.2.4.

[0057] 2. Testing process

[0058] The instrument used is the CIPAC MT 36.3 instrument for emulsification and reemulsification.

[0059] The test was performed according to the operating procedure in CIPAC MT 36.3 Emulsifying and Remulsifying Properties.

[0060] The stability of clethodim emulsifiable concentrate was evaluated according to the following criteria:

[0061] Example 1

[0062] 5.5g of clethodim was placed in a 100ml round-bottom flask, and 12.9g of 150# solvent oil was added. After stirring for 5 minutes, 0.8g of calcium dodecylbenzenesulfonate, 0.16g of Tween 80 and 0.64g of polyoxyethylene oleate A110 were added respectively. After stirring for 10 minutes, the initial content of clethodim was determined by HPLC to be 25.3%. The emulsion stability was as follows: complete initial emulsification at 0h, no oil or paste at 0.5h, no oil or paste at 2h, 1ml of floating oil and 1ml of paste appeared at 24h (but could be completely re-emulsified), and no oil or paste at 24.5h. After heat storage at 54℃±2℃ for 2 weeks, the content of clethodim decreased to 24.5%, the degradation rate was 3.2%, and the emulsion stability was as follows: complete initial emulsification at 0h, no oil or paste at 0.5h, no oil or paste at 2h, 1.8ml of paste appeared at 24h (but could be completely re-emulsified), and 1ml of paste appeared at 24.5h.

[0063] Comparative Example 1

[0064] 5.5g of clethodim was placed in a 100ml round-bottom flask, and 12.9g of 150# solvent oil was added. After stirring for 5 minutes, 0.8g of calcium dodecylbenzenesulfonate and 0.8g of Tween 80 were added respectively. After stirring for 10 minutes, the initial content of clethodim was determined by HPLC to be 25.2%. Emulsion stability: complete emulsification at 0h, 1.5ml of cream appeared at 0.5h, 4ml of cream appeared at 2h, 8ml of cream appeared at 24h (but could be completely re-emulsified), and 1.5ml of cream appeared at 24.5h. The emulsion stability was not up to standard, so no further heat storage experiments were conducted.

[0065] The results of Comparative Example 1 show that when only the first nonionic surfactant is used and the second nonionic surfactant is not used, the resulting emulsion composition has unacceptable stability.

[0066] Comparative Example 2

[0067] 5.5g of clethodim was placed in a 100ml round-bottom flask, and 12.9g of 150# solvent oil was added. After stirring for 5 minutes, 0.8g of calcium dodecylbenzenesulfonate and 0.8g of polyoxyethylene oleate A110 were added respectively. After stirring for 10 minutes, the initial content of clethodim was determined by HPLC to be 25.2%. Emulsion stability: complete emulsification at 0h, 0.5ml of floating oil appeared at 0.5h, 1ml of floating oil appeared at 2h, 1.8ml of floating oil and 0.6ml of cream appeared at 24h (but could be completely re-emulsified), and 1ml of floating oil appeared at 24.5h. The emulsion stability was not up to standard, so no further heat storage experiments were conducted.

[0068] The results of Comparative Example 2 show that when only the second nonionic surfactant is used and the first nonionic surfactant is not used, the resulting emulsion composition has unacceptable stability.

[0069] Comparative Example 3

[0070] 5.5g of clethodim was placed in a 100ml round-bottom flask, and 12.7g of 150# solvent oil was added. After stirring for 5 minutes, 0.8g of calcium dodecylbenzenesulfonate, 0.5g of Tween 80, and 0.5g of castor oil polyoxyethylene ether CO40 were added respectively. After stirring for 10 minutes, the initial content of clethodim was determined by HPLC to be 25.2%. The emulsion stability was as follows: complete initial emulsification at 0h, no oil or paste at 0.5h, no oil or paste at 2h, 0.5ml of floating oil and 0.5ml of paste appeared at 24h (but could be completely re-emulsified), and no oil or paste at 24.5h. After being stored at 54℃±2℃ for 2 weeks, the content of clethodim decreased to 22.7%, the degradation rate was 9.9%, and the emulsion stability was as follows: complete initial emulsification at 0h, no oil or paste at 0.5h, no oil or paste at 2h, 2ml of paste appeared at 24h (but could be completely re-emulsified), and no oil or paste at 24.5h. The emulsion stability was qualified.

[0071] The results of Comparative Example 3 show that when castor oil polyoxyethylene ether CO40 is used instead of oleic acid polyoxyethylene ester as the second nonionic surfactant, the degradation rate of the resulting composition is close to 10%.

[0072] Comparative Example 4

[0073] 5.5g of clethodim was placed in a 100ml round-bottom flask, and 12.5g of 150# solvent oil was added. After stirring for 5 minutes, 1g of calcium dodecylbenzenesulfonate, 0.5g of tristyrylphenol polyoxyethylene ether 601#, and 0.5g of C12-C14 fatty alcohol polyoxyethylene ether MOA3 were added. After stirring for 10 minutes, the initial content of clethodim was determined by HPLC to be 25.3%. The emulsion stability was as follows: complete emulsification at 0h, 7ml of cream appeared at 0.5h, 1ml of floating oil and 7.5ml of cream appeared at 2h, 4.5ml of floating oil and 4.5ml of cream appeared at 24h (but could be completely re-emulsified), and 1.5ml of floating oil and 6.5ml of cream appeared at 24.5h. The emulsion stability was not up to standard, so no further heat storage experiments were conducted.

[0074] When the amounts of tristyrene-phenylphenol polyoxyethylene ether 601# and C12-C14 fatty alcohol polyoxyethylene ether MOA3 were changed to 1.7% and 3.4% respectively, the emulsion stability was as follows: complete initial emulsification at 0h, 7ml of cream at 0.5h, 1ml of floating oil and 8ml of cream at 2h, 4ml of floating oil and 6ml of cream at 24h (but could be completely re-emulsified), and 1ml of floating oil and 8ml of cream at 24.5h. The emulsion stability was also unqualified, so no further heat storage tests were conducted.

[0075] When the amounts of tristyrene-phenylphenol polyoxyethylene ether 601# and C12-C14 fatty alcohol polyoxyethylene ether MOA3 were changed to 1.3% and 3.9% respectively, the emulsion stability was as follows: complete initial emulsification at 0h, 11.5ml of cream appeared at 0.5h, 1ml of floating oil and 9.5ml of cream appeared at 2h, 6ml of floating oil and 2ml of cream appeared at 24h (but could be completely re-emulsified), and 2ml of floating oil and 5.5ml of cream appeared at 24.5h. The emulsion stability was also unqualified, so no further heat storage tests were conducted.

[0076] The results of Comparative Example 4 show that when tristyrylphenol polyoxyethylene ether 601# and C12-C14 fatty alcohol polyoxyethylene ether MOA3 are used as nonionic surfactants, the resulting emulsion composition has unsatisfactory stability.

[0077] Comparative Example 5

[0078] 5.5g of clethodim was placed in a 100ml round-bottom flask, and 12.5g of 150# solvent oil was added. After stirring for 5 minutes, 1g of calcium dodecylbenzenesulfonate, 0.5g of tristyrylphenol polyoxyethylene ether 601#, and 0.5g of Tween 80 were added respectively. After stirring for 10 minutes, the initial content of clethodim was determined by HPLC to be 25.1%. Emulsion stability: complete initial emulsification at 0h, 2.5ml of cream appeared at 0.5h, 2.8ml of cream appeared at 2h, 4.5ml of cream appeared at 24h (but could be completely re-emulsified), and 2.3ml of cream appeared at 24.5h. The emulsion stability was not up to standard, so no further heat storage experiments were conducted.

[0079] When the amounts of tristyrene-based phenolic polyoxyethylene ether 601# and Tween 80 were changed to 1.7% and 3.4% respectively, the emulsion stability was as follows: complete initial emulsification at 0h, 2.3ml of cream appeared at 0.5h, 3.5ml of cream appeared at 2h, 5.5ml of cream appeared at 24h (but could be completely re-emulsified), and 2.3ml of cream appeared at 24.5h. The emulsion stability was also unqualified, so no further heat storage tests were conducted.

[0080] When the amounts of tristyrene-based phenolic polyoxyethylene ether 601# and Tween 80 were changed to 1.3% and 3.9% respectively, the emulsion stability was as follows: complete initial emulsification at 0h, 2.5ml of cream appeared at 0.5h, 4.3ml of cream appeared at 2h, 6ml of cream appeared at 24h (but could be completely re-emulsified), and 2.2ml of cream appeared at 24.5h. The emulsion stability of the oil was also unqualified, so no further heat storage tests were conducted.

[0081] The results of Comparative Example 5 show that when styrene-phenylphenol polyoxyethylene ether 601# and Tween 80 are used as nonionic surfactants, the resulting emulsion composition does not meet the stability requirements.

[0082] Comparative Example 6

[0083] 5.5g of clethodim was placed in a 100ml round-bottom flask, and 12.5g of 150# solvent oil was added. After stirring for 5 minutes, 1g of calcium dodecylbenzenesulfonate, 0.5g of C12-C14 fatty alcohol polyoxyethylene ether MOA3, and 0.5g of Tween 80 were added respectively. After stirring for 10 minutes, the initial content of clethodim was determined by HPLC to be 25.1%. Emulsion stability: complete initial emulsification at 0h, 1ml of floating oil appeared at 0.5h, 1ml of floating oil appeared at 2h, 3ml of floating oil appeared at 24h (but could be completely re-emulsified), and 1ml of floating oil appeared at 24.5h. The emulsion stability was not up to standard, so no further heat storage experiments were conducted.

[0084] When the amounts of C12-C14 fatty alcohol polyoxyethylene ether MOA3 and Tween 80 were changed to 1.7% and 3.4% respectively, the emulsion stability was as follows: complete initial emulsification at 0h, 3ml of cream appeared at 0.5h, 4ml of cream appeared at 2h, 1ml of floating oil and 4ml of cream appeared at 24h (but could be completely re-emulsified), and 3ml of cream appeared at 24.5h. The emulsion stability was also unqualified, so no further heat storage tests were conducted.

[0085] When the amounts of C12-C14 fatty alcohol polyoxyethylene ether MOA3 and Tween 80 were changed to 3.4% and 1.7% respectively, the emulsion stability was as follows: complete initial emulsification at 0h, 0.5ml floating oil appeared at 0.5h, 1.1ml floating oil appeared at 2h, 3.5ml floating oil and 0.5ml cream appeared at 24h (but could be completely re-emulsified), and 1ml floating oil appeared at 24.5h. The emulsion stability was also unqualified, so no further heat storage tests were conducted.

[0086] The results of Comparative Example 6 show that when C12-C14 fatty alcohol polyoxyethylene ether MOA3 and Tween 80 are used as nonionic surfactants, the resulting emulsion composition has unsatisfactory stability.

Claims

1. A clethodim composition, comprising, relative to the total mass of the composition: (a) 1-70%, preferably 10-60% of clethodim; (b) 0.1-10%, preferably 2-8%, of anionic surfactants; (c) 0.1-10%, preferably 0.5-5%, of a first nonionic surfactant, wherein the first nonionic surfactant is polyoxyethylene dehydrated sorbitan fatty acid ester; (d) 0.1-10%, preferably 1-6%, of a second nonionic surfactant, wherein the second nonionic surfactant is oleic acid polyoxyethylene ester; (e) 20-85%, preferably 30-75% solvent.

2. The composition of claim 1, wherein the anionic surfactant is a sulfonate type, preferably C 8-20 Alkylbenzene sulfonates or C 8-20 Alkyl sulfonate, more preferably C 10-18 Alkylbenzene sulfonate, more preferably C 12-18 Alkylbenzene sulfonates, particularly calcium dodecylbenzene sulfonate or sodium dodecylbenzene sulfonate.

3. The composition of claim 1 or 2, wherein the average degree of polymerization of the first nonionic surfactant polyoxyethylene dehydrated sorbitan fatty acid ester is 1 to 200, more preferably 1 to 100, further preferably 1 to 50, and even more preferably 1 to 30.

4. The composition of any one of claims 1 to 3, wherein the first nonionic surfactant, polyoxyethylene sorbitan fatty acid ester, is a Tween series product, preferably polyoxyethylene sorbitan monooleate.

5. The composition according to any one of claims 1 to 4, wherein the average degree of polymerization of the second nonionic surfactant oleic acid polyoxyethylene ester is 1 to 200, more preferably 1 to 100, further preferably 1 to 50, and even more preferably 1 to 30.

6. The composition according to any one of claims 1 to 5, wherein the solvent is a solvent oil, preferably 150# solvent oil or 200# solvent oil.

7. The composition according to any one of claims 1 to 6, wherein the total content of the anionic surfactant, the first nonionic surfactant, and the second nonionic surfactant relative to the total mass of the composition is not more than 15%, preferably not more than 12%, and more preferably 8-10%.

8. The composition according to any one of claims 1 to 6, wherein, relative to the total mass of the composition, it comprises 10-60% clethodim and 2-8% C. 10-18 Alkylbenzene sulfonate, 0.5-5% of a first nonionic surfactant, 1-6% of a second nonionic surfactant, and 30-75% of solvent.

9. The composition according to any one of claims 2 to 8, wherein C 10-18 Alkylbenzene sulfonate is calcium dodecylbenzene sulfonate.