Dispersible oil suspensions containing benzylazoles and methods for their preparation

Abstract

The present invention relates to the technical field of A01P13 / 00, more particularly to a dispersible oil suspension agent containing benzylazole and a method for preparing the same. The dispersible oil suspension agent containing benzylazole comprises, as components, by weight, 22-44 parts of glyphosate ammonium salt, 0.5-1.5 parts of benzylazole, 3-8 parts of wetting and dispersing agent, 10-15 parts of emulsifier, 1-2 parts of structure modifier, and 100 parts of supplementary solvent. The dispersible oil suspension agent in the present application solves the decomposition problem of benzylazole in the prior art, and the dispersible oil suspension agent does not have the problem of pasting, has excellent high and low temperature resistance, and has favorable dilution stability, sustained foaming property, and suspension rate.

Description

[Technical field]

[0001] The present invention relates to the technical field of A01P13 / 00, more particularly to a dispersible oil suspension containing a benzylazole and a method for preparing the same. [Background technology]

[0002] Benzylazole can be combined with glyphosate to produce significant synergistic effects, effectively improving the immediate and sustained effects, and can be used to prepare formulations such as dispersible oil suspensions, suspensions, aqueous emulsions, water-dispersible granules, granules, etc. However, the addition of high glyphosate content makes it easy for pipe clogging to occur during the production process, and dispersible oil suspensions can cause problems such as pasting and degradation of the active pharmaceutical ingredient.

[0003] Chinese Patent CN113491269A provides a herbicide composition containing benzylazole, glyphosate, a surfactant, a pH adjuster, a structure stabilizer, a solvent and an oil base. However, there is a risk of pasting even in scale-up experiments in the production process, and the large number of components leads to a decrease in production efficiency. In addition, depending on the raw materials and preparation method, the composition may cause pipe clogging problems.

[0004] Therefore, there is a need to provide a dispersible oil suspension containing benzylazole and glyphosate ammonium salt, which can reduce the number of raw materials and solve the problems of pasting, clogging of pipes, etc. Summary of the Invention [Means for solving the problem]

[0005] In response to some of the problems present in the prior art, a first aspect of the present invention provides a benzylazole-containing dispersible oil suspension comprising as ingredients, by weight, 22-44 parts of glyphosate ammonium salt, 0.5-1.5 parts of benzylazole, 3-8 parts of a wetting and dispersing agent, 10-15 parts of an emulsifier, 1-2 parts of a structure modifier, and 100 parts of a supplemental solvent.

[0006] In one embodiment, the weight ratio of the glyphosate ammonium salt to benzylazole is (28-38:1), preferably 33:1.

[0007] In one embodiment, the wetting and dispersing agent is one or more of sulfonate, polycarboxylate, and sulfate dispersants, preferably, the wetting and dispersing agent is one or more selected from TSC-930, SP-OF3498D, GY-EM05, and WELOD461.

[0008] In one embodiment, the emulsifier is one or more selected from OD21, ODE286, TSC901.

[0009] In one embodiment, when the emulsifier is OD21, the wetting and dispersing agent is one or more selected from TSC-930, SP-OF3498D, GY-EM05, when the emulsifier is ODE286, the wetting and dispersing agent is SP-OF3498D, when the emulsifier is TSC901, the wetting and dispersing agent is SP-OF3498D.

[0010] Preferably, the weight ratio of the wetting / dispersing agent to the emulsifying agent is 5:(11 to 14), more preferably 5:12.

[0011] The applicant unexpectedly discovered through experiments that by selecting the combination of emulsifier and wetting dispersant of a specific type and mixing ratio in this application, under the condition of the presence of a small number of auxiliary agents, the obtained dispersible oil suspension has better viscosity, is free from the risk of pasting during the grinding process and at room temperature, and reduces the decomposition rate of benzylazole after hot / low temperature storage, thereby extending the shelf life. The applicant believes that the possible reasons are the system formed by the specific wetting dispersant and emulsifier, the interaction between the long carbon chains, and the polar groups carried by the specific wetting dispersant and emulsifier can enhance the dispersion stability between the pharmaceutical ingredient molecules through the comb structure of the wetting dispersant, thereby avoiding the escape of the benzylazole molecules under extreme conditions.

[0012] In one embodiment, the structure modifier is white carbon black and / or organobentonite.

[0013] Preferably, the structure-controlling agent is white carbon black and organic bentonite in a weight ratio of (1-3):1, more preferably in a weight ratio of (1-2):1.

[0014] The applicant unexpectedly found through experiments that under the condition of the presence of the specific auxiliary in the present application, a small amount of solids would aggregate at the bottom of the obtained dispersible oil suspension, and even after adding organic bentonite, a small amount of solids would aggregate at the bottom. To solve the situation of solid aggregation, those skilled in the art usually improve the dispersibility of the raw pharmaceutical ingredients by adjusting the auxiliary to be added. However, the applicant found that adjusting the specific auxiliary in the present application would cause high oil deposition rate and decomposition problem of benzylazole under hot / low temperature storage conditions. The applicant unexpectedly found that when the structure modifier is white carbon black and organic bentonite in a weight ratio of (1-2):1, under the condition of blending the specific wetting dispersant and emulsifier auxiliary in the present application, the obtained dispersible oil suspension has no solids aggregate at its bottom, and at the same time does not affect the oil deposition property and cold resistance and heat resistance of the dispersible oil suspension in the present application, and avoids the impact of the structure modifier on the oil deposition property and cold resistance and heat resistance. The applicant believes that the possible cause is that, under the conditions of the presence of the specific wetting and dispersing agent and emulsifying agent in this application, the specific weight ratio of white carbon black and organic bentonite forms a three-dimensional structure in the oleic acid methyl ester solvent, maintains a constant viscosity, and there is no risk of pasting.

[0015] In addition, the applicant unexpectedly discovered that, by the combination of the specific structure adjuster, wetting dispersant and emulsifier in the present application, and at the same time, by the specific preparation method in the present application, in the presence of single solvent methyl oleate, the resulting dispersible oil suspension has better dilution stability and sustained foaming. The applicant believes that each molecule is controlled in the space of the three-dimensional structure, and the large and small molecular chains are blended with each other, avoiding the tighter entanglement over time, and the whole system maintains a more stable viscosity.

[0016] Moreover, the applicant has unexpectedly discovered that the dispersible oil suspension obtained in the present application has favorable dispersibility, penetration, wettability, adhesion, target adhesion, evaporation resistance, spreadability, and the like, without the addition of additional fast penetrating agents, other surfactants, and the like.

[0017] In the present application, the solvent is not particularly limited and can be conventionally selected by those skilled in the art. In a preferred embodiment, the solvent is methyl oleate.

[0018] In one embodiment, the benzylazole-containing dispersible oil suspension further comprises 5 to 10 parts by weight of a synergist.

[0019] In the present application, examples of the synergist include anionic surfactants such as fast penetrating agent T, diethylhexyl sodium sulfosuccinate, and dioctyl sodium sulfosuccinate, anionic-nonionic double-structure sulfonates, nonionic surfactants such as aliphatic alcohol polyoxyethylene ether, aliphatic alcohol polyoxyethylene ether polyoxypropylene ether, and Tween, and decanamide-based substances.

[0020] Trademarks of synergists in this application include 3075V, FTRT (FTRT is a registered trademark) TT, FIRT (FIRT is a registered trademark) TV3, T-100, 245-LQ-(TH), L-1505-LQ-(AP), 4166, and the like.

[0021] A second aspect of the present invention provides a method for preparing a dispersible oil suspension comprising mixing a benzylazole, a wetting and dispersing agent, an emulsifier, a structure modifier and a solvent to form an oil phase, adding the oil phase to a sand mill, circulating the oil phase, followed by adding ammonium glyphosate salt and grinding.

[0022] In one embodiment, the method for preparing the dispersible oil suspension includes dissolving benzylazole in methyl oleate, then adding the remaining raw materials and shearing to form a uniform oil phase; adding hot water of 0 to 50°C into a sand mill, adding the oil phase, and adding glyphosate ammonium salt for grinding after the circulation of the oil phase becomes normal.

[0023] The applicant has found through experiments that the weight ratio of glyphosate ammonium salt in the dispersible oil suspension in this application is relatively high, and in the preparation process, glyphosate ammonium salt is prone to settling and blocking, which leads to clogging of the circulation line. However, the applicant has unexpectedly found that the benzylazole, specific wetting and dispersing agent, emulsifier, structure modifier, and solvent in this application are first mixed, and then the oil phase is circulated, and then glyphosate ammonium salt is added, in this case, the problem of clogging of the pipeline caused by glyphosate ammonium salt is avoided, and in the later stage, the processability during grinding is good, and an ideal particle size distribution can be obtained. The applicant believes that the possible cause is that glyphosate ammonium salt is added to the oil phase formed in this application, and in this case, due to the fluidity of the oil phase, glyphosate ammonium salt can be dispersed and circulated well in the early stage after adding it, which avoids clogging of the pipeline caused by localized precipitation of glyphosate ammonium salt, and the dispersible oil suspension obtained by this method has little residue after falling over.

[0024] The present invention has the following beneficial effects compared with the prior art:

[0025] The dispersible oil suspension in the present application solves the decomposition problem of benzylazole in the prior art, and the dispersible oil suspension does not have the problem of pasting, has excellent high and low temperature resistance, and has favorable dilution stability, sustained foaming property and suspension rate. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 is a graph showing the effect of weed control (ageratum, foxtail grass, and willow plantain) after 3 days using the dispersible oil suspension formulation of Example 1 of the present application. [Diagram 2] FIG. 2 is a graph showing the effect of weed control (ageratum, foxtail grass, and willow plantain) after 7 days using the dispersible oil suspension formulation of Example 1 of the present application. [Diagram 3] FIG. 3 is a graph showing the effect of weed control (goosegrass, green foxtail, reed, chickweed, crabgrass, Japanese laurel, Japanese railroad grass, Japanese knotweed, Japanese quince, Japanese knotweed, Japanese knotweed, and Japanese sedge) three days after using the dispersible oil suspension formulation of Example 1 of the present application. [Figure 4] FIG. 4 is a graph showing the effect of weed control (goosegrass, green foxtail, reed, chickweed, crabgrass, Japanese laurel, Japanese railroad grass, Japanese knotweed, Japanese quince, Japanese knotweed, Japanese knotweed, and Japanese sedge) after 15 days using the dispersible oil suspension formulation of Example 1 of the present application. [Diagram 5] FIG. 5 is a graph showing the effect of weed control (goosegrass, green foxtail, reed, chickweed, crabgrass, Japanese laurel, Japanese railroad grass, Japanese knotweed, Japanese quince, Japanese mustard spinach, and Japanese boxwood) after 30 days using the dispersible oil suspension formulation of Example 1 of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The present invention will be described below with reference to specific embodiments, but is not limited to the specific examples shown below. Example 1

[0028] The benzylazole-containing dispersible oil suspension contains, by weight, specific ingredients: 33 parts glyphosate ammonium salt, 1 part benzylazole, 5 parts wetting and dispersing agent TSC-930, 12 parts emulsifier OD21, 1 part white carbon black, 1 part organic bentonite, and 100 parts supplemental methyl oleate.

[0029] Here, the glyphosate ammonium salt is produced by our company and has a purity of more than 96%, the benzyl azole is produced by our company and has a purity of more than 92%, the wetting and dispersing agent TSC-930 is purchased from Takemoto Oil Co., Ltd., the emulsifier OD21 is purchased from Wuxi Yi Jingfeng Technology Co., Ltd., the white carbon black is purchased from Nantong Ye Lu New Materials Sales Co., Ltd., and the organic bentonite is purchased from Zhangjiagang Bonded Zone Guangxing International Trade Co., Ltd.

[0030] The method for preparing the dispersible oil suspension is as follows. (1) After dissolving benzylazole in methyl oleate, add the remaining ingredients and shear for 5 minutes at speed 5 of a high-speed shear machine to form a uniform oil phase and prepare it for use. (2) Pour 50°C water into a horizontal sand mill, add the oil phase first in the appropriate ratio, and after the circulation becomes normal, add glyphosate ammonium salt and grind until the particle size D97 is 6.235 μm, D10 is 0.527 μm, D50 is 1.090 μm, and D90 is 3.446 μm.

[0031] The dispersible oil suspensions obtained in this example were tested and the test results are shown in Table 1. [Table 1] Note: The test environment for the oil precipitation rate was high-temperature storage for 14 days, leaving it at room temperature for a long period of time, and then transferring it from high-temperature storage to room temperature. No obvious oil precipitation was observed in any of the tests.

[0032] The dispersible oil suspension obtained in this example was subjected to efficacy testing.

[0033] The laboratory tests are as follows: "Test weeds": Abutilon japonica, purslane, goosegrass, crabgrass, barnyard grass "Test Unit" Zhejiang Agriculture and Forestry University Green Pesticide Collaborative Innovation Center (Chen Jie) Test Method The stems and leaves of potted plants in a greenhouse (28±5℃) were misted with the mist, with three duplicates and a blank control set up separately. After the plants were treated, they were grown normally in the greenhouse, and the reaction symptoms of the plants were observed at regular intervals. Ten days after spraying, the fresh weight of the aboveground parts of the weeds was measured, and the fresh weight and control effect were calculated. The control effect of weeds that were completely dead was calculated as 100%. "Test Results" The herbicidal activity of velvetleaf, purslane, goosegrass, crabgrass, and barnyard grass was all 90.0% or higher.

[0034] The field tests are as follows:

[0035] Test 1 "Test site": Lujunyi Village, Jingshan Town, Lin'an City "Test Unit" Zhejiang Agriculture and Forestry University Green Pesticide Collaborative Innovation Center (Chen Jie) "Exam time" 2021.07.06~2021.08.05 "Formulation usage amount" 190g / mo "Major weeds" Ageratum, foxtail, willow weed, weeds are in the mature fruiting stage, coverage is 80-100%. "Test Results" As shown in Figure 1, on the third day after spraying the drug, certain symptoms of poisoning were observed and the weed leaves began to wilt, and as shown in Figure 2, on the seventh day after spraying the drug, the effect was obvious.

[0036] Test 2 "Test site": Vacant lot in the East Market Area of ​​Jiangshan Company (completed by in-house staff of the Business Development Department) "Exam time" 2021.8.9~2021.9.8 "Formulation usage amount" 180g / mo "Major weeds" goosegrass, foxtail, reeds, sedge, crabgrass, Japanese bush clover, fleabane, rail grass, Japanese knotweed, sedge, Japanese knotweed, Japanese knotweed, and octopus foot "Test Results" As shown in Figure 3, three days after spraying the drug, certain symptoms of poisoning were observed; as shown in Figure 4, 15 days after spraying the drug, the effect was remarkable; and as shown in Figure 5, 30 days after spraying the drug, the weeds had almost disappeared. Example 2

[0037] For the benzylazole-containing dispersible oil suspension, the specific components are the same as those in Example 1, with the difference being that the wetting and dispersing agent TSC-930 was replaced with the wetting and dispersing agent SP-OF3494D, which was purchased from Jiangsu Chinyu Chemical Technology Co., Ltd.

[0038] The method for preparing the benzylazole-containing dispersible oil suspension was the same as in Example 1, except that the wetting and dispersing agent TSC-930 was replaced with the wetting and dispersing agent SP-OF3494D. Example 3

[0039] For the benzylazole-containing dispersible oil suspension, the specific components are the same as in Example 1, except for 0.5 parts of organic bentonite.

[0040] The method for preparing the benzylazole-containing dispersible oil suspension was the same as in Example 1.

[0041] In both the dispersible oil suspensions of Example 2 and Example 3, no obvious oil precipitation phenomenon occurred. Example 4

[0042] For the benzylazole-containing dispersible oil suspension, the specific ingredients are the same as in Example 1, except that 5 parts of wetting and dispersing agent TSC-930 and 12 parts of emulsifier OD21 were replaced with 17 parts of Huntsman WELOD461.

[0043] The preparation method of dispersible oil suspension was the same as that of Example 1, except that the wetting and dispersing agent TSC-930 and emulsifier OD21 were replaced by 461. Example 5

[0044] For the benzylazole-containing dispersible oil suspension, the specific components are the same as in Example 1, except that the wetting and dispersing agent TSC-930 is replaced with the wetting and dispersing agent SP-OF3498D.

[0045] The method for preparing the dispersible oil suspension was the same as that in Example 1, except that the wetting dispersant TSC-930 was replaced with the wetting dispersant SP-OF3498D, and the particle size D97 was ground to 2.824 μm in step (2). Example 6

[0046] For the benzylazole-containing dispersible oil suspension, the specific components are the same as those in Example 1, with the difference being that the wetting and dispersing agent TSC-930 is replaced by the wetting and dispersing agent SP-OF3498D, and the emulsifier OD21 is replaced by ODE286.

[0047] The preparation method of the dispersible oil suspension is the same as that of Example 1, except that the wetting dispersant TSC-930 is replaced by the wetting dispersant SP-OF3498D, and the emulsifier OD21 is replaced by ODE286. Example 7

[0048] For the benzylazole-containing dispersible oil suspension, the specific components are the same as those in Example 1, except that the wetting and dispersing agent TSC-930 is replaced by the wetting and dispersing agent SP-OF3498D, and the emulsifier OD21 is replaced by TSC901.

[0049] The preparation method of the dispersible oil suspension was the same as that of Example 1, except that the wetting dispersant TSC-930 was replaced with the wetting dispersant 3498D, the emulsifier OD21 was replaced with TSC901, and the particle size D97 was ground to 2.577 μm. Example 8

[0050] For the benzylazole-containing dispersible oil suspension, the specific components are the same as in Example 1, except that the wetting and dispersing agent TSC-930 is replaced with the wetting and dispersing agent GY-EM05.

[0051] The preparation method of the dispersible oil suspension was the same as that of Example 1, except that the wetting dispersant TSC-930 was replaced with the wetting dispersant GY-EM05, and the particle size D97 was ground to 2.458 μm. Example 9

[0052] For the benzylazole-containing dispersible oil suspension, the specific ingredients are the same as in Example 1.

[0053] The method for preparing the dispersible oil suspension was the same as that in Example 1, except that in step (2), the powder was ground until the particle size D97 reached 2.787 μm.

[0054] The test results of Examples 4 to 9 are shown in Table 2. [Table 2]

[0055] The test methods for viscosity, dilution stability, and sustained foaming were the same as those in Example 1.

[0056] The test method or standard for suspension rate is to prepare a suspension of the test sample at an appropriate concentration using standard hard water. The suspension is left in a measuring cylinder for a certain period of time under specified conditions, and the mass of the active ingredient in the suspension and sediment at the bottom is measured.

[0057] During the test, the dilution stability of the dispersible oil suspensions obtained in Examples 5 and 9 was acceptable, and the dispersibility of the dispersible oil suspension obtained in Example 9 was superior to that of the dispersible oil suspension of Example 5, and the dispersible oil suspension of Example 9 dispersed in a cloud-like form. Examples 10 to 15

[0058] Examples 10 to 15 provide dispersible oil suspensions, the specific components of which are the same as those of Example 1, and the difference is that the contents of white carbon black and organic bentonite are different; the preparation methods and specific embodiments are the same as those of Example 1, and the difference is that the particle diameters D97 are different, see Table 3 for details. [Table 3] Examples 16 to 26

[0059] Examples 16 to 26 provide dispersible oil suspensions, the specific components of which are the same as those of Example 1, except that the types of wetting dispersants and emulsifiers are different, see Table 4 for details. [Table 4] Examples 27-33

[0060] For the benzylazole-containing dispersible oil suspension, the specific components are the same as those in Example 1, except that the types of wetting and dispersing agents and emulsifying agents are different, see Table 5 for details.

[0061] The preparation method and specific embodiment are the same as those in Example 1, except that the corresponding wetting and dispersing agents and emulsifying agents added are different. [Table 5]

[0062] The compounding methods of Example 5 and Example 28 of the present application are the same, and the variation of the test results is within a reasonable range, and the test results are stable. Examples 34 to 39

[0063] Regarding the dispersible oil suspension, the specific components are the same as those in Example 1, with the difference being that the glyphosate ammonium salt is glyphosate acid, the wetting and dispersing agent, the emulsifying agent are different, and the components further include the stabilizer sodium polyphosphate, see Table 6 for details. [Table 6]

Claims

1. A dispersible oil suspension containing benzylazole, characterized in that it comprises 22 to 44 parts by weight of glyphosate ammonium salt, 0.5 to 1.5 parts by weight of benzylazole, 3 to 8 parts by weight of a wetting and dispersing agent, 10 to 15 parts by weight of an emulsifier, 1 to 2 parts by weight of a structural modifier, and 100 parts by weight of a supplementing solvent.

2. A dispersible oil suspension containing benzylazole according to claim 1, characterized in that the weight ratio of the glyphosate ammonium salt to the benzylazole is (28-38):

1.

3. The dispersible oil suspension containing benzylazole according to claim 2, wherein the wetting and dispersing agent is one or more of sulfonates, polycarboxylates, and sulfate dispersants, and preferably the wetting and dispersing agent is one or more selected from TSC-930, SP-OF3498D, GY-EM05, and WELOD461.

4. The dispersible oil suspension containing benzylazole according to claim 3, characterized in that the emulsifier is one or more selected from OD21, OD286, and TSC901.

5. A dispersible oil suspension containing benzylazole according to claim 4, characterized in that the weight ratio of the wetting dispersant to the emulsifier is 5:(11-14).

6. A dispersible oil suspension containing benzylazole according to any one of claims 1 to 5, characterized in that the structural modifier is white carbon black and / or organic bentonite.

7. The dispersible oil suspension containing benzylazole according to claim 6, characterized in that the structural modifier is white carbon black and organic bentonite in a weight ratio of (1 to 3):

1.

8. The dispersible oil suspension containing benzylazole according to claim 7, characterized in that the dispersible oil suspension further comprises 5 to 10 parts by weight of a synergistic agent.

9. A method for preparing a dispersible oil suspension containing benzylazole according to any one of claims 1 to 7, characterized by comprising mixing benzylazole, a wetting and dispersing agent, an emulsifier, a structural modifier, a solvent, and a glyphosate ammonium salt, and then polishing the mixture.

10. A method for preparing a dispersible oil suspension according to claim 9, characterized by comprising: mixing benzylazole, a wetting and dispersing agent, an emulsifier, a structural modifier, and a solvent to form an oil phase; adding the oil phase to a sand mill, circulating the oil phase, adding a glyphosate ammonium salt, and polishing.

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