Hydrated boscalid suspending agent and preparation method thereof

Abstract

The invention relates to the field of pesticide bactericides, in particular to A01N43 / 00, and more particularly relates to a hydrated boscalid suspending agent and a preparation method thereof. The preparation raw materials comprise hydrated boscalid, a wetting dispersant, a defoaming agent, an antifreezing agent, a preservative, a thickening agent and water. According to the preparation method of the hydrated boscalid suspending agent, multiple times of grinding treatment are adopted in the process, so that the particle size of suspended particles is controlled to be below 5 microns, and the suspension rate is larger than 90%. The problems that hydrated boscalid is difficult to sand, the particle size is increased and the like due to the fact that the crystal form of the boscalid active compound is incorrect are solved.

Description

Technical Field

[0001] The present invention relates to the field of pesticide fungicides, in particular to A01N43 / 00, and more specifically to a hydrated boscalid suspension concentrate and a preparation method thereof. Background Art

[0002] Boscalid is a new type of nicotinamide fungicide developed by BASF of Germany. It is mainly used to control various plant fungal diseases and was registered in the UK, Germany and Switzerland in 2004. Boscalid mainly acts on the mitochondrial respiratory chain complex II of fungi, inhibiting the activity of succinate dehydrogenase (SDH) and thus hindering the tricarboxylic acid cycle, leading to amino acid and sugar deficiency and energy reduction, thereby interfering with cell division and growth, and ultimately killing the fungi.

[0003] Boscalid has a broad fungicidal spectrum and is active against almost all types of fungal diseases. It is especially effective in preventing and controlling powdery mildew, gray mold, sclerotinia and various rot diseases. It also has a certain antibacterial effect on bacteria resistant to other agents. Boscalid is mainly used for the prevention and control of diseases of rapeseed, grapes, fruit trees, vegetables and field crops. Currently, the products of boscalid sold on the market are mainly water-dispersible granules and suspensions.

[0004] Regarding boscalid, BASF has already laid out relevant patents such as CN100494179C, CN101304658B, and CN101808521A. Due to the technical barriers of related patents, domestic experts, colleges and universities, and various pesticide manufacturers are actively developing type I boscalid and boscalid hydrate. Type I boscalid has problems such as easy water absorption and swelling to paste when used as a suspension, the sand milling particle size cannot be fine, and the crystal form is easy to transform, so it is difficult to make a suspension formulation; while boscalid hydrate can perfectly solve the problem of type I boscalid as a suspension, and the efficacy after application can basically reach the effect of type II boscalid. Summary of the invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a hydrated boscalid suspension concentrate which is easy to use and has stable physical and chemical properties, and the D98 particle size of the suspension concentrate is less than 5 μm; the raw materials of each component of the hydrated boscalid suspension concentrate are calculated by mass percentage and include:

[0006] Hydrated boscalid: 10-50%;

[0007] Wetting and dispersing agent: 5-15%;

[0008] Defoaming agent: 0.3-5%;

[0009] Thickener: 1-5%;

[0010] Antifreeze: 0.5-5%;

[0011] Preservatives: 0.1-3%;

[0012] Water: Make up to 100%.

[0013] The wetting and dispersing agent includes: one or more of methyl taurine sodium salt, phenethylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether sulfate sodium salt, polyethylene oxide polypropylene oxide monobutyl ether, polyethylene oxide polypropylene oxide monobutyl ether, castor oil polyoxyethylene ether, and polyethylene glycol.

[0014] The hydrated boscalid suspension concentrate is an unstable dispersion system with relatively large particles that are easily deposited and aggregated. The addition of a wetting dispersant can prevent the particles from agglomerating with each other, thereby maintaining the stability of the suspension dispersion system. The wetting dispersant forms a protective film by adsorbing on the surface of the suspended particles, which creates a repulsive force between the particles and prevents them from re-agglomerating; a suitable wetting dispersant can also improve the wettability and spreadability of boscalid on the leaves of crops, allowing the pesticide to better adhere to the crop surface, thereby improving the utilization rate and control effect of the pesticide.

[0015] Preferably, the defoamer comprises organic silicone and / or modified polyether defoamer.

[0016] Both silicone defoamers and modified polyether defoamers have excellent defoaming and antifoaming capabilities. In the preparation process of hydrated boscalid suspension concentrate, foam is easily generated due to stirring, shaking or impact; these foams not only affect the preparation and spraying effect of pesticides, but may also have an adverse effect on the quality and stability of pesticides. Defoamers can quickly spread on the foam surface and destroy the foam structure through their low surface tension characteristics, thereby achieving the purpose of defoaming; at the same time, defoamers can also enhance the effect of hydrated boscalid suspension concentrate by improving the permeability and adhesion of the liquid.

[0017] Preferably, the thickener comprises: one or more of xanthan gum, polyvinyl alcohol, bentonite, and magnesium aluminum silicate.

[0018] In the hydrated boscalid suspension pesticide, the addition of thickener can improve the viscosity and consistency of the pesticide, ensuring that the pesticide can be evenly distributed during storage and use, and will not affect the efficacy due to stratification or sedimentation. Therefore, the hydrated boscalid suspension can better adhere to the surface of crops during spraying, reduce loss and volatilization, and improve the utilization rate of the pesticide.

[0019] Preferably, the antifreeze agent comprises: polyol and / or urea.

[0020] More preferably, the polyol includes one or more of ethylene glycol, 1,2-propylene glycol, glycerol, diethylene glycol, triethylene glycol, and polyethylene glycol.

[0021] The addition of antifreeze can lower the freezing point of the hydrated boscalid suspension, prevent it from freezing at low temperatures, and ensure that its active ingredients remain stable during storage and use. The antifreeze not only has an antifreeze function, but also requires low volatility and will not destroy the active ingredients of the pesticide. The present invention preferably uses polyol antifreeze and / or urea, which can not only stably exist in the hydrated boscalid suspension, but also will not react chemically with the active ingredient of the pesticide, boscalid, thereby protecting the effectiveness and activity of the pesticide, but also can play an antiseptic role.

[0022] Preferably, the preservative includes one or more of benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and calcium propionate.

[0023] The second aspect of the present invention provides a method for preparing a hydrated boscalid suspension concentrate, comprising:

[0024] S1. Calculate the amount of each component according to the ratio and weight ratio, weigh and mix the hydrated boscalid, wetting and dispersing agent, defoamer, thickener, antifreeze agent and preservative and stir evenly;

[0025] S2, add water and mix well to form a formula;

[0026] S3, using a grinder to wet grind the formula material to prepare a suspension;

[0027] S4. Analysis, inspection, measurement, packaging and storage.

[0028] Preferably, the grinder comprises a horizontal tandem grinder.

[0029] The horizontal tandem grinder adopts continuous circulation process and circulation grinding process, which can realize large flow and ultra-fine wet preparation, ensuring that the suspension agent reaches the ideal fineness in a shorter time, thereby achieving the technical effect of high suspension rate.

[0030] Preferably, the grinding times are not less than 2 times.

[0031] Beneficial Effects

[0032] (i) The hydrated boscalid suspension concentrate of the present invention is subjected to multiple grinding treatments in the preparation process, so that the D98 particle size of the suspension concentrate is below 5 μm and the suspension rate is greater than 90%; the hydrated boscalid suspension concentrate product has the characteristics of good dispersibility, good wettability, high suspension rate, etc.

[0033] (ii) The hydrated boscalid suspension provided by the present invention also has the characteristics of easy packaging, easy storage, and excellent stability.

[0034] (III) The present invention mainly solves the problem of difficulty in sand grinding and increase in particle size due to inappropriate crystal form of hydrated boscalid technical, thereby increasing the stability of the hydrated boscalid suspension product.

[0035] (IV) The hydrated boscalid suspension concentrate of the present invention circumvents the crystal form protection during the patent protection period of BASF's boscalid original drug crystal form, and its efficacy is almost the same as that of the boscalid preparation product produced by BASF, opening up a new sales highlight.

[0036] (V) The preparation method of the hydrated boscalid suspension concentrate provided by the present invention is relatively simple and is expected to achieve large-scale industrial production. DETAILED DESCRIPTION

[0037] Our laboratory once made a type I boscalid suspension, including: 50.5g type I boscalid; 4.5g wetting and dispersing agent sodium methyl taurine; 0.5g defoaming agent organic silicone; 1.5g thickener xanthan gum; 2.0g antifreeze 1,2-propylene glycol; 1.0g preservative sodium benzoate, and water was added to make up to 100g. In actual operation, when the hydrated boscalid, wetting and dispersing agent, defoaming agent, thickener, antifreeze, and preservative were mixed in proportion and stirred evenly, paste phenomenon occurred and could not be sanded.

[0038] In the following embodiments:

[0039] Hydrated boscalid was purchased from Taizhou Baili Chemical Co., Ltd.

[0040] Methyltaurate sodium salt was purchased from Nanjing Jierun Technology Co., Ltd.

[0041] Sodium lauryl polyoxyethylene ether sulfate was purchased from Shandong Suihua Biotechnology Co., Ltd.

[0042] Polyethylene oxide polypropylene oxide monobutyl ether was purchased from Tesco Chemical (Hubei) Co., Ltd.

[0043] Castor oil polyoxyethylene ether was purchased from Jiangsu Rayen Environmental Protection Technology Co., Ltd.

[0044] Phenylethylphenol polyoxyethylene ether was purchased from Nantong Chenrun Chemical Co., Ltd.

[0045] Polyethylene glycol was purchased from Xingtai Xinlanxing Technology Co., Ltd., model PEG-12.

[0046] Organic silicone was purchased from Nanjing Jierun Technology Co., Ltd., model number is Momentive Silwet408.

[0047] The modified polyether defoamer was purchased from Xingrui (Shandong) Environmental Technology Co., Ltd., model number SGR-1810.

[0048] Xanthan gum was purchased from Zhejiang Shangfang Biotechnology Co., Ltd.

[0049] Magnesium aluminum silicate was purchased from Suzhou Sinoma Mineral Materials Co., Ltd.

[0050] Bentonite was purchased from Zhejiang Yuhong New Materials Co., Ltd.

[0051] The test standard for hydrated boscalid suspension concentrate is:

[0052]

[0053] Example 1

[0054] In the first aspect of this example, a hydrated boscalid suspension concentrate is provided. The raw materials of the components of the hydrated boscalid suspension concentrate are calculated by mass and include: 10.5 g of hydrated boscalid; 4.5 g of a wetting and dispersing agent; the wetting and dispersing agent includes sodium methyl taurate and lauryl polyoxyethylene polyoxypropylene monobutyl ether, and the mass ratio of the two is 2:1; 0.5 g of a defoaming agent silicone; 1.5 g of a thickener xanthan gum; 2.0 g of an antifreeze agent 1,2-propylene glycol; 1.0 g of a preservative sodium benzoate, and water is added to make up to 100 g.

[0055] The second aspect of this example provides a method for preparing a hydrated boscalid suspension concentrate, comprising:

[0056] S1. Calculate the amount of each component according to the ratio and weight ratio, weigh and mix the hydrated boscalid, wetting and dispersing agent, defoamer, thickener, antifreeze agent and preservative and stir evenly;

[0057] S2, add water and mix well to form a formula;

[0058] S3, wet-grinding the formula material three times using a horizontal tandem grinder to prepare a hydrated boscalid suspension concentrate with a mass concentration of about 10%;

[0059] S4. Analysis, inspection, measurement, packaging and storage.

[0060] The content of active ingredients was tested to be 10.2%, pH = 7.8, fineness (through 325 mesh sieve) ≥ 98%, suspension rate ≥ 90%, persistent foaming (1 min) ≤ 10 mL, and cold and hot storage stability were qualified.

[0061] Example 2

[0062] In the first aspect of this example, a hydrated boscalid suspension is provided. The raw materials of the components of the boscalid suspension are calculated by mass and include: 21.0 g of hydrated boscalid; 4.5 g of a wetting and dispersing agent; the wetting and dispersing agent includes sodium methyl taurate and polyethylene oxide polypropylene oxide monobutyl ether, and the mass ratio of the two is 2:1; 0.5 g of a defoaming agent organic silicone; 1.5 g of a thickener magnesium aluminum silicate; 2.0 g of an antifreeze agent ethylene glycol; 1.0 g of a preservative potassium sorbate, and water is added to make up to 100 g.

[0063] The second aspect of this example provides a method for preparing a hydrated boscalid suspension concentrate, comprising:

[0064] S1. Calculate the amount of each component according to the ratio and weight ratio, weigh and mix the hydrated boscalid, wetting and dispersing agent, defoamer, thickener, antifreeze agent and preservative and stir evenly;

[0065] S2, add water and mix well to form a formula;

[0066] S3, wet-grinding the formula material three times using a horizontal tandem grinder to prepare a hydrated boscalid suspension concentrate with a mass concentration of about 20%;

[0067] S4. Analysis, inspection, measurement, packaging and storage.

[0068] The content of active ingredients was tested to be 20.5%, pH = 8.0, fineness (through 325 mesh sieve) ≥ 98%, suspension rate ≥ 90%, persistent foaming (1 min) ≤ 10 mL, and cold and hot storage stability were qualified.

[0069] Example 3

[0070] In the first aspect of this example, a hydrated boscalid suspension is provided. The raw materials of the components of the boscalid suspension are calculated by mass and include: 31.0 g of hydrated boscalid; 5.5 g of a wetting and dispersing agent; the wetting and dispersing agent includes castor oil polyoxyethylene ether and polyethylene glycol, and the mass ratio of the two is 8:3; 0.5 g of a defoaming agent silicone; 1.5 g of a thickener bentonite; 2.0 g of an antifreeze agent glycerol; 1.0 g of a preservative sorbic acid, and water is added to make up to 100 g.

[0071] The second aspect of this example provides a method for preparing a hydrated boscalid suspension concentrate, comprising:

[0072] S1. Calculate the amount of each component according to the ratio and weight ratio, weigh and mix the hydrated boscalid, wetting and dispersing agent, defoamer, thickener, antifreeze agent and preservative and stir evenly;

[0073] S2, add water and mix well to form a formula;

[0074] S3, wet-grinding the formula material three times using a horizontal tandem grinder to prepare a hydrated boscalid suspension concentrate with a mass concentration of about 30%;

[0075] S4. Analysis, inspection, measurement, packaging and storage.

[0076] The content of active ingredients was tested to be 30.4%, pH = 7.9, fineness (through 325 mesh sieve) ≥ 98%, suspension rate ≥ 90%, persistent foaming (1 min) ≤ 10 mL, and cold and hot storage stability were qualified.

[0077] Example 4

[0078] In the first aspect of this example, a hydrated boscalid suspension concentrate is provided. The raw materials of the components of the boscalid suspension concentrate are calculated by mass and include: 40.5 g of hydrated boscalid; 5.5 g of a wetting and dispersing agent; the wetting and dispersing agent includes phenethylphenol polyoxyethylene ether and polyethylene oxide polypropylene oxide monobutyl ether, and the mass ratio of the two is 8:3; 0.5 g of a defoamer modified polyether defoamer; 1.5 g of a thickener xanthan gum; 2.0 g of an antifreeze agent urea; 1.0 g of a preservative benzoic acid, and water is added to make up to 100 g.

[0079] The second aspect of this example provides a method for preparing a hydrated boscalid suspension concentrate, comprising:

[0080] S1. Calculate the amount of each component according to the ratio and weight ratio, weigh and mix the hydrated boscalid, wetting and dispersing agent, defoamer, thickener, antifreeze agent and preservative and stir evenly;

[0081] S2, add water and mix well to form a formula;

[0082] S3, wet-grinding the formula material three times using a horizontal tandem grinder to prepare a hydrated boscalid suspension concentrate with a mass concentration of about 40%;

[0083] S4. Analysis, inspection, measurement, packaging and storage.

[0084] The content of active ingredients was tested to be 40.0%, pH = 8.3, fineness (through 325 mesh sieve) ≥ 98%, suspension rate ≥ 90%, persistent foaming (1 min) ≤ 10 mL, and cold and hot storage stability were qualified.

[0085] Example 5

[0086] In the first aspect of this example, a hydrated boscalid suspension is provided. The raw materials of the components of the boscalid suspension are calculated by mass and include: 51.5 g of hydrated boscalid; 10 g of a wetting and dispersing agent; the wetting and dispersing agent includes sodium methyl taurate and polyethylene oxide polypropylene oxide monobutyl ether, and the mass ratio of the two is 2:3; 0.5 g of a defoaming agent silicone; 1.5 g of a thickener xanthan gum; 2.0 g of an antifreeze agent 1,2-propylene glycol; 1.0 g of a preservative sodium benzoate, and water is added to make up to 100 g.

[0087] The second aspect of this example provides a method for preparing a hydrated boscalid suspension concentrate, comprising:

[0088] S1. Calculate the amount of each component according to the ratio and weight ratio, weigh and mix the hydrated boscalid, wetting and dispersing agent, defoamer, thickener, antifreeze agent and preservative and stir evenly;

[0089] S2, add water and mix well to form a formula;

[0090] S3, wet-grinding the formula material three times using a horizontal tandem grinder to prepare a hydrated boscalid suspension concentrate with a mass concentration of about 50%;

[0091] S4. Analysis, inspection, measurement, packaging and storage.

[0092] The content of active ingredients was tested to be 50.8%, pH = 8.3, fineness (through 325 mesh sieve) ≥ 98%, suspension rate ≥ 90%, persistent foaming (1 min) ≤ 10 mL, and cold and hot storage stability were qualified.

Claims

1. A hydrated boscalid suspension concentrate, characterized in that: The D98 particle size of the hydrated boscalid suspension concentrate is less than 5 μm; the raw materials of the hydrated boscalid suspension concentrate, calculated by mass percentage, include: Hydrated boscalid: 10-50%; Wetting and dispersing agent: 5-15%; Defoaming agent: 0.3-5%; Thickener: 1-5%; Antifreeze: 0.5-5%; Preservatives: 0.1-3%; Water: Make up to 100%.

2. The hydrated boscalid suspension concentrate according to claim 1, characterized in that: The wetting and dispersing agent includes: one or more of methyl taurine sodium salt, phenethylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether sulfate sodium salt, polyethylene oxide polypropylene oxide monobutyl ether, polyethylene oxide polypropylene oxide monobutyl ether, castor oil polyoxyethylene ether, and polyethylene glycol.

3. The hydrated boscalid suspension concentrate according to claim 1, characterized in that: The defoamer includes organic silicone and / or modified polyether defoamer.

4. The hydrated boscalid suspension concentrate according to claim 1, characterized in that: The thickener comprises: one or more of xanthan gum, polyvinyl alcohol, bentonite and magnesium aluminum silicate.

5. The hydrated boscalid suspension concentrate according to claim 1, characterized in that: The antifreeze agent includes: polyol and / or urea.

6. The hydrated boscalid suspension concentrate according to claim 5, characterized in that: The polyols include one or more of ethylene glycol, 1,2-propylene glycol, glycerol, diethylene glycol, triethylene glycol, and polyethylene glycol.

7. The hydrated boscalid suspension concentrate according to claim 1, characterized in that: The preservatives include: one or more of benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and calcium propionate.

8. A method for preparing the hydrated boscalid suspension concentrate according to any one of claims 1 to 7, characterized in that: include: S1. Calculate the amount of each component according to the ratio and weight ratio, weigh and mix the hydrated boscalid, wetting and dispersing agent, defoamer, thickener, antifreeze agent and preservative and stir evenly; S2, add water and mix well to form a formula; S3, using a grinder to wet grind the formula material to prepare a suspension; S4. Analysis, inspection, measurement, packaging and storage.

9. The method for preparing the hydrated boscalid suspension concentrate according to claim 8, characterized in that: The grinding machine comprises a horizontal tandem grinding machine.

10. The method for preparing the hydrated boscalid suspension concentrate according to claim 8, characterized in that: The grinding times are not less than 2 times.

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