CN113575582A

CN113575582A - Synergistic herbicide containing cyhalofop-butyl

Info

Publication number: CN113575582A
Application number: CN202110996118.4A
Authority: CN
Inventors: 陈金如; 钱同兰; 范泽求; 范进林
Original assignee: Anhui Shengdan Biochemical Co ltd
Current assignee: Anhui Shengdan Biochemical Co ltd
Priority date: 2021-08-27
Filing date: 2021-08-27
Publication date: 2021-11-02

Abstract

The invention discloses a synergistic herbicide containing cyhalofop-butyl, belonging to the technical field of pesticides, and comprising the following components in percentage by weight: 15-60% of cyhalofop-butyl, 10-45% of composite synergist, 0.5-4% of defoaming agent and the balance of auxiliary components. The modified castor oil and alkylphenol ethoxylates are used as the compound synergist, so that the toxicity and the pesticide effect of the pesticide can be greatly improved, and the effect is better than that of a single pesticide synergist; the modified castor oil is obtained by utilizing the gradual reaction of the maleic anhydride, the monoethanolamine, the polytetrahydrofuran, the epichlorohydrin and the castor oil, does not contain a hard chain segment of polyester, has good affinity and adhesiveness with a wax layer on the surface layer of a plant due to the main molecular chain mainly comprising ether bonds, is beneficial to the permeation, the spreading and the adhesion of the cyhalofop-butyl on the surface body of the plant, promotes the absorption of the cyhalofop-butyl by a target crop, and improves the pesticide effect of the cyhalofop-butyl.

Description

Synergistic herbicide containing cyhalofop-butyl

Technical Field

The invention belongs to the technical field of pesticides, and particularly relates to a synergistic herbicide containing cyhalofop-butyl.

Background

Cyhalofop-butyl is an aryloxycarboxylic acid herbicide developed by the dow agricultural science corporation of america. The aryloxy phenoxy propionic acid herbicide is a variety with high safety on rice, has systemic conductivity, is absorbed by leaves and leaf sheaths of plants, conducts phloem, accumulates in meristematic regions of the plants, inhibits acetyl coenzyme A carboxylase, stops fatty acid synthesis, and prevents cell division from normally proceeding, thus causing damage to ester-containing structures such as membrane systems and finally causing plant death. The cyhalofop-butyl herbicide has the following distinct characteristics: (1) the rice is highly safe, and even if the dosage exceeds the recommended dosage by several times, the rice is not harmed by pesticide; (2) the weeding composition has a wide prevention and removal range, has a special effect on moleplant seeds and barnyard grass, and can prevent more than 30 gramineous weeds such as paspalum distichum, crabgrass, green bristlegrass, goosegrass herb, aloesmus vaginalis and the like; (3) the application range is wide, the application period is wide, the fertilizer can be used for indica rice and japonica rice, various cultivation modes can be used, such as dry seedling raising, water seedling raising, direct seeding, seedling throwing, seedling transplanting and the like, and the pesticide damage cannot be generated when the fertilizer is used from the seedling stage to the jointing stage.

When the cyhalofop-butyl is used for the herbicide, the herbicide often forms liquid drops on the surface of the herbicide due to paraffin existing on the leaf surface of a target object, and the herbicide is poor in wettability, so that a large amount of cyhalofop-butyl is lost and not absorbed by plants, the dosage of the herbicide is increased, and the environment is polluted. In order to solve the problem, a synergist is usually added into the herbicide, so that the wetting, spreading, dispersing, retaining and penetrating performances of the herbicide can be obviously improved, the drift of spraying liquid medicine along with wind (airflow) is reduced, the damage to adjacent sensitive crops and the like is prevented or reduced, the spreading and adhesion of the liquid medicine on leaf surfaces are facilitated, the decomposition of effective components in a pesticide preparation by ultraviolet rays is reduced, and the aims of prolonging the effective period of the pesticide effect, improving the biological activity of the pesticide preparation, reducing the dosage, reducing the cost and protecting the ecological environment are fulfilled. However, the conventional synergist cannot greatly improve the weeding effect of cyhalofop-butyl and has a limited synergistic effect.

Therefore, the invention provides a synergistic herbicide containing cyhalofop-butyl.

Disclosure of Invention

The invention aims to provide a synergistic herbicide containing cyhalofop-butyl, which solves the technical problems that the prior synergistic agent can not greatly improve the weeding effect of the cyhalofop-butyl and has limited synergistic effect.

The purpose of the invention can be realized by the following technical scheme:

the cyhalofop-butyl-containing synergistic herbicide comprises the following components in percentage by weight: 15-60% of cyhalofop-butyl, 10-45% of composite synergist, 0.5-4% of defoaming agent and the balance of auxiliary components.

Furthermore, the pesticide formulation prepared from the synergistic herbicide containing cyhalofop-butyl is one of aqueous emulsion, suspending agent, microemulsion and water dispersible granule.

Further, the auxiliary components comprise a solvent and an auxiliary agent.

Further, the solvent is one or a mixture of several of deionized water, toluene, diesel oil, ethanol, DMF and vegetable oil in any ratio.

Furthermore, the auxiliary agent is one or a mixture of several of an antifreezing agent, a thickening agent, a disintegrating agent, a stabilizing agent and a filler in any ratio, and can be selected according to the prepared pesticide dosage form.

Further, the antifreezing agent is one or a mixture of several of ethylene glycol, propylene glycol and glycerol in any ratio.

Further, the thickening agent is one or a mixture of several of xanthan gum, carboxyethyl cellulose and methyl cellulose in any ratio.

Further, the disintegrating agent is one or a mixture of more of ammonium sulfate, aluminum chloride, citric acid and urea in any ratio.

Further, the stabilizer is one or a mixture of several of epoxidized vegetable oil, sodium citrate and resorcinol in any ratio.

Further, the filler is one or a mixture of several of silicon dioxide, diatomite, attapulgite and montmorillonite in any ratio.

Further, the composite synergist is formed by mixing modified castor oil and alkylphenol ethoxylates according to the mass ratio of 1-3: 1.

Further, the defoaming agent is organic silicone oil.

Further, the modified castor oil is prepared by the following steps:

step A, adding maleic anhydride and monoethanolamine into a four-neck flask, adding ethanol to completely dissolve the maleic anhydride and the monoethanolamine, then placing the four-neck flask into an oil bath pot, heating to 70-95 ℃, refluxing for 10 hours, then cooling to room temperature, transferring the solution into a container, placing the container into an oven, and performing vacuum drying at 35 ℃ to obtain an intermediate product 1, wherein the reaction formula is shown as follows;

step B, adding the intermediate product 1 obtained in the step A and polytetrahydrofuran into a four-neck flask, heating the temperature of a reaction system to 50-70 ℃, uniformly stirring, dropwise adding p-toluenesulfonic acid by using a dropping funnel at the dropping speed of 1 drop/second, stirring and reacting for 3 hours under the protection of nitrogen after complete dropwise addition, then reducing the temperature to 20 ℃, and performing rotary evaporation to remove small molecules, transferring the reaction solution into a container, and placing the container into an oven to perform vacuum drying at 85 ℃ to finally obtain an intermediate product 2, wherein the reaction formula is shown as follows;

step C, placing the intermediate product 2 obtained in the step B into a reactor, heating to 60-70 ℃ for melting, then placing into a nitrogen glove box, adding boron trifluoride diethyl etherate complex, dropwise adding epoxy chloropropane by using a metering pump, wherein the dropwise adding speed is 1 drop/second, reacting for 3.5 hours at 60-70 ℃ after completely dropwise adding to obtain an intermediate product 3, and the reaction formula is shown as follows;

and D, sequentially adding the castor oil and the absolute ethyl alcohol into a four-neck flask with a stirrer, adding the intermediate product 3 obtained in the step C under the stirring state, then adding a tert-butyl alcohol solution of potassium tert-butoxide, stirring and reacting for 2.5-5h at room temperature, taking out the reactant, and washing with water to obtain the modified castor oil.

Further, the dosage ratio of the maleic anhydride, the monoethanolamine and the ethanol in the step A is 0.1-0.14 mol: 0.1 mol: 150 and 250 mL.

Further, the using ratio of the intermediate product 1, the polytetrahydrofuran and the p-toluenesulfonic acid in the step B is 0.04-0.044 mol: 0.01 mol: 0.2-0.4g, and the number average molecular weight of the polytetrahydrofuran is 1000-1500.

Furthermore, the dosage ratio of the intermediate product 2, the epichlorohydrin and the boron trifluoride diethyl etherate in the step C is 0.01 mol: 0.02-0.022 mol: 0.1-0.25 g.

Further, the dosage ratio of the castor oil, the ethanol, the intermediate product 3 and the tert-butyl alcohol solution of the potassium tert-butoxide in the step D is 5-25g:100-300 g: 300-600 mL: 3.5-6g, the mass concentration of the potassium tert-butoxide in the tert-butyl alcohol solution of the potassium tert-butoxide is 60-80%.

The invention has the beneficial effects that:

1. the invention utilizes the modified castor oil and the alkylphenol ethoxylates to be mixed as the compound synergist, can greatly improve the toxicity and the efficacy of the pesticide, and has better effect than the single pesticide synergist;

2. the invention utilizes maleic anhydride and monoethanolamine to prepare an intermediate product 1, then utilizes the intermediate product 1 and polytetrahydrofuran to synthesize an intermediate product 2, then utilizes the intermediate product 2 and epichlorohydrin to synthesize an intermediate product 3, and then utilizes the intermediate product 3 to react with castor oil to obtain modified castor oil, a large amount of polyether chains are introduced into molecular chains of the modified castor oil to increase the hydrophilicity of the castor oil, and the modified castor oil does not contain hard chain segments of polyester, the molecular chains of the obtained modified castor oil mainly contain ether bonds, the flexibility of the molecular chains is larger, so that the shearing emulsification process of the castor oil is easy to carry out, the particle size is smaller, the permeability is improved, and the castor oil belongs to natural vegetable oil, has good similar compatibility with natural vegetable surfaces and good affinity and adhesiveness with wax layers (hydrophobic substrates) on the vegetable surfaces, the modified castor oil can accelerate the absorption efficiency of crops on cyhalofop-butyl, can form uniform and stable emulsion with pesticide, water and the like, is beneficial to the permeation, the spreading and the adhesion of cyhalofop-butyl on the surface of plants, promotes the absorption of the target crops on the cyhalofop-butyl, improves the pesticide effect of the cyhalofop-butyl, is a plant-based synergist, and has good degradation performance and good environmental protection.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the modified castor oil is prepared by the following steps:

step A, adding maleic anhydride and monoethanolamine into a four-neck flask, adding ethanol to completely dissolve the maleic anhydride and the monoethanolamine, then placing the four-neck flask into an oil bath pot, heating to 70 ℃, refluxing for 10 hours, then cooling to room temperature, transferring the solution into a container, placing the container into an oven, and performing vacuum drying at 35 ℃ to obtain an intermediate product 1;

step B, adding the intermediate product 1 obtained in the step A and polytetrahydrofuran into a four-neck flask, heating the temperature of a reaction system to 50 ℃, uniformly stirring, dropwise adding p-toluenesulfonic acid by using a dropping funnel at the dropping speed of 1 drop/second, stirring and reacting for 3 hours under the protection of nitrogen after complete dropwise addition, then reducing the temperature to 20 ℃, performing rotary evaporation to remove small molecules, transferring the reaction solution into a container, and placing the container in an oven to perform vacuum drying at 85 ℃ to finally obtain an intermediate product 2;

step C, placing the intermediate product 2 obtained in the step B into a reactor, heating to 60-70 ℃ for melting, then placing into a nitrogen glove box, adding boron trifluoride diethyl etherate complex, dropwise adding epoxy chloropropane by using a metering pump at the dropwise adding speed of 1 drop/second, and reacting for 3.5 hours at 60 ℃ after completely dropwise adding to obtain an intermediate product 3;

and D, sequentially adding the castor oil and the absolute ethyl alcohol into a four-neck flask with a stirrer, adding the intermediate product 3 obtained in the step C under the stirring state, then adding a tert-butyl alcohol solution of potassium tert-butoxide, stirring and reacting for 2.5h at room temperature, taking out the reactant, and washing with water to obtain the modified castor oil.

The ratio of the amounts of the raw materials used in the respective steps is shown in Table 1.

TABLE 1

Example 2:

the modified castor oil is prepared by the following steps: reference is made to the steps in example 1;

the ratio of the amounts of the raw materials used in the respective steps is shown in Table 2.

TABLE 2

Example 3:

the ratio of the amounts of the raw materials used in the respective steps is shown in Table 3.

TABLE 3

Example 4:

the synergistic herbicide containing cyhalofop-butyl is prepared into an aqueous emulsion, and the raw materials and the weight percentage thereof are shown in Table 4.

TABLE 4

The preparation method comprises the following steps: mixing the cyhalofop-butyl, the organic solvent, the composite synergist and the sodium citrate in the weight parts in the table to dissolve the mixture into a uniform oil phase; mixing part of water, glycerol in the weight parts in the table and a defoaming agent together to form a uniform water phase; adding the oil phase into the water phase while stirring at a high speed in a reaction kettle, adding the methyl cellulose in parts by weight in the table, slowly adding water until the phase inversion point is reached, starting a shearing machine to carry out high-speed shearing, adding the rest water, and shearing for about half an hour to obtain the synergistic herbicide aqueous emulsion.

Example 5:

the synergistic herbicide containing cyhalofop-butyl is prepared into a pesticide formulation which is a suspending agent, and the raw materials and the weight percentage thereof are shown in Table 5.

TABLE 5

The preparation method comprises the following steps: and (3) uniformly shearing and mixing the composite synergist, the glycerol, the methyl cellulose, the defoaming agent, the resorcinol and the water in parts by weight in the table at a high speed, adding the cyhalofop-butyl in parts by weight in the table, and grinding the mixture in a ball grinder for 2 hours to ensure that the particle diameter is below 5mm, thus preparing the suspending agent preparation of the synergistic herbicide.

Example 6:

a synergistic herbicide containing cyhalofop-butyl is prepared into microemulsion, and the raw materials and the weight percentage thereof are shown in Table 6.

TABLE 6

The preparation method comprises the following steps: the microemulsion preparation of the composite herbicide is prepared by completely dissolving the cyhalofop-butyl in the weight parts in the table by using an organic solvent, then adding the composite synergist, the carboxyethyl cellulose, the propylene glycol and the organic silicone oil in the weight parts in the table, uniformly mixing, finally adding the water, and fully stirring.

Example 7:

a cyhalofop-butyl-containing synergistic herbicide is prepared into a pesticide formulation of water dispersible granules, and the raw materials and the weight percentage thereof are shown in Table 7.

TABLE 7

The preparation method comprises the following steps: the water dispersible granule of the synergistic herbicide can be prepared by uniformly mixing the cyhalofop-butyl, the composite synergist, the mixture of ammonium sulfate and aluminum chloride, water and diatomite in parts by weight in the table, crushing by using an ultramicro jet mill, kneading, adding into a fluidized bed granulation dryer for granulation, drying and screening, and then sampling and analyzing.

Comparative example 1:

the herbicide containing cyhalofop-butyl is prepared into an aqueous emulsion, and the raw materials and the weight percentage thereof are shown in Table 8.

TABLE 8

Cyhalofop-butyl	15％
		Alkylphenol ethoxylates	10％
Glycerol	6％
		Methyl cellulose	5％
Defoaming agent: organic silicone oil	0.5％
		Citric acid sodium salt	3.5％
Organic solvent: DMA	15％
		Water (W)	Balance of

The preparation method comprises the following steps: refer to the procedure in example 4.

Comparative example 2:

the synergistic herbicide containing cyhalofop-butyl is prepared into a pesticide formulation which is a suspending agent, and the raw materials and the weight percentage thereof are shown in Table 9.

TABLE 9

Cyhalofop-butyl	20％
		Modified Castor oil preparation for example 2	18％
Glycerol	6％
		Resorcinol	4.5％
Methyl cellulose	5％
		Defoaming agent: organic silicone oil	2％
Water (W)	Balance of

The preparation method comprises the following steps: refer to the procedure in example 5.

Comparative example 3:

a synergistic herbicide containing cyhalofop-butyl is prepared into microemulsion, and the raw materials and the weight percentage thereof are shown in Table 10.

Watch 10

The preparation method comprises the following steps: refer to the procedure in example 6.

Comparative example 4:

the pesticide formulation prepared from the synergistic herbicide containing cyhalofop-butyl is water dispersible granules, and the raw materials and the weight percentage thereof are shown in Table 11.

TABLE 11

The preparation method comprises the following steps: refer to the procedure in example 7.

Example 8:

and (3) field test:

the synergistic herbicide obtained in examples 4-7 and comparative examples 1-4 is used for field efficacy test of annual gramineous weeds in a direct seeding field of paddy rice, 9 groups of test fields are selected, 8 groups are selected as treatment groups (corresponding to examples 4-7 and comparative examples 1-4), and 1 group is selected as a control group; spraying time: the herbicide is applied to the rice weeds at the 2-3 leaf stage, water is added for uniform spraying, the weeding effect is observed after 30 days, the weeding effect is calculated according to the following calculation formula, and the finished test data are shown in table 12.

K₁The number of weeds in the control test field, K the number of weeds in the treatment test field, G₀The fresh weight of the weeds in the control group test field and G is the fresh weight of the weeds in the treatment group test field.

TABLE 12

As can be seen from the data in Table 12, the synergistic herbicides obtained in examples 4-7 exhibited better plant control and fresh weight control than the herbicides of comparative examples 1-4.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims

1. The cyhalofop-butyl-containing synergistic herbicide is characterized by comprising the following components in percentage by weight: 15-60% of cyhalofop-butyl, 10-45% of composite synergist, 0.5-4% of organic silicone oil and the balance of auxiliary components;

the composite synergist is formed by mixing modified castor oil and alkylphenol ethoxylates according to the mass ratio of 1-3: 1;

the modified castor oil is prepared by the following steps:

step A, adding maleic anhydride and monoethanolamine into ethanol, stirring uniformly, heating the temperature of a reaction system to 70-95 ℃, refluxing for 10 hours, then cooling to room temperature, and drying the solution in vacuum to obtain an intermediate product 1;

step B, mixing the intermediate product 1 obtained in the step A with polytetrahydrofuran, heating the temperature of a reaction system to 50-70 ℃, uniformly stirring, dropwise adding p-toluenesulfonic acid at the dropping speed of 1 drop/second, stirring and reacting for 3 hours under the protection of nitrogen after complete dropwise adding, then performing rotary evaporation, and performing vacuum drying on the reaction solution to obtain an intermediate product 2;

step C, placing the intermediate product 2 obtained in the step B into a reactor, heating to 60-70 ℃ for melting, then adding boron trifluoride diethyl etherate complex in the nitrogen atmosphere, dropwise adding epoxy chloropropane at the dropping speed of 1 drop/second, and reacting for 3.5 hours at 60-70 ℃ after complete dropwise addition to obtain an intermediate product 3;

and D, mixing the castor oil and the absolute ethyl alcohol, adding the intermediate product 3 obtained in the step C under the stirring state, then adding a tert-butyl alcohol solution of potassium tert-butoxide, stirring and reacting for 2.5-5h at room temperature, taking out the reactant, and washing with water to obtain the modified castor oil.

2. The synergistic herbicide containing cyhalofop-butyl as claimed in claim 1, wherein the ratio of the amount of the maleic anhydride, the monoethanolamine and the ethanol in step A is 0.1-0.14 mol: 0.1 mol: 150 and 250 mL.

3. The synergistic cyhalofop-butyl-containing herbicide as claimed in claim 1, wherein the amount ratio of the intermediate product 1, polytetrahydrofuran and p-toluenesulfonic acid in step B is 0.04-0.044 mol: 0.01 mol: 0.2-0.4 g.

4. The synergistic herbicide containing cyhalofop-butyl as claimed in claim 1, wherein the ratio of the amount of intermediate 2, epichlorohydrin and boron trifluoride etherate in step C is 0.01 mol: 0.02-0.022 mol: 0.1-0.25 g.

5. The cyhalofop-butyl-containing synergistic herbicide as claimed in claim 1, wherein the cyhalofop-butyl-containing synergistic herbicide is prepared in a pesticide form of one of an aqueous emulsion, a suspending agent, a microemulsion and water dispersible granules.