Two-component fluopyram soluble concentrate and preparation method thereof

Abstract

The invention discloses a bi-component fluopyram soluble concentrate, the bi-component fluopyram soluble concentrate comprises a fluopyram active compound and an amino-oligosaccharin active compound, and the weight ratio of the fluopyram active compound to the amino-oligosaccharin active compound is (0.5-1.5): (0.05-0.5); the soluble concentrate is prepared from the following raw materials: a wetting agent, a thickening agent, a preservative, a dispersing agent, a stabilizing agent and water. The fluopyram active compound and the amino-oligosaccharin active compound are combined, and the weight ratio of the fluopyram active compound to the amino-oligosaccharin active compound is 1.04: 0.12, so that the prepared soluble concentrate can achieve a good insecticidal effect by using a relatively low dosage, and is not easy to generate drug resistance. The solubility and dispersity of the fluopyram and the amino-oligosaccharin in the soluble concentrate are improved, the stability of the soluble concentrate is improved, and the fluopyram and the amino-oligosaccharin are not layered after being stored and stood for a long time.

Description

Technical Field

[0001] The invention relates to A01N and the field of biocides, and in particular to a two-component soluble solution of fluopyram and a preparation method thereof. Background Art

[0002] Fluopyram is a commonly used pesticide, which has good control effects on new leaves, stems, tubers, young fruits, etc. Amino-oligosaccharides have certain inhibitory effects on some pathogens and are widely used in the agricultural field. However, when fluopyram and amino-oligosaccharides are used alone, the control effect of the drugs is not good. It is necessary to increase the concentration of the single-component agent to achieve good bactericidal and insecticidal effects. However, high concentrations of agents have certain harm to the environment. At the same time, a large concentration of the agent will have a certain impact on the tender roots, stems and leaves of plants. Therefore, it is very important to develop a two-component pesticide agent suitable for low-concentration use.

[0003] Chinese invention patent CN103766353A discloses a bactericidal composition containing fluopyram, which plays a synergistic role through the compounding of fluopyram and amino oligosaccharides, and is used for the prevention and control of fungal diseases of crops such as fruit trees, flowers, cotton, wheat, and vegetables, but is applied to the prevention and control of powdery mildew of cucumbers, and the concentration used is relatively high. Chinese invention patent CN114938806A discloses a composite pesticide of amino oligosaccharides and fluopyram and a preparation method thereof, which greatly improves the dispersion and suspension properties of amino oligosaccharides and fluopyram by introducing antifreeze, preservatives, and adjuvants, and improves storage performance. However, the dosage of fluopyram is large, and the safety of use is not high. Summary of the invention

[0004] In order to develop a two-component soluble agent of fluopyram and amino-oligosaccharide for use at a low concentration, the first aspect of the present invention provides a two-component soluble agent of fluopyram, wherein the raw materials for preparing the soluble agent include fluopyram technical and amino-oligosaccharide technical, and the weight ratio of the fluopyram technical to the amino-oligosaccharide technical is (0.5-1.5): (0.05-0.5); the raw materials for preparing the soluble agent also include a wetting agent, a thickener, a preservative, a dispersant, a stabilizer and water.

[0005] As a preferred embodiment, the weight ratio of the fluopyram technical and the amino oligosaccharide technical is (1-1.5): (0.1-0.2).

[0006] As a preferred embodiment, the weight ratio of the fluopyram technical to the amino oligosaccharide technical is 1.04:0.12.

[0007] As a preferred embodiment, the raw materials for preparing the two-component fluopyram soluble agent include, by weight, 1-1.5 parts of fluopyram technical, 0.1-0.2 parts of amino oligosaccharide technical, 1-3 parts of wetting agent, 1-2 parts of thickener, 0.1-1 parts of preservative, 1-3 parts of dispersant, 1-2 parts of stabilizer, and 90-95 parts of water.

[0008] As a preferred embodiment, the raw materials for preparing the two-component fluopyram soluble agent include, by weight, 1.04 parts of fluopyram technical, 0.12 parts of amino oligosaccharide technical, 2 parts of wetting agent, 1 part of thickener, 0.5 parts of preservative, 2 parts of dispersant, 1 part of stabilizer, and 93 parts of water.

[0009] As a preferred embodiment, the purity of the fluopyram technical is 90-99%.

[0010] As a preferred embodiment, the purity of the fluopyram technical is 96%.

[0011] As a preferred embodiment, the purity of the amino oligosaccharide original drug is 80-89%.

[0012] As a preferred embodiment, the purity of the amino oligosaccharide original drug is 85%.

[0013] During the experiment, the applicant found that by using a combination of fluopyram and amino-oligosaccharides, and using a weight ratio of 1.04:0.12, the drugs can be mixed evenly, and a lower dosage can achieve a good insecticidal effect, and it is not easy to develop drug resistance. The possible reasons are speculated to be: fluopyram and amino-oligosaccharides have different mechanisms of action, and they achieve insecticidal effects based on the different physiological activities of organisms, preventing root-knot nematodes from easily developing drug resistance. In addition, the combination of fluopyram and amino-oligosaccharides has a high mixing uniformity and is easy to contact pests, thereby achieving an insecticidal effect at a small dose.

[0014] As a preferred embodiment, the wetting agent is an anionic surfactant, and the anionic surfactant is selected from at least one of sodium alkylbenzene sulfonate, sodium alkyl sulfate, alkyl sulfonate, fatty acid sulfonalkylamide, fatty acid sulfonalkyl ester, alkylnaphthalene sulfonate, and lignin sulfonate.

[0015] As a preferred embodiment, the wetting agent is sodium alkyl sulfate; preferably, the wetting agent is sodium dodecyl sulfate.

[0016] As a preferred embodiment, the dispersant is a polymer dispersant, and the dispersant is selected from at least one of polycarboxylates, polymethacrylic acid derivatives, and maleic anhydride copolymers.

[0017] As a preferred embodiment, the dispersant is a polycarboxylate.

[0018] As a preferred embodiment, the viscosity of the polycarboxylate dispersant is 1500-2000 mPa·s at 5° C. and 60 rpm.

[0019] As a preferred embodiment, the viscosity of the polycarboxylate dispersant is 1700 mPa·s at 5° C. and 60 rpm.

[0020] The inventors found during the experiment that the use of sodium dodecyl sulfate as a wetting agent and polycarboxylates as dispersants can improve the low-temperature stability of soluble solutions, and it is not easy to precipitate crystals or stratify. It is speculated that the possible reasons are: the anionic surfactant sodium dodecyl sulfate and polycarboxylates work synergistically, contain a large number of anions, and can increase the solubility of the original drug in the soluble solution, and the pesticide agent is often diluted with hard water when used, which can avoid the influence of salt ions in hard water on the pesticide, and avoid crystallization and stratification. The applicant further found that the use of polycarboxylates with high viscosity at low temperatures can prevent the original drug particles from crystallizing at low temperatures, especially in low temperature environments, root control can be carried out smoothly, and the drug effect is significant.

[0021] As a preferred embodiment, the thickener is an inorganic thickener, and the inorganic thickener is selected from at least one of bentonite, attapulgite, aluminum silicate, and magnesium aluminum silicate.

[0022] As a preferred embodiment, the thickener is magnesium aluminum silicate.

[0023] As a preferred embodiment, the stabilizer is selected from at least one of xanthan gum, carrageenan, guar gum, pectin and locust bean gum.

[0024] As a preferred embodiment, the stabilizer is xanthan gum.

[0025] As a preferred embodiment, the weight ratio of the magnesium aluminum silicate to the xanthan gum is (1-3): (1-3).

[0026] As a preferred embodiment, the weight ratio of the magnesium aluminum silicate to the xanthan gum is 1:1.

[0027] As a preferred embodiment, the weight ratio of the wetting agent to the dispersant is (1-5): (1-5).

[0028] As a preferred embodiment, the weight ratio of the wetting agent to the dispersant is 2:2.

[0029] During the experiment, the inventors found that the combination of aluminum magnesium silicate and xanthan gum in a weight ratio of 1:1 can make the soluble solution have a suitable consistency and viscosity, have good adhesion to the cucumber root system, and prolong the efficacy time of the agent on the cucumber root system. The possible reasons are speculated to be: the surface of the cucumber root system is smooth, and higher viscosity and adhesion are required to fit the root surface. However, if the viscosity of the agent is too high, it will lead to a greater infiltration resistance of the agent when irrigating the roots, and the deep roots of the plant cannot contact the agent, which is not conducive to the insecticidal effect.

[0030] As a preferred embodiment, the preservatives include but are not limited to kasone, sodium benzoate, formaldehyde, potassium benzoate, sorbate, and paraben.

[0031] The second aspect of the present invention provides a method for preparing a two-component soluble solution of fluopyram, comprising the following steps:

[0032] S1: mixing fluopyram technical, amino oligosaccharide technical, wetting agent, thickener, preservative, dispersant, stabilizer and water, and stirring to form a uniform slurry;

[0033] S2: Pour the slurry into a sand mill containing sand mill beads and continue sand milling for 1-1.5 hours to obtain a soluble solution.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The two-component soluble agent of fluopyram of the present invention adopts a combination of fluopyram technical and amino-oligosaccharide technical, wherein the weight ratio of fluopyram technical to amino-oligosaccharide technical is 1.04:0.12. The prepared soluble agent can achieve good insecticidal effect with a lower dosage and is not easy to produce drug resistance.

[0036] (2) The two-component soluble agent of fluopyram of the present invention uses sodium dodecyl sulfate as a wetting agent and polycarboxylate as a dispersant, thereby improving the solubility and dispersibility of fluopyram and amino-oligosaccharides in the soluble agent, improving the stability of the soluble agent, and preventing stratification after long-term storage and standing.

[0037] (3) The two-component soluble agent of fluopyram of the present invention adopts a combination of magnesium aluminum silicate and xanthan gum, wherein the weight ratio of magnesium aluminum silicate and xanthan gum is 1:1, so as to increase the adhesion between the agent and the object of application, prolong the efficacy time, slowly release the active ingredients of the drug, avoid irritation to the object of application, and at the same time have significant efficacy.

[0038] (4) The two-component soluble solution of fluopyram of the present invention has an excellent killing effect on cucumber root-knot nematodes. It can be applied in the early stage of cucumber seedlings with a small amount of application, which does not affect the normal growth of cucumber seedlings and has a good control effect.

[0039] (5) The two-component soluble preparation of fluopyram of the present invention has good storage stability, does not have the problem of stratification after long-term storage, and does not precipitate crystals or produce stratification in low temperature environment or high temperature environment. DETAILED DESCRIPTION

[0040] Example 1

[0041] A two-component fluopyram soluble agent, wherein the raw materials for preparation include, by weight, 1.04 parts of fluopyram technical, 0.12 parts of amino oligosaccharide technical, 2 parts of wetting agent, 1 part of thickener, 0.5 parts of preservative, 2 parts of dispersant, 1 part of stabilizer and 93 parts of water.

[0042] The purity of the fluopyram technical is 96%, and it is purchased from Bayer AG, with CAS number: 658066-35-4.

[0043] The amino oligosaccharide technical has a purity of 85% and is purchased from Qingdao Zhongda Agricultural Technology Co., Ltd., CAS No.: 9012-76-4.

[0044] The wetting agent is sodium lauryl sulfate, the thickener is magnesium aluminum silicate, the stabilizer is xanthan gum, and the preservative is kason.

[0045] The dispersant is polycarboxylate, with a viscosity of 1700 mPa·s at 5° C. and 60 rpm, purchased from Shandong Youso Chemical Technology Co., Ltd., model 5040, CAS number: 62601-60-9.

[0046] A method for preparing a two-component soluble solution of fluopyram comprises the following steps:

[0047] S1: mixing fluopyram technical, amino oligosaccharide technical, wetting agent, thickener, preservative, dispersant, stabilizer and water, and stirring to form a uniform slurry;

[0048] S2: Pour the slurry into a sand mill containing sand mill beads and continue sand milling for 1.5 hours to obtain a soluble solution.

[0049] Example 2

[0050] A two-component fluopyram soluble agent, wherein the raw materials for preparation include, by weight, 1.5 parts of fluopyram technical, 0.05 parts of amino oligosaccharide technical, 1 part of wetting agent, 2 parts of thickener, 0.1 part of preservative, 1 part of dispersant, 2 parts of stabilizer and 90 parts of water.

[0051] Example 3

[0052] A two-component soluble preparation of fluopyram. The raw materials for preparation include, by weight, 0.5 parts of fluopyram technical, 0.5 parts of amino oligosaccharide technical, 3 parts of wetting agent, 2 parts of thickener, 1 part of preservative, 3 parts of dispersant, 2 parts of stabilizer and 95 parts of water.

[0053] Comparative Example 1

[0054] A two-component soluble preparation of fluopyram and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the preparation raw materials, by weight, include 1.04 parts of fluopyram technical, 0.12 parts of amino oligosaccharide technical, 2.5 parts of wetting agent, 1 part of thickener, 0.5 parts of preservative, 2.5 parts of dispersant, and 93 parts of water.

[0055] Comparative Example 2

[0056] A two-component soluble preparation of fluopyram and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the preparation raw materials include, by weight, 1.04 parts of fluopyram technical, 0.12 parts of amino oligosaccharide technical, 1 part of thickener, 0.5 parts of preservative, 3 parts of dispersant, 2 parts of stabilizer, and 93 parts of water.

[0057] Comparative Example 3

[0058] A two-component soluble preparation of fluopyram and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the preparation raw materials include, by weight, 1.04 parts of fluopyram technical, 0.12 parts of amino oligosaccharide technical, 3 parts of wetting agent, 1 part of thickener, 0.5 parts of preservative, 2 parts of stabilizer, and 93 parts of water.

[0059] Comparative Example 4

[0060] A two-component soluble preparation of fluopyram and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the dispersant replaces the polycarboxylate with polyethylene glycol monomethyl ether, and the polyethylene glycol monomethyl ether is purchased from Hai'an Petrochemical Plant in Jiangsu Province with a brand name of MPEG-350.

[0061] Comparative Example 5

[0062] A two-component soluble agent of fluopyram and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that the wetting agent replaces sodium dodecyl sulfate with sodium dodecylbenzene sulfonate.

[0063] Comparative Example 6

[0064] A two-component soluble solution of fluopyram and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that the stabilizer replaces xanthan gum with konjac gum, and the konjac gum is purchased from Jiangsu Peptize Biotechnology Co., Ltd. with a brand name of KJ30.

[0065] Performance Testing

[0066] 1. Field efficacy experiment:

[0067] The experiment was conducted in Lvheng Ecological Park, Ansha Town, Changsha County, Hunan Province from August to November 2023. Fifteen days after the cucumbers were transplanted, each plant was irrigated once with 200 ml of liquid per plant. Each treatment was repeated four times, with a plot area of ​​15m 2 , a total of 24 plots, arranged in random blocks. The first survey was conducted when the blank control group was fully ill, and the second survey was conducted 14 days later, for a total of two surveys, the results are shown in Table 1 below.

[0068] Adopt diagonal five-point sampling or random sampling method, investigate two plants at each point, and calculate the number of diseased plants at each level, disease index and control effect.

[0069] The grading method is as follows:

[0070] Level 0: healthy root system, no root knots;

[0071] Level 1: The root system has only a small number of root knots, accounting for 1-25% of the total root system;

[0072] Level 3: moderate root-knot nematode presence, accounting for 26-50% of the total root system;

[0073] Level 5: The root system has a large number of nodes, accounting for 51-75% of the total root system;

[0074] Level 7: The root system has a large number of root nodes, accounting for 76-100% of the entire root system.

[0075] Observe whether the crops are damaged by pesticides. If so, record the symptoms and extent of the damage. In addition, the beneficial effects on the crops (such as promoting maturity, stimulating growth, etc.) should also be recorded. Record the effects of the pesticide on wild life and beneficial insects in the test area.

[0076] Calculation method of drug efficacy:

[0077] Root knot index = (number of plants at each disease level × corresponding level) / (7 × total number of plants) × 100

[0078] Control effect % = (root knot index of control area - root knot index of treatment area) / root knot index of control area × 100

[0079] The Duncan new multiple range method in DPS statistical analysis software was used to perform significance analysis of differences. In the analysis results, the same lowercase letters indicate insignificant differences at the 5% level, and the same uppercase letters indicate insignificant differences at the 1% level.

[0080] Table 1

[0081]

[0082] Crop safety testing:

[0083] A yield survey was conducted during the cucumber harvest period to determine the actual yield of each plot, expressed in kg / hectare, and the yield increase rate compared with the blank control was calculated.

[0084] Yield increase rate (%) = (yield of treatment area - yield of blank control area) / yield of blank control area × 100

[0085] The production statistics are shown in Table 2.

[0086] Table 2

[0087]

[0088]

[0089] The test results show that the test agent 1.1% amino oligosaccharide·fluopyram soluble solution has a good preventive effect on cucumber root knot nematode disease when the active ingredient dosage is 0.0088-0.011 g / plant. No adverse effects of the test agent on other pests and non-target organisms were observed. It is safe for cucumbers and can be used to prevent and control cucumber root knot nematode disease.

[0090] 2. Stability test:

[0091] The physicochemical properties of the soluble agent product provided in Example 1 were tested, with reference to NY / T 1860-2016 "Test Guidelines for Determination of Physicochemical Properties of Pesticides", and the test items and test results are shown in Table 3

[0092] The soluble preparations prepared in the examples and comparative examples were subjected to stability tests. The soluble preparations prepared in the examples and comparative examples were placed in 50 mL centrifuge tubes (Corning 50 mL PP centrifuge tubes, self-standing, with sealing caps, outer diameter 29.1 mm, length 114.9 mm) and left to stand at 25° C. for 0-72 h to record the appearance of the products. The test results are shown in Table 4. A transition layer thickness of 50-90 mm was considered as slight delamination, a transition layer thickness of 20-50 mm was considered as delamination, and a transition layer thickness of 0-20 mm was considered as severe delamination.

[0093] Table 3

[0094]

[0095] Table 4

[0096]

Claims

1. A two-component soluble agent of fluopyram, characterized in that: The raw materials for preparing the soluble concentrate include fluopyram technical and amino-oligosaccharide technical, and the weight ratio of the fluopyram technical to the amino-oligosaccharide technical is (0.5-1.5):(0.05-0.5); the raw materials for preparing the soluble concentrate also include a wetting agent, a thickener, a preservative, a dispersant, a stabilizer and water.

2. The two-component soluble agent of fluopyram according to claim 1, characterized in that: The purity of the fluopyram technical is 90-99%.

3. The two-component soluble agent of fluopyram according to claim 1, characterized in that: The purity of the amino oligosaccharide original drug is 80-89%.

4. The two-component soluble agent of fluopyram according to claim 1, characterized in that: The wetting agent is an anionic surfactant, and the anionic surfactant is selected from at least one of sodium alkylbenzene sulfonate, sodium alkyl sulfate, alkyl sulfonate, fatty acid sulfonalkylamide, fatty acid sulfonalkyl ester, alkylnaphthalene sulfonate, and lignin sulfonate.

5. The two-component soluble agent of fluopyram according to claim 1, characterized in that: The dispersant is a polymer dispersant, and the dispersant is selected from at least one of polycarboxylates, polymethacrylic acid derivatives, and maleic anhydride copolymers.

6. The two-component soluble preparation of fluopyram according to claim 5, characterized in that: The viscosity of the polycarboxylate dispersant is 1500-2000 mPa·s at 5° C. and 60 rpm.

7. The two-component soluble preparation of fluopyram according to claim 1, characterized in that: The thickener is an inorganic thickener, and the inorganic thickener is selected from at least one of bentonite, attapulgite, aluminum silicate, and magnesium aluminum silicate.

8. The two-component soluble preparation of fluopyram according to claim 1, characterized in that: The stabilizer is selected from at least one of xanthan gum, carrageenan, guar gum, pectin and locust bean gum.

9. The two-component soluble preparation of fluopyram according to claim 1, characterized in that: The weight ratio of the wetting agent to the dispersant is (1-5): (1-5).

10. A method for preparing the two-component soluble solution of fluopyram according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1: mixing fluopyram technical, amino oligosaccharide technical, wetting agent, thickener, preservative, dispersant, stabilizer and water, and stirring to form a uniform slurry; S2: Pour the slurry into a sand mill containing sand mill beads and continue sand milling for 1-1.5 hours to obtain a soluble solution.

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