Prothioconazole suspending agent for inhibiting particle size increase and preparation method thereof

Abstract

The invention discloses a prothioconazole suspending agent for inhibiting particle size increase and a preparation method thereof. The prothioconazole suspending agent comprises the following components in percentage by mass: 20% of prothioconazole, 20% of tebuconazole, 1%-5% of an anti-freezing agent, 1%-10% of a dispersing agent, 1%-5% of a wetting agent, 0.1%-2% of a thickening agent, 0.2%-1% of a defoaming agent, 0.05%-0.9% of a preservative and the balance of deionized water. The preparation method is simple, environment-friendly and low in cost, the carboxylate dispersing agent and the sulfonate wetting dispersing agent with different structures are combined according to a certain proportion, so that a formula system is stable, and increase of particle sizes of prothioconazole and tebuconazole is inhibited. The prothioconazole tebuconazole granule can effectively inhibit increase of particle size, the particle size is increased by 25%-29% after 14 days of heat storage, the problem of particle size increase of prothioconazole tebuconazole can be effectively solved, and finally the problem of long-term stability of the product in the storage process is solved, the utilization rate is increased, and the drug effect of the product is guaranteed.

Description

Technical Field

[0001] The invention relates to the technical field of pesticide preparations, in particular to a prothioconazole suspension capable of inhibiting particle size growth and a preparation method thereof. Background Art

[0002] Prothioconazole Chemical formula: C 14 H 15 Cl 2 N 3 OS, solubility in water (20℃): 0.005g / L (pH4), 0.3g / L (pH8), 2.0g / L (pH9). Solubility in organic solvents (20℃): n-heptane <0.1g / L, xylene 8g / L, n-octanol 58g / L, acetonitrile 69g / L, isopropanol 87g / L, dichloromethane 88g / L, dimethyl sulfoxide 126g / L, acetone, ethyl acetate and polyethylene glycol are all >250g / L. Stable at room temperature, stable to hydrolysis at pH 4-9. Prothioconazole is mainly used to control many diseases of cereal crops such as wheat, barley, rapeseed, peanuts, rice and legumes. It has a good control effect on almost all wheat diseases, such as powdery mildew, sheath blight, wilt, leaf spot, rust, sclerotinia, web spot, and moire of wheat and barley. It can also prevent and control soil-borne diseases of rapeseed and peanuts, such as sclerotinia, and major foliar diseases, such as gray mold, black spot, brown spot, black shank, sclerotinia and rust.

[0003] Tebuconazole belongs to the triazole fungicide class and is a thiol demethylation inhibitor with a chemical formula of C 16 H 22 C1N 3 O, solubility in water (20℃) 32mg / L, toluene 50-100g / L. It can effectively prevent and treat various rusts, powdery mildew, web blotch, root rot, head blight, smut, seed-borne ring spot, tea cake disease, banana leaf spot, etc. of cereal crops. It is an inhibitor of ergosterol biosynthesis. It can be used to prevent and treat diseases caused by powdery mildew, rust, spore, pyrocoel and Septoria in cereal crops.

[0004] At present, the combination scheme containing prothioconazole has problems such as excessive water precipitation, bottoming, paste formation, poor fluidity, increased viscosity, wall sticking, and increased particle size during hot storage. Summary of the invention

[0005] The object of the present invention is to provide a prothioconazole suspension capable of inhibiting particle size growth and a preparation method thereof. The preparation method of the present invention is simple, environmentally friendly and low in cost. Two carboxylate dispersants with different structures and a sulfonate wetting dispersant are combined in a certain proportion to stabilize the formulation system, inhibit the growth of the particle sizes of prothioconazole and tebuconazole, and ultimately solve the time stability of the product during storage, improve the utilization rate, ensure the efficacy of the product, and solve the problem of quality degradation proposed in the above-mentioned background technology.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] The prothioconazole suspension for inhibiting particle size growth contains the following components in percentage by mass: 20% of prothioconazole, 20% of tebuconazole, 1%-5% of antifreeze agent, 1-10% of dispersant, 1%-5% of wetting agent, 0.1%-2% of thickener, 0.2%-1% of defoamer, 0.05%-0.9% of preservative, and the balance is deionized water.

[0008] Furthermore, the antifreeze agent is one or a combination of more than one of glycerol, propylene glycol, ethylene glycol and urea.

[0009] Furthermore, the dispersant is one or a combination of more than one of polycarboxylates, alkylnaphthalene sulfonates, sulfate anions, polymeric acidic dispersants, lignin sulfonates, and polyoxyethylene ether phosphates.

[0010] Furthermore, the wetting agent is one or a combination of more than one of fatty alcohol polyoxyethylene ether, EO / PO block copolymer and fatty alcohol polyoxyethylene ether sulfate.

[0011] Furthermore, the thickener is one or a combination of more than one of the polymer compound LT-908, carboxyalkyl cellulose, magnesium aluminum silicate, xanthan gum, and bentonite.

[0012] Furthermore, the defoaming agent is one or a combination of more than one of an organosilicon defoaming agent, a mineral oil, and a polyether defoaming agent.

[0013] Furthermore, the preservative is one or a combination of more than one of kason, sodium benzoate, isothiazolin, benzoic acid, formaldehyde, and polyhydroxypropyl benzoate of sorbic acid.

[0014] Furthermore, the preparation method of the prothioconazole suspension concentrate for inhibiting particle size growth comprises the following steps:

[0015] Prothioconazole technical, tebuconazole technical, antifreeze, dispersant, thickener, defoamer, preservative and carrier water are stirred into a uniform slurry by wet sand milling, and then the slurry is sand milled in three stages by a horizontal sand mill to obtain a suspension with a required particle size.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The preparation method provided by the invention is simple, environmentally friendly and low in cost. Two carboxylate dispersants with different structures and a sulfonate wetting dispersant are combined in a certain proportion to stabilize the formulation system, inhibit the growth of the particle sizes of prothioconazole and tebuconazole, and can effectively inhibit the growth of the particle sizes. The particle size increases by 25%-29% after 14 days of hot storage, and the problem of the growth of the particle size of prothioconazole and tebuconazole can be effectively solved. Finally, the time stability of the product during storage is solved, the utilization rate is improved, and the efficacy of the product is guaranteed. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example 1: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by weight:

[0020] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0021] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0022] SC9160 4% (sulfonate anionic dispersant);

[0023] 820S2% (polymeric carboxylate wetting and dispersing agent);

[0024] 1340 2% (carboxylate dispersant);

[0025] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0026] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0027] Ethylene glycol 3% (antifreeze);

[0028] BI T-20 0.2% (preservative);

[0029] 630 0.2% (defoaming agent);

[0030] Water make up 100%.

[0031] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0032] Example 2: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by weight:

[0033] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0034] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0035] SC9160 4% (sulfonate anionic dispersant);

[0036] 1340 4% (carboxylate dispersant);

[0037] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0038] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0039] Ethylene glycol 3% (antifreeze);

[0040] BI T-20 0.2% (preservative);

[0041] 630 0.2% (defoaming agent);

[0042] Water make up 100%.

[0043] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0044] Example 3: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by weight:

[0045] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0046] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0047] SC9160 4% (sulfonate anionic dispersant);

[0048] 820S 2% (polymeric carboxylate wetting and dispersing agent);

[0049] 1340 2% (carboxylate dispersant);

[0050] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0051] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0052] Ethylene glycol 5% (antifreeze);

[0053] BI T-20 0.2% (preservative);

[0054] 630 0.2% (defoaming agent);

[0055] Water make up 100%.

[0056] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0057] Example 4: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by mass:

[0058] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0059] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0060] SC9160 3% (sulfonate anionic dispersant);

[0061] 820S 2% (polymeric carboxylate wetting and dispersing agent);

[0062] 1340 2% (carboxylate dispersant);

[0063] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0064] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0065] Ethylene glycol 3% (antifreeze);

[0066] BI T-20 0.2% (preservative);

[0067] 630 0.2% (defoaming agent);

[0068] Water make up 100%.

[0069] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0070] Example 5: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by mass:

[0071] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0072] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0073] SC9160 4% (sulfonate anionic dispersant);

[0074] 820S2% (polymeric carboxylate wetting and dispersing agent);

[0075] 788 2% (carboxylate dispersant);

[0076] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0077] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0078] Ethylene glycol 3% (antifreeze);

[0079] BI T-20 0.2% (preservative);

[0080] 630 0.2% (defoaming agent);

[0081] Water make up 100%.

[0082] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0083] Example 6: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by mass:

[0084] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0085] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0086] SC9160 4% (sulfonate anionic dispersant);

[0087] 820S2% (polymeric carboxylate wetting and dispersing agent);

[0088] D305 2% (carboxylate dispersant);

[0089] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0090] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0091] Ethylene glycol 3% (antifreeze);

[0092] BI T-20 0.2% (preservative);

[0093] 630 0.2% (defoaming agent);

[0094] Water make up 100%.

[0095] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0096] Example 7: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by weight:

[0097] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0098] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0099] SC9160 4% (sulfonate anionic dispersant);

[0100] 820S2% (polymeric carboxylate wetting and dispersing agent);

[0101] D251 2% (carboxylate dispersant);

[0102] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0103] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0104] Ethylene glycol 3% (antifreeze);

[0105] BI T-20 0.2% (preservative);

[0106] 630 0.2% (defoaming agent);

[0107] Water make up 100%.

[0108] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0109] Example 8: A prothioconazole suspension concentrate for inhibiting particle size growth, comprising the following components in percentage by weight:

[0110] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0111] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0112] SC9160 4% (sulfonate anionic dispersant);

[0113] 820S2% (polymeric carboxylate wetting and dispersing agent);

[0114] 500LQ 2% (EO / PO block copolymer);

[0115] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0116] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0117] Ethylene glycol 3% (antifreeze);

[0118] BI T-20 0.2% (preservative);

[0119] 630 0.2% (defoaming agent);

[0120] Water make up 100%.

[0121] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0122] Comparative Example 1: Prothioconazole suspension for inhibiting particle size growth, composed of the following components in percentage by weight:

[0123] Prothioconazole 20% (active ingredient, produced by Hailier Group Co., Ltd.);

[0124] Tebuconazole 20% (active ingredient, produced by Jiangsu Qizhou Green Chemical Co., Ltd.);

[0125] SC9160 4% (sulfonate anionic dispersant);

[0126] 820S 4% (polymeric carboxylate wetting and dispersing agent);

[0127] Magnesium aluminum silicate 0.7% (high-efficiency suspending agent thickener);

[0128] Xanthan gum 0.15% (high-efficiency suspending agent and thickener);

[0129] Ethylene glycol 3% (antifreeze);

[0130] BI T-20 0.2% (preservative);

[0131] 630 0.2% (defoaming agent);

[0132] Water make up 100%.

[0133] According to the above formula, in a dispersion tank with a high-speed stirrer, wet sand milling is used to stir and shear prothioconazole, tebuconazole technical, dispersant, thickener, defoamer, preservative and carrier water into a uniform slurry, and the product particle size reaches the requirement through three-stage circulation sand milling with a horizontal sand mill.

[0134] Sample flow states of the suspensions of Examples 1-8 of the present invention and Comparative Example 1 during hot storage at 54° C. or after cold storage.

[0135] The thermal storage stability test shall be carried out in accordance with the provisions of GB / T 19136-2021, and the dispersion stability indicators shall meet the standard requirements.

[0136] The low temperature stability test is carried out in accordance with the provisions of GB / T 19137-2003. The dispersion stability index is qualified if it meets the standard requirements.

[0137] The particle size analyzer used was the OMEC LS-909 laser particle size analyzer, and the particle size was measured using a fully automatic detection method. The test results are shown in Table 1.

[0138] Table 1: Particle size test results

[0139]

[0140]

[0141] (Note 1. The hot storage samples in the table are stored at 54℃ for 14 days, 2. The low temperature stability is stored at 0℃ for 7 days, 3. The unqualified hot storage samples have the following phenomena: excessive water precipitation, bottoming, paste, poor fluidity, increased viscosity, wall sticking, internal agglomeration, etc.)

[0142] As can be seen from Table 1, in Example 1, two carboxylate dispersants with different structures and sulfonate wetting dispersants are combined in a certain proportion to stabilize the formulation system, inhibit the growth of the particle size of prothioconazole and tebuconazole, and the particle size growth rate after 14 days of hot storage is 26.3% (the maximum particle size growth of similar products after hot storage is between 200% and 300%). At the same time, for the combination of the two active ingredients, there are phenomena such as more water precipitation during hot storage, bottoming or creaming, poor fluidity, increased viscosity and wall adhesion, and more particle size growth. The formulation invention can effectively solve the above-mentioned quality degradation problem, and ultimately solve the time stability of the product during storage, improve the utilization rate, and ensure the efficacy of the product.

[0143] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A prothioconazole suspension concentrate for inhibiting particle size growth, characterized in that: The invention contains the following components in percentage by mass: 20% of prothioconazole, 20% of tebuconazole, 1%-5% of antifreeze agent, 1-10% of dispersant, 1%-5% of wetting agent, 0.1%-2% of thickener, 0.2%-1% of defoamer, 0.05%-0.9% of preservative, and the balance is deionized water.

2. The prothioconazole suspension concentrate for inhibiting particle size growth as claimed in claim 1, characterized in that: The antifreeze agent is one or a combination of glycerol, propylene glycol, ethylene glycol and urea.

3. The prothioconazole suspension concentrate for inhibiting particle size growth as claimed in claim 1, characterized in that: The dispersant is one or a combination of polycarboxylates, alkylnaphthalene sulfonates, sulfate anions, polymeric acidic dispersants, lignin sulfonates, and polyoxyethylene ether phosphates.

4. The prothioconazole suspension concentrate for inhibiting particle size growth as claimed in claim 1, characterized in that: The wetting agent is one or a combination of more than one of fatty alcohol polyoxyethylene ether, EO / PO block copolymer and fatty alcohol polyoxyethylene ether sulfate.

5. The prothioconazole suspension concentrate for inhibiting particle size growth as claimed in claim 1, characterized in that: The thickener is one or a combination of more than one of the polymer compound LT-908, carboxyalkyl cellulose, magnesium aluminum silicate, xanthan gum and bentonite.

6. The prothioconazole suspension concentrate for inhibiting particle size growth as claimed in claim 1, characterized in that: The defoaming agent is one or a combination of silicone defoaming agent, mineral oil, polyether defoaming agent.

7. The prothioconazole suspension concentrate for inhibiting particle size growth as claimed in claim 1, characterized in that: The preservative is one or a combination of more than one of kason, sodium benzoate, isothiazolin, benzoic acid, formaldehyde, and polyhydroxypropyl benzoate of sorbic acid.

8. A method for preparing a prothioconazole suspension concentrate capable of inhibiting particle size growth, the method being used for preparing the prothioconazole suspension concentrate capable of inhibiting particle size growth as claimed in claim 1, characterized in that: The preparation process is as follows: Prothioconazole technical, tebuconazole technical, antifreeze, dispersant, thickener, defoamer, preservative and carrier water are stirred into a uniform slurry by wet sand milling, and then the slurry is sand milled in three stages by a horizontal sand mill to obtain a suspension with a required particle size.

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