Weeding composition containing picloram

Abstract

The invention provides a synergistic weeding composition containing picloram. The synergistic weeding composition comprises an effective component and an auxiliary agent, the effective components comprise 2, 4-dichlorphenoxyacetic acid (2, 4-D) and picloram, and the weight ratio of the 2, 4-dichlorphenoxyacetic acid (2, 4-D) to the picloram is (1: 15)-(18: 1); the auxiliary agent comprises a basic auxiliary agent and a functional auxiliary agent, and the functional auxiliary agent is a combination of a gramineous weed synergist and an anti-drifting agent; the weight percentage of the effective components in the weeding composition is 5%-90%, and the weight percentage of the auxiliary agent in the weeding composition is 10%-95%. According to the scheme, through collaborative screening of the solvent and the auxiliaries, the heat storage (54 + / -2 DEG C, 14 days) layering rate of the soluble concentrate is smaller than or equal to 1%, the suspension rate is larger than or equal to 98%, the stability is remarkably superior to that of an existing compound preparation, and the soluble concentrate is suitable for the uncultivated land complex storage and use environment.

Description

TECHNICAL FIELD

[0001] The application discloses a herbicidal composition containing aminoclopyralid, belongs to the field of herbicides, and is used for preventing and treating non-cultivated land weeds. BACKGROUND

[0002] To avoid the competition of weeds and crops for nutrients, water, light and space, reduce the risk of disease and pest transmission due to weed growth, and improve the utilization value of non-cultivated land in agricultural operation, land planning and the like, non-cultivated land weeds are usually also applied with some herbicides.

[0003] 2,4-D is a phenoxyacetic acid selective hormone herbicide, which can be absorbed by the roots, stems and leaves of plants, conducted through the phloem and xylem, and interfere with the hormone balance in the plant body, thereby causing abnormal growth of weeds and eventually leading to death. It has good control effect on a variety of broadleaf weeds, but has two major defects: one is that it has poor control effect on grass weeds such as Digitaria sanguinalis and Echinochloa crus-galli, and perennial weeds such as Sonchus oleraceus and Sonchus arvensis (the control effect on plants is usually less than 70%); the other is that long-term single use has led to significant resistance of weeds such as Descurainia sophia and Galium aparine, and the use amount needs to be continuously increased to maintain the control effect, which not only increases the cost but also increases the environmental burden. Aminoclopyralid is a pyridine carboxylic acid herbicide, which mainly absorbs and conducts through the leaf surface, and has outstanding control effect on broadleaf weeds such as Asteraceae and Leguminosae, and perennial weeds such as Sonchus oleraceus (fresh weight control effect can reach more than 90%), but has almost no activity on grass weeds, and weeds (such as sow thistle) are easy to produce resistance by increasing the activity of detoxification enzymes when used alone, and the half-life of aminoclopyralid in soil is relatively long (about 30-60 days), which may cause drift phytotoxicity to surrounding sensitive crops (such as beans and cotton). To solve the above problems, there are simple attempts of 2,4-D and aminoclopyralid in the prior art, but such schemes have three major technical defects: one is that only the proportion of the two active ingredients is considered (usually 1:5-5:1), and the synergistic effect of the active ingredients and adjuvants is not considered, which leads to poor stability of the preparation (such as the delamination rate of the suspension agent is more than 5%), poor dispersion of the liquid medicine, and affects the field control effect; the second is that the control spectrum is not optimized for the characteristics of non-cultivated land "complex weed species and inconsistent growth period", and the synergistic control effect on grass weeds and perennial weeds is not as expected; the third is that the mechanism of the resistance delay of the compound system is not clear, and the problem of rapid development of weed resistance cannot be fundamentally solved. SUMMARY

[0004] In view of the defects in the prior art, the core purpose of the present application is to provide a synergistic herbicidal composition containing 2,4-D and aminoclopyralid, which realizes the following objectives through the synergistic design of "active ingredient proportion optimization + functional adjuvant compound + dosage form adaptation": 1. Significantly improve the comprehensive control effect on non-cultivated broadleaf weeds, grass weeds and perennial weeds, with a total control effect of ≥90% 30 days after application; 2. Reduce the active ingredient dosage by 15%-25%, while delaying the development of weed resistance and extending the service life of the pesticide; 3. Improve the stability and environmental compatibility of the preparation, avoid drift and phytotoxicity, and adapt to complex non-cultivated use scenarios.

[0005] A herbicidal composition with 2,4-D and aminocyclopyrachlor as active ingredients, the weight ratio of 2,4-D to aminocyclopyrachlor in the herbicidal composition is 1:15-18:1, preferably 1:8-12:1, and more preferably 1:4-8:1; the weight percentage of active ingredients in the herbicidal composition is 5%-90%, and the adjuvant (total percentage 10%-95%) includes basic adjuvant and functional adjuvant, wherein the basic adjuvant is at least three of solvent, dispersant, wetting agent, stabilizer, antifreeze, defoamer, and preservative, and the functional adjuvant is a combination of grass weed synergist (such as lignin sulfonate polyoxyethylene ether, accounting for 0.5%-3%) and anti-drift agent (such as N-lauroyl-N-methyl glucamide, accounting for 0.1%-1%).

[0006] Further, the active ingredients in the composition can be selected from one or more of 2,4-D technical material, 2,4-D sodium salt, and 2,4-D dimethylamine salt; and the aminocyclopyrachlor can be selected from one or both of aminocyclopyrachlor water agent and aminocyclopyrachlor technical material.

[0007] Further, the solvent in the basic adjuvant of the composition can be selected from one or more of water, a mixture of N,N-dimethylformamide and ethanol (mixed weight ratio 3:1), or cyclohexanone, dimethyl sulfoxide; the dispersant: preferably one or both of sodium lignosulfonate and naphthalene sulfonate formaldehyde condensate; the wetting agent: preferably one or both of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; the stabilizer: preferably one or both of epichlorohydrin and triphenyl phosphite; the antifreeze: preferably one or both of ethylene glycol and propylene glycol; the defoamer: preferably silicone defoamer (such as polydimethylsiloxane); the preservative: preferably one or both of sodium benzoate and potassium sorbate; and one or more of methanol, ethanol, acetone, butanone, cyclohexanone, N,N-dimethylformamide, dimethyl sulfoxide, toluene, xylene, and solvent oil.

[0008] Further, the functional adjuvant of the composition is grass weed synergist: preferably lignin sulfonate polyoxyethylene ether (which can destroy the wax layer of grass weeds and promote the penetration and absorption of active ingredients); and anti-drift agent: preferably N-lauroyl-N-methyl glucamide (which can reduce the surface tension of the pesticide solution to 25-30 mN / m and improve the uniformity of the droplet size to 100-200 μm.

[0009] The herbicidal composition can be prepared into an agricultural dosage form commonly used, such as a soluble liquid, a suspension, and an emulsion in water, wherein the 2,4-D·aminopyralid soluble liquid with a content of 25%-30% is the optimal dosage form (high stability, convenient use, and low drift risk), and the specific preparation method is as follows: According to parts by weight, 2,4-D dimethylamine salt 20 parts, aminopyralid technical material 5 parts (the weight ratio of the two is 4:1), solvent (N,N-dimethylformamide: ethanol = 3:1) 30 parts, dispersing agent sodium lignosulfonate 3 parts, wetting agent sodium dodecyl sulfate 2 parts, stabilizer epichlorohydrin 0.5 parts, antifreeze ethylene glycol 3 parts, defoaming agent polydimethylsiloxane 0.3 parts, preservative sodium benzoate 0.2 parts, graminaceous weed synergist lignosulfonate polyoxyethylene ether 1 part, anti-drift agent N-lauroyl-N-methyl glucamide 0.5 parts, and water are added to 100 parts.

[0010] 2,4-D dimethylamine salt and aminopyralid technical material are added into the solvent, stirred at a constant temperature of 50-60 DEG C in a water bath at a speed of 300 r / min for 30 minutes, until the effective components are completely dissolved, and a transparent mother liquor is obtained.

[0011] The dispersing agent, the wetting agent, the stabilizer, the antifreeze, the defoaming agent, and the preservative are sequentially added into the mother liquor, the temperature is kept at 50-60 DEG C, and stirring is carried out at a speed of 200 r / min for 15 minutes, so as to ensure that the adjuvants are completely dispersed.

[0012] The graminaceous weed synergist and the anti-drift agent are added, and stirring is continuously carried out for 10 minutes.

[0013] The measured water is slowly added, the speed is adjusted to 300 r / min, and stirring is carried out for 20 minutes, so as to obtain a uniform mixed solution.

[0014] The mixed solution is filtered through a 0.45 mu m microporous filter membrane, impurities are removed, and thus 25.8% 2,4-D·aminopyralid soluble liquid is prepared.

[0015] The present application is mainly used for non-cultivated land weed control, including highway lines, railway slopes, mine reclamation areas, airport runway perimeters, power transmission line corridors and other areas; it is suitable for broadleaf weeds such as Descurainia sophia, Galium aparine, Chenopodium album, Digitaria sanguinalis, Eleusine indica and Setaria viridis, and perennial weeds such as Sonchus oleraceus, Sonchus arvensis and Phragmites australis; at the 3-5 leaf stage (the vigorous growth period) of weeds, the soluble liquid of the present application is diluted by 500-800 times, and uniform spraying is carried out by using a knapsack sprayer or a motorized sprayer, so as to ensure that the weed leaves are fully coated.

[0016] This product, a functional adjuvant combination of "grass weed synergist (lignin sulfonate polyoxyethylene ether) + anti-drift agent (N-lauroyl-N-methylglucosamine)," not only solves the problem of poor control efficacy of 2,4-D against grass weeds, but also reduces the amount of herbicide drift, filling the technological gap in non-arable land herbicides that "balance broad-spectrum efficacy with environmental safety." Furthermore, through the synergistic screening of solvents and adjuvants, the soluble formulation exhibits a stratification rate of ≤1% and a suspension rate of ≥98% during heat storage (54℃±2℃, 14 days), demonstrating significantly better stability than existing compound formulations and making it suitable for the complex storage and use environments of non-arable land. Detailed Implementation

[0017] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0018] To verify the technical effects of the present invention, seven sets of examples (different proportions of active ingredients, combinations of adjuvants, and dosage forms) were designed, and two control groups (existing single-agent formulations) were set up. The specific parameters are shown in Table 1 below: Table 1. Components and parameters of the examples and controls

[0019] According to national standards, the thermal stability (54℃±2℃, 14 days), cold storage stability (-10℃±2℃, 7 days), and suspension rate of each example and control formulation were tested. Example 1 (optimal adjuvant combination + soluble concentrate), Example 3 (no functional adjuvant + soluble concentrate), and Example 5 (optimal adjuvant combination + suspension concentrate) were selected as representative samples for testing (based on the "bracketing method" design, covering two key variables: presence or absence of adjuvants and dosage form differences, which can be used to deduce the stability patterns of other samples). The results are shown in Table 2 below. Table 2 Results of Formulation Stability Tests

[0020] According to the test results, Example 1 (a soluble concentrate containing functional adjuvants) showed the best stability, with a heat storage stratification rate of only 0.8% and a suspension rate of 98.2%, which was significantly better than Example 3 without functional adjuvants and controls 1 and 2, proving that functional adjuvants can effectively improve the dispersibility and stability of the formulation. Example 5 (a suspension concentrate) showed stability that met the requirements for agricultural use, but was slightly lower than that of the soluble concentrate (Example 1), further verifying that the soluble concentrate is the optimal formulation.

[0021] Based on the above test results, the present invention conducted field efficacy tests on the compound formulations obtained in Examples 1-7.

[0022] Test reagents: The compound preparations obtained in Examples 1-7 of this invention.

[0023] Control reagents: 720 g / L 2,4-D dimethylamine salt soluble concentrate (laboratory-made); 24% aminopyridine acid soluble concentrate (Anhui Yinong Chemical Co., Ltd.).

[0024] Experimental conditions and application methods: Experimental subjects: A farmland with relatively uniform weed growth was selected, with the main weed species being shepherd's purse (broadleaf weed), crabgrass (grass weed), and thistle (perennial weed). Experimental design: Set up the following treatment groups: Treatment groups 1-7: The 2,4-D-aminochloropyridine acid compound preparations prepared in Examples 1-7 were used, with an effective ingredient dosage of 150 g / ha; Treatment group 8: 720 g / L 2,4-D dimethylamine salt soluble concentrate, with an active ingredient dosage of 150 g / ha; Treatment group 9: 24% aminopyridine acid soluble concentrate, with an active ingredient dosage of 150 g / ha; The experimental site was located in Yichang City, Hubei Province, with a pH of 6.8 and soil organic matter content of 1.1%. A MATABI-16 backpack manual sprayer was used for uniform spraying. The entire experiment involved one application of the pesticide, using 900 L / hm² of water. 2 The absolute value (numerical measurement) survey method was adopted, with 4 sampling points taken in each community, and each sampling point being 0.25m. 2 The number of weeds and their fresh weight (g) were assessed 15 days and 30 days after application. The efficacy was calculated based on the results, and a multiple range test was used for significance analysis. The effects of each herbicide treatment on maize were continuously monitored post-application, and yield was measured at harvest. No other herbicides were applied during the experiment.

[0025] Control efficacy = [(Number of weeds in control area - Number of weeds in treatment area) / Number of weeds in control area] × 100%; Fresh weight control efficacy = [(fresh weight of weeds in control area - fresh weight of weeds in treatment area) / fresh weight of weeds in control area] × 100%; Table 3. Statistical table of prevention and control effects 15 days after application of the drug.

[0026] Table 4. Statistical table of prevention and control effects 30 days after application.

[0027] As shown in the table above, the efficacy survey results indicate that Example 1 (25.8% soluble concentrate, active ingredient ratio 4:1 + functional adjuvant) achieved a total efficacy of 93.36% 15 days after application and 93.92% 30 days after application, significantly higher than Control 1 (75.33%, 76.02%) and Control 2 (83.98%, 84.58%). Furthermore, it showed significant differences from other examples (such as Examples 2-7) (P<0.05), demonstrating that the synergistic design of "preferred active ingredient ratio + functional adjuvant" can produce a strong synergistic effect, consistent with the core objective of this invention: "improving efficacy." Example 1 showed that the plant control efficacy against the grass weed *Digitaria sanguinalis* (93.22% 30 days after application) was 35.5% higher than that of control 1 (68.80%). The plant control efficacy against the perennial weed *Sonchus oleraceus* (95.04%) was comparable to that of control 2 (95.03%). The plant control efficacy against the broadleaf weed *Desmodium styracifolium* (93.49%) was close to that of control 1 (92.47%). This achieved full coverage control of "broadleaf + grass + perennial" weeds, overcoming the shortcomings of existing single-agent herbicides with a narrow spectrum. Compared with Example 3 (without functional adjuvant), Example 1 (containing functional adjuvant) showed a 12.69% increase in overall control efficacy 30 days after application, with a 16.94% increase in control efficacy against crabgrass. This demonstrates that the lignin sulfonate polyoxyethylene ether (LISU) effectively enhances the control efficacy against gramineous weeds. Furthermore, droplet size analysis showed that the average droplet size of Example 1 was 152 μm, with a drift of 1.2 mg / m³. 2 Compared to Example 3 (drift amount 3.8 mg / m³) 2 The herbicide concentration was reduced by 71.1%, verifying the environmental safety of the anti-drift agent (N-lauroyl-N-methylglucosamine). In Example 2, the 25.8% 2,4-D·aminopyridine acid soluble concentrate showed the best control effect, with a control efficacy of 93.36% 15 days after application and 93.92% 30 days after application, significantly better than the two single-agent formulations and other combinations. Combined from the two investigations, the sample prepared in Example 2 not only improved the rapid-acting properties but also broadened the herbicidal spectrum, reducing phytotoxicity.

[0028] To verify the delaying effect of the composition of the present invention on herbicide resistance, a population of *Hemiberlesia lataniae* that had developed moderate resistance to 2,4-D was selected (referring to NY / T 1859.2-2010 "Guidelines for Pesticide Resistance Risk Assessment"). Three consecutive generations of treatment were performed using both Example 1 and Control 1, with each generation applying 150 g / hm² of the active ingredient. 2 After harvesting the seeds, the resistance ratio of the next generation was determined, and the results are shown in Table 5 below: Table 5. Changes in resistance folds after three consecutive generations of *Artemisia annua* treatment.

[0029] After three consecutive generations of treatment, the resistance multiple of *Hedysarum heterotropoides* in Example 1 increased only from 5.2 to 5.5, with a resistance growth rate of 0.1 times per generation, significantly lower than that of Control Group 1 (resistance growth rate of 1.17 times per generation). This demonstrates that the composition of the present invention can effectively delay the development of herbicide resistance in weeds and extend the lifespan of the herbicide through a "dual mechanism of action (hormone interference + photosynthesis inhibition) + reduced herbicide use," which meets the technical objective of "delaying herbicide resistance" of the present invention.

[0030] Based on the above test results, the optimal formulation of this invention (Example 1: 25.8% 2,4-D·aminopyridine acid soluble concentrate, active ingredient ratio 4:1 + lignin sulfonate polyoxyethylene ether 1% + N-lauroyl-N-methylglucosamine 0.5%) has a heat storage stratification rate of 0.8% and a suspension rate of 98.2%, demonstrating excellent formulation stability. The total control efficacy is 93.92% 30 days after application, significantly superior to existing single-agent formulations, and achieves full coverage control of multiple weed types. The resistance growth rate is only 0.1 times / generation, while the active ingredient dosage is reduced by 20% compared to existing technologies, combining economic and environmental benefits and fully meeting the technical requirements for weed control in non-arable land.

Claims

1. A synergistic herbicidal composition containing aminopyridine acid, characterized in that, The composition includes an active ingredient and adjuvants; the active ingredient is composed of 2,4-dichlorophenoxyacetic acid (2,4-D) and aminopyridine acid in a weight ratio of 1:15-18:1; the adjuvants include basic adjuvants and functional adjuvants, the functional adjuvants being a combination of gramineous weed synergists and anti-drift agents; the active ingredient accounts for 5%-90% of the weight percentage of the herbicidal composition, and the adjuvants account for 10%-95% of the weight percentage of the herbicidal composition.

2. The herbicidal composition according to claim 1, characterized in that, The weight ratio of 2,4-D to aminochloropyridine acid is 1:8-12:1; preferably, the weight ratio of 2,4-D to aminochloropyridine acid is 1:4-8:

1.

3. The herbicidal composition according to claim 1, characterized in that, The herbicide is a lignin sulfonate polyoxyethylene ether, and the weight percentage of the lignin sulfonate polyoxyethylene ether in the herbicide composition is 0.5%-3%; the anti-drift agent is N-lauroyl-N-methylglucosamine, and the weight percentage of the N-lauroyl-N-methylglucosamine in the herbicide composition is 0.1%-1%.

4. The herbicidal composition according to claim 1, characterized in that, The lignin sulfonate polyoxyethylene ether is a self-made additive, which is produced by sequentially adding, hydrogenating and amidating glucose, methylamine and methyl laurate as raw materials to generate N-lauroyl-N-methylglucosamine.

5. The herbicidal composition according to claim 1, characterized in that, The N-lauroyl-N-methylglucosamine is a self-made adjuvant obtained by condensation reaction of lignin sulfonate with ethylene oxide.

6. The herbicidal composition according to claim 1, characterized in that, The basic additives are selected from at least three of the following: solvents, dispersants, wetting agents, stabilizers, antifreeze agents, defoamers, and preservatives; wherein: The solvent is selected from one or more of N,N-dimethylformamide and ethanol, cyclohexanone, and dimethyl sulfoxide, and the solvent accounts for 5%-50% by weight in the herbicidal composition. The dispersant is selected from one or two of sodium lignosulfonate and naphthalenesulfonate formaldehyde condensate, and the weight percentage of the dispersant in the herbicidal composition is 1%-8%. The wetting agent is selected from one or two of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate, and the weight percentage of the wetting agent in the herbicidal composition is 1%-5%. The stabilizer is selected from one or two of epichlorohydrin and triphenyl phosphite, and the stabilizer is 0.1%-3% by weight in the herbicidal composition; The antifreeze agent is selected from one or both of ethylene glycol and propylene glycol, and the weight percentage of the antifreeze agent in the herbicidal composition is 1%-5%. The defoamer is an organosilicone defoamer, and the weight percentage of the defoamer in the herbicidal composition is 0.1%-2%. The preservative is selected from one or two of sodium benzoate and potassium sorbate, and the preservative is present in the herbicidal composition at a weight percentage of 0.1%-2%.

7. The herbicidal composition according to claim 1, characterized in that, The 2,4-D is selected from one or more of 2,4-D sodium salt, 2,4-D dimethylamine salt, and 2,4-D isooctyl ester; the aminochloropyridine acid is selected from one or two of aminochloropyridine acid aqueous solution and aminochloropyridine acid technical.

8. The herbicidal composition according to claim 1, characterized in that, The herbicidal composition is in the form of a soluble concentrate, a suspension concentrate, or an emulsion; preferably, the herbicidal composition is in the form of a soluble concentrate, and the active ingredient in the soluble concentrate has a weight percentage of 25%-30%.

9. The herbicidal composition according to claim 6, characterized in that, When the herbicidal composition is a 25.8% 2,4-D-aminopyridine soluble concentrate, its components, by weight, include: 20 parts of 2,4-D dimethylamine salt, 5 parts of aminopyridine technical grade, 30 parts of solvent (N,N-dimethylformamide:ethanol = 3:1), 3 parts of sodium lignosulfonate, 2 parts of sodium dodecyl sulfate, 0.5 parts of epichlorohydrin, 3 parts of ethylene glycol, 0.3 parts of polydimethylsiloxane, 0.2 parts of sodium benzoate, 1 part of lignosulfonate polyoxyethylene ether, 0.5 parts of N-lauroyl-N-methylglucosamine, and water to a total of 100 parts.

10. A method for preparing a herbicidal composition according to any one of claims 1-7, characterized in that, When the herbicidal composition is a soluble concentrate, the preparation method includes the following steps: S1: Weigh 2,4-D, aminochloropyridine acid and solvent according to the weight parts, stir at 200r / min for 30 minutes under constant temperature water bath at 50-60℃ until the active ingredients are completely dissolved to obtain a transparent mother liquor; S2: Add dispersant, wetting agent, stabilizer, antifreeze, defoamer and preservative to the transparent mother liquor, maintain the temperature at 50-60℃, and stir at 300r / min for 15 minutes to obtain mixture A; S3: Add a grass weed synergist and an anti-drift agent to the mixture A, and continue stirring for 10 minutes to obtain mixture B; S4: Add the remaining water to the mixture B, stir at 300 r / min for 20 minutes, and filter through a 0.45 μm microporous membrane to obtain the soluble solvent.

Images