A suspension containing fluopyram and copper oxyquinoline and a method for preparing the same

Abstract

The application provides a fluopimycin and quinoline copper suspension agent and a preparation method thereof, and belongs to the technical field of fungicide preparation. The fluopimycin and quinoline copper suspension agent comprises fluopimycin 1-10%, quinoline copper 1-50% and the rest of agricultural acceptable wetting dispersant 1-20%, thickening agent 0.1-2%, antifreeze 1-10%, preservative 0.01-0.3%, defoaming agent 0.1-5%, synergist 3-6% and deionized water, according to the weight percentage. The suspension agent improves the stability of the pesticide, has the effects of compatible control, delay of development of drug resistance and improvement of safety.

Description

Technical Field

[0001] This invention belongs to the field of pesticide formulation technology, and particularly relates to a suspension containing fluopyram and quinoline copper and its preparation method. Background Technology

[0002] The widespread use of chemical pesticides has played a significant role in ensuring high and stable crop yields. However, traditional pesticide formulations suffer from drawbacks such as high organic solvent usage, dust drift, and poor dispersibility, resulting in the vast majority of pesticides being lost into the environment, with less than 1% reaching the target site, thus causing serious environmental pollution.

[0003] Fluopyram is a novel benzamide fungicide that inhibits mitochondrial respiration by blocking electron transfer from succinate dehydrogenase in the respiratory chain. It is mainly used on broadleaf crops to control diseases caused by *Agropyron cristatum*. It has good control effects on downy mildew and powdery mildew in vegetables such as cucumbers and zucchini, as well as downy mildew in fruit trees, and other diseases caused by the fungus. The chemical name of fluopyram is N-[2-[3-chloro-5-(trifluoromethyl)-2-pyridine]ethyl]-2-(trifluoromethyl)benzamide, and its solubility in water is 16 mg / L (20℃).

[0004] Quinoline copper is a chelated organic ketone broad-spectrum fungicide. It forms a dense protective film on the crop surface, blocking contact between pathogens and the crop, preventing pathogen infection. It can also act inside pathogens, inhibiting the activity and translocation of their main transport mechanisms, thereby killing the pathogens. Quinoline copper is effective against fungal and bacterial diseases and is suitable for controlling various diseases in fruit trees, vegetables, melons, tobacco, and other crops. The chemical name of quinoline copper is bis(quinoline-8-hydroxy-O,N)copper, and its solubility in water is 1.04 mg / L (20℃).

[0005] CN107660539A discloses a fungicide composition containing fluopyram and quinoline copper. The fungicide composition is a binary compound of fluopyram and quinoline copper, with the remainder being auxiliary components. The mass ratio of the active ingredient fluopyram to quinoline copper is 1-25:25-1. The CN107660539A also discloses that when the formulation is a suspension, the adjuvants include pesticide adjuvants such as dispersants, antifreeze agents, thickeners, defoamers, penetration enhancers, and pH adjusters.

[0006] Existing pesticide suspensions containing fluopyram and quinoline copper have problems in practical use, such as lower-than-expected efficacy, poor stability of quinoline copper leading to stratification and crystallization, which seriously affect the normal use of pesticides during production and processing. This invention provides a suspension containing fluopyram and quinoline copper and its preparation method. This formulation can significantly improve the stability of the active ingredients, has strong wetting and penetrating ability, and is environmentally safe. Summary of the Invention

[0007] The present invention addresses the shortcomings of the prior art by providing a suspension containing fluopyram and quinoline copper and its preparation method, thereby improving the stability of fluopyram and quinoline copper, and having the effects of treating both, delaying the development of drug resistance, and improving safety.

[0008] To achieve the above-mentioned objectives, the technical solution adopted in this invention is as follows: a suspension containing fluopyram and quinoline copper, comprising, by weight percentage: 1%–10% fluopyram, 1%–50% quinoline copper, with the remainder being 1%–20% agriculturally acceptable wetting and dispersing agent, 0.1%–2% thickener, 1%–10% antifreeze agent, 0.01%–0.3% preservative, 0.1%–5% defoamer, 3%–6% synergist, and deionized water to bring the total to 100%.

[0009] Furthermore, the mass ratio of the active ingredient fluopyram to quinoline copper is 5:1 to 1:14;

[0010] Furthermore, the mass ratio of the active ingredient fluopyram to quinoline copper is 2:1 to 1:10;

[0011] Furthermore, the mass ratio of fluopyram to quinoline copper is 2:1, 1:1, 2:3, 1:2, 1:3, 1:6, 1:8, 1:10, or 1:14.

[0012] Furthermore, calculated by weight percentage, it includes: 5% fluopyram, 30% quinoline copper, the remainder being agriculturally acceptable wetting and dispersing agents 6%–8%, thickeners 1.2%, antifreeze agents 5%, preservatives 0.02%, defoamers 0.5%, synergists 5%, and deionized water to make up to 100%.

[0013] Furthermore, the mass ratio of the wetting and dispersing agent is 6% to 8%;

[0014] Furthermore, the mass ratio of the wetting and dispersing agent is 6%, 6.5%, 7%, 7.5%, 8%, or any value between the above values;

[0015] Furthermore, the wetting and dispersing agent is any one or more of the following: polyether, phenethylphenol polyether phosphate salt, Guerbert alcohol polyoxyethylene ether, polycarboxylate, naphthalene sulfonate, isotridecyl alcohol polyoxyethylene ether, alkyl sulfonate, lignin sulfonate, sodium dioctyl sulfosuccinate, tristyrylphenol polyoxyethylene polyoxypropylene ether, octadecyl phosphate, and fatty alcohol polyoxyethylene ether.

[0016] Furthermore, the wetting and dispersing agent is any one or more selected from polyether, phenethylphenol polyether phosphate salt, Guerbert alcohol polyoxyethylene ether, polycarboxylate, alkyl glycoside, naphthalene sulfonate, and lignin sulfonate.

[0017] Furthermore, the wetting and dispersing agent comprises polyether and phenethylphenol polyether phosphate salt in a mass ratio of 1:1;

[0018] Furthermore, the wetting and dispersing comprises Guerbert alcohol polyoxyethylene ether and naphthalene sulfonate in a mass ratio of 2:1;

[0019] Furthermore, the wetting and dispersing agent comprises phenethylphenol polyether phosphate salt and Guerbert alcohol polyoxyethylene ether in a mass ratio of 2:1;

[0020] Furthermore, the wetting and dispersing agent comprises polyether and Guerbert alcohol polyoxyethylene ether in a mass ratio of 3:2;

[0021] Furthermore, the wetting and dispersing agent is polyether, phenethylphenol polyether phosphate salt, and Guerbert alcohol polyoxyethylene ether, in a mass ratio of 3:3:2;

[0022] Furthermore, the wetting and dispersing agent is polyether, phenethylphenol polyether phosphate salt, and polycarboxylate salt, in a mass ratio of 3:3:1;

[0023] Furthermore, the wetting and dispersing agent is phenylethylphenol polyether phosphate salt, Guerbert alcohol polyoxyethylene ether, and naphthalene sulfonate, in a mass ratio of 4:2:1;

[0024] Furthermore, the wetting and dispersing agent is polyether, Gelbert alcohol polyoxyethylene ether, and naphthalene sulfonate, in a mass ratio of 3:2:1;

[0025] Furthermore, the wetting and dispersing agent is sodium lignosulfonate, Gelbert alcohol polyoxyethylene ether, and naphthalene sulfonate, in a mass ratio of 3:2:1.

[0026] Furthermore, the thickener is a mixture of magnesium aluminum silicate and xanthan gum.

[0027] Furthermore, the mass ratio of magnesium aluminum silicate to xanthan gum is (3-6):1;

[0028] Furthermore, the mass ratio of magnesium aluminum silicate to xanthan gum is 3:1, 4:1, 5:1, or 6:1;

[0029] Furthermore, the mass ratio of magnesium aluminum silicate to xanthan gum is 5:1;

[0030] Furthermore, the antifreeze agent is propylene glycol;

[0031] Furthermore, the preservative is benzisothiazolinone;

[0032] Furthermore, the defoamer is dimethyl silicone oil;

[0033] Furthermore, the synergist is an alkyl glycoside;

[0034] A method for preparing a suspension containing fluopyram and quinoline copper involves adding fluopyram and additives other than preservatives and thickeners to a reactor, shearing, adding quinoline copper, shearing until uniform, sand milling, adding preservatives and thickeners after sand milling, adding water to make up the balance, shearing until uniform, and obtaining the product.

[0035] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows: the formulation is reasonable and the effect is good; the production process of the present invention is simple, the product quality is stable, it is suitable for industrial production, it can effectively improve the stability of quinoline copper in the system, with almost no precipitation or sedimentation, and can effectively improve the efficacy. Detailed Implementation

[0036] This invention provides a suspension concentrate of fluopyram and quinoline copper, comprising the following components by mass percentage:

[0037] Table 1. Components and content of suspension concentrate

[0038]

[0039]

[0040] Processing technology: Add fluopyram and additives (excluding preservatives and thickeners) to the feeding tank, and start the shearing process to dissolve all the additives. Add quinoline copper under high shear stirring, and after shearing evenly, perform sand milling. After sand milling, transfer to a homogenizing tank, add preservatives and thickeners, add the remaining water to make up the balance, and then shear and homogenize to obtain the corresponding product.

[0041] Methods for testing the quality and physicochemical properties of pharmaceutical preparations:

[0042] Table 2. Basis for testing various indicators of the preparation.

[0043]

[0044] 35% Fluopyram·Quiloline Copper Suspension (5+30)

[0045] Preparation Example 1:

[0046] Formula composition: Fluopyram 5%, Quinoline Copper 30%, Polyether (D800) 3%, Phenethylphenol Polyether Phosphate Salt (LX-851) 3%, Gelbert Alcohol Polyoxyethylene Ether (XP-70) 2%, Magnesium Aluminum Silicate 1%, Xanthan Gum 0.2%, Propylene Glycol 5%, Benzo[a](xanthan) Thiazolone 0.02%, Dimethyl Silicone Oil 0.5%, Alkyl Glucoside 5%, Deionized Water to make up the balance;

[0047] Preparation method: Add fluopyram and adjuvants (excluding preservatives and thickeners) to a feeding vessel, and start shearing to dissolve all adjuvants. Add quinoline copper under high shear stirring, and after shearing evenly, perform sand milling. After sand milling, transfer to a homogenizing vessel, add preservatives and thickeners, add the remaining water to make up the balance, and then shear and homogenize to obtain the corresponding product.

[0048] Preparation Example 1 Quality Inspection Results:

[0049] Table 3 Detection Results

[0050]

[0051]

[0052] Preparation Example 2:

[0053] Formula composition: Fluopyram 5%, Quinoline Copper 30%, Polyether (D800) 3%, Phenethylphenol Polyether Phosphate Salt (LX-851) 3%, Polycarboxylate (T / 36) 1%, Magnesium Aluminum Silicate 1%, Xanthan Gum 0.2%, Propylene Glycol 5%, Benzo[a](xanthan](xanthan) Thiazolone 0.02%, Dimethyl Silicone Oil 0.5%, Alkyl Glucoside 5%, Deionized Water to make up the balance;

[0054] Preparation method: Same as preparation 1.

[0055] Preparation Example 2 Quality Inspection Results:

[0056] Table 4 Test Results

[0057] Serial Number project Test results Single item judgment 1 Appearance Pale green suspension, no irritating odor qualified 2 Fluopyram mass fraction, % 5 qualified 3 Quinoline copper mass fraction, % 30.2 qualified 4 Total copper content, % 5.6 qualified 5 Fluopyram suspension rate, % 94 qualified 6 Quinoline copper suspension rate, % 96 qualified 7 pH range 7.2 qualified 8 Dumping residue, % 3.4 qualified 9 Residue after pouring wash, % 0.2 qualified 10 Wet sieve test (passing through a 75μm sieve), % 99 qualified 11 Long-lasting foaming properties (after 1 minute), ml 8 qualified

[0058] Preparation Example 3:

[0059] Formula composition: Fluopyram 5%, Quinoline copper 30%, Phenethylphenol polyether phosphate salt (LX-851) 4%, Gelbert alcohol polyoxyethylene ether (XP-70) 2%, Naphthalene sulfonate (D425) 1%, Magnesium aluminum silicate 1%, Xanthan gum 0.2%, Propylene glycol 5%, Benzo[a](xanthan](xanthan) 0.02%, Dimethyl silicone oil 0.5%, Alkyl glycoside 5%, Deionized water to make up the balance;

[0060] Preparation method: Same as preparation 1.

[0061] Preparation Example 3 Quality Inspection Results:

[0062] Table 5 Test Results

[0063] Serial Number project Test results Single item judgment 1 Appearance Pale green suspension, no irritating odor qualified 2 Fluopyram mass fraction, % 4.92 qualified 3 Quinoline copper mass fraction, % 30.1 qualified 4 Total copper content, % 5.61 qualified 5 Fluopyram suspension rate, % 95 qualified 6 Quinoline copper suspension rate, % 95 qualified 7 pH range 7.3 qualified 8 Dumping residue, % 3.3 qualified 9 Residue after pouring wash, % 0.3 qualified 10 Wet sieve test (passing through a 75μm sieve), % 99 qualified 11 Prolonged foaming (after 1 minute), ml 9 qualified

[0064] Preparation Example 4:

[0065] Formula composition: Fluopyram 5%, Quinoline Copper 30%, Polyether (D800) 3%, Gelbert Alcohol Polyoxyethylene Ether (XP-70) 2%, Naphthalene Sulfonate (D425) 1%, Magnesium Aluminum Silicate 1%, Xanthan Gum 0.2%, Propylene Glycol 5%, Benzo[a]isothiazolinone 0.02%, Dimethyl Silicone Oil 0.5%, Alkyl Glucoside 5%, Deionized Water to make up the balance;

[0066] Preparation method: Same as preparation 1.

[0067] Preparation Example 4 Quality Inspection Results:

[0068] Table 6 Test Results

[0069]

[0070] Preparation Example 5:

[0071] Formula composition: Fluopyram 5%, Quinoline Copper 30%, Sodium Lignosulfonate (WG4) 3%, Gelbert Alcohol Polyoxyethylene Ether (XP-70) 2%, Naphthalene Sulfonate (D425) 1%, Magnesium Aluminum Silicate 1%, Xanthan Gum 0.2%, Propylene Glycol 5%, Benzo[a]isothiazolinone 0.02%, Dimethyl Silicone Oil 0.5%, Alkyl Glucoside 5%, Deionized Water to make up the balance;

[0072] Preparation method: Same as preparation 1.

[0073] Preparation Example 5 Quality Inspection Results:

[0074] Table 7 Test Results

[0075]

[0076] Compare with Example 1:

[0077] Formula composition: Fluopyram 5%, Quinoline Copper 30%, Naphthalene Sulfonate (D425) 2%, Lignosulfonate (WG4) 3%, Polycarboxylate (2700) 1%, Magnesium Aluminum Silicate 1%, Xanthan Gum 0.2%, Propylene Glycol 5%, Benzo[a]isothiazolinone 0.02%, Dimethyl Silicone Oil 0.5%, Alkyl Glucoside 5%, Deionized Water to make up the balance;

[0078] Preparation method: Same as preparation 1.

[0079] Compare with the quality inspection results of Example 1:

[0080] Table 8 Test Results

[0081]

[0082]

[0083] Compare with Example 2:

[0084] Formula composition: Fluopyram 5%, Quinoline Copper 30%, Polycarboxylate (GYD900) 2%, Naphthalene Sulfonate (2020) 2%, Magnesium Aluminum Silicate 1%, Xanthan Gum 0.2%, Propylene Glycol 5%, Benzo[a]isothiazolinone 0.02%, Dimethyl Silicone Oil 0.5%, Alkyl Glucoside 5%, Deionized Water to make up the balance;

[0085] Preparation method: Same as preparation 1.

[0086] Compare with the quality inspection results of Example 2:

[0087] Table 9 Test Results

[0088]

[0089] Example 1

[0090] The performance test results of each preparation example and control example are as follows:

[0091] Table 11 Performance Test Results

[0092]

[0093]

[0094] As can be seen from Table 11, the performance of Preparation Examples 1-5 is superior to that of Control Examples 1 and 2 in all aspects. The suspension rates of fluopyram and quinoline copper are all above 90%, and the low-temperature stability and thermal storage stability are qualified, with no stratification or precipitation. In addition, they have strong resistance to hard water (20 times hard water dilution for 1 hour) and no stratification or precipitation.

[0095] Field Example 1

[0096] Field trials for the control of cucumber target spot disease

[0097] Experiment location: Vegetable base of Yangzizhou Farm in the northern suburbs of Nanchang City, Jiangxi Province.

[0098] Experiment date: September 3, 2017;

[0099] Experimental site conditions: The soil type was mainly sandy loam, with a loose, deep, and relatively fertile topsoil layer. Irrigation conditions were good, making it easy to cultivate and suitable for a wide range of crops. At the time of the experiment, the cucumbers were in their peak flowering and fruiting stage, having grown to 10-15 leaves. Cucumber target spot disease had historically been a serious problem in the experimental area, but other cultivation conditions in the experimental field were generally uniform.

[0100] Experimental method: 4 replicates, plot area 24m² 2 Protective measures were implemented; pesticides were applied once on September 3rd and once on September 17th.

[0101] Investigation Methods: The control effect was investigated 15 days after the second application, on October 2, 2017. Sampling was conducted diagonally across each plot, with 5 sampling points. At each sampling point, all leaves of 2 plants were examined. The total number of leaves, the number of diseased leaves, and the disease severity were recorded, and the control efficacy was calculated. Disease severity was determined based on the percentage of diseased area (C) relative to the total area, according to the following grading standards (by leaf).

[0102] Grade 0: No lesions;

[0103] Grade 1: The lesion area accounts for less than 5% of the total leaf area;

[0104] Grade 3: The lesion area accounts for 6% to 10% of the total leaf area;

[0105] Level 5: The lesion area accounts for 11% to 20% of the total leaf area;

[0106] Level 7: Lesions cover 21% to 50% of the total leaf area;

[0107] Level 9: The lesion area accounts for more than 51% of the total leaf area.

[0108] Survey data and calculations: Disease index and control efficacy were calculated based on the "Guidelines for Field Efficacy Trials of Pesticides".

[0109] Disease index = {∑(number of diseased leaves at each level × relative grade value) / (total number of leaves surveyed × 9)} × 100

[0110] Efficacy (%) = {(Control disease index - Treatment disease index) / Control disease index} × 100

[0111] Table 12 Results of field trials for cucumber target spot disease

[0112]

[0113] The data in the table are the average of four studies. The letters indicate significance (uppercase 0.01, lowercase 0.05, DMRT).

[0114] 35% fluopyram·quinoline copper suspension showed good control effect against cucumber target spot disease. Applying the pesticide before or at the onset of cucumber target spot disease, spraying evenly twice with an interval of 14 days, has a good control effect.

[0115] Safety: Cucumbers grew normally during the experiment, and no symptoms of pesticide damage were observed.

[0116] Field Example 2

[0117] Field trials for the control of cucumber target spot disease

[0118] Test location: Qiaozicun Village, Shouguang City, Shandong Province;

[0119] Test date: July 4, 2019;

[0120] Experimental site conditions: Sandy loam soil in the experimental field; cucumber planting size 0.55m×0.5m, two plants per hill; growth period was the fruiting period, at the early stage of cucumber target spot disease.

[0121] Experimental methods: Plot size and replication: 4 replicates, plot size 20m² 2 Protective measures were in place; the pesticide was applied once on July 4, 2019.

[0122] Survey method: Diagonal sampling was conducted in each plot, with 5 sampling points. At each sampling point, all leaves of 2 plants were examined. The plants were then classified according to the following method.

[0123] Grade 0: No lesions;

[0124] Grade 1: The lesion area accounts for less than 5% of the total leaf area;

[0125] Grade 3: The lesion area accounts for 6% to 10% of the total leaf area;

[0126] Level 5: The lesion area accounts for 11% to 20% of the total leaf area;

[0127] Level 7: Lesions cover 21% to 50% of the total leaf area;

[0128] Level 9: The lesion area accounts for more than 51% of the total leaf area.

[0129] Investigation time and frequency: Investigation was conducted 14 days after drug application.

[0130] Survey data and calculations: Disease index and control efficacy were calculated based on the "Guidelines for Field Efficacy Trials of Pesticides".

[0131] Disease index = {∑(number of diseased leaves at each level × relative grade value) / (total number of leaves surveyed × 9)} × 100

[0132] Efficacy (%) = {(Control disease index - Treatment disease index) / Control disease index} × 100

[0133] Weather conditions during the experiment: July 4, 2019 to July 18, 2019. The daily high temperature during the experiment was 30℃ and the daily low temperature was 21℃. There were 8 rainy days during the entire experiment, with a total rainfall of 205mm.

[0134] Table 13 Results of field trials for cucumber target spot disease

[0135]

[0136] The data in the table are the average of four studies. The letters indicate significance (uppercase 0.01, lowercase 0.05, DMRT).

[0137] The experiment took place during the rainy season, and rainfall occurred multiple times after the pesticide was applied.

[0138] As shown in Table 13, 35% fluopyram·quinoline copper suspension showed good control effect against cucumber target spot disease. When the disease was first treated at the onset of the disease, one spray was applied. Preparations 1, 2 and 5 all showed high control efficacy and good resistance to rain washout.

[0139] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A suspension concentrate comprising fluopyram and copper oxyquinoline, characterized in that, According to the weight percentage, it comprises: fluazinam 5%, copper quinolinolate 30%, polyether D800 3%, phenylethyl phenol polyether phosphate salt LX-851 3%, gilbert alcohol polyoxyethylene ether XP-70 2%, magnesium aluminum silicate 1%, xanthan gum 0.2%, propylene glycol 5%, benzisothiazolinone 0.02%, dimethyl silicone oil 0.5%, alkyl glycoside 5%, and deionized water to 100%.

2. A suspension concentrate comprising fluopyram and copper oxyquinoline, characterized in that, According to the weight percentage, it comprises: fluazinam 5%, copper quinolinolate 30%, polyether D800 3%, phenylethyl phenol polyether phosphate salt LX-851 3%, polycarboxylate T / 36 1%, magnesium aluminum silicate 1%, xanthan gum 0.2%, propylene glycol 5%, benzisothiazolinone 0.02%, dimethyl silicone oil 0.5%, alkyl glycoside 5%, and deionized water to 100%.

3. A suspension containing fluopyram and copper oxyquinoline, characterized in that, According to the weight percentage, it comprises: fluazinam 5%, copper quinolinolate 30%, phenylethyl phenol polyether phosphate salt LX-851 4%, gilbert alcohol polyoxyethylene ether XP-70 2%, naphthalene sulfonate D425 1%, magnesium aluminum silicate 1%, xanthan gum 0.2%, propylene glycol 5%, benzisothiazolinone 0.02%, dimethyl silicone oil 0.5%, alkyl glycoside 5%, and deionized water to 100%.

4. A suspension containing fluopyram and copper oxyquinoline, characterized in that, According to the weight percentage, it comprises: fluazinam 5%, copper quinolinolate 30%, polyether D800 3%, gilbert alcohol polyoxyethylene ether XP-70 2%, naphthalene sulfonate D425 1%, magnesium aluminum silicate 1%, xanthan gum 0.2%, propylene glycol 5%, benzisothiazolinone 0.02%, dimethyl silicone oil 0.5%, alkyl glycoside 5%, and deionized water to 100%.

5. A suspension of fluopyram and copper oxyquinoline, characterized in that, According to the weight percentage, it comprises: fluazinam 5%, copper quinolinolate 30%, lignin sulfonate sodium WG4 3%, gilbert alcohol polyoxyethylene ether XP-70 2%, naphthalene sulfonate D425 1%, magnesium aluminum silicate 1%, xanthan gum 0.2%, propylene glycol 5%, benzisothiazolinone 0.02%, dimethyl silicone oil 0.5%, alkyl glycoside 5%, and deionized water to 100%.

6. The method of preparing a suspension concentrate according to any one of claims 1 to 5, characterized in that, The kettle is added with fluazinam and adjuvants except benzisothiazolinone and alkyl glycoside, and then copper quinolinolate is added after shearing. After uniform shearing, sanding is carried out. After sanding, benzisothiazolinone and alkyl glycoside are added, and then water is added to make up the balance and sheared uniformly to prepare the product.

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