阅读说明：本技术 一种用于磺酰脲类除草剂的稳定剂及其制备方法和应用 (Stabilizing agent for sulfonylurea herbicide and preparation method and application thereof ) 是由 佟雨佳 赵军 魏亚 于 2019-09-04 设计创作，主要内容包括：本发明公开了一种磺酰脲类除草剂稳定剂及其制备方法,以所述用于磺酰脲类除草剂的稳定剂的总重量为100％计,所述用于磺酰脲类除草剂的稳定剂包括如下重量份的组分：10％～50％金属皂类稳定剂；5％～30％辅助稳定剂；5％～30％抗氧化剂；溶剂补足至100％；其中,所述金属皂类稳定剂为钙盐稳定剂与锌盐稳定剂的混合物。本发明稳定剂适用于甲基二磺隆、苄嘧磺隆、吡嘧磺隆、氯吡嘧磺隆、氟唑磺隆等磺酰脲类除草剂的各种液体剂型,较好的剂型有乳油、可分散油悬浮剂或展膜油剂。本发明所述稳定剂可显著降低磺酰脲类除草剂在农药制剂加工中的有效成分分解,保持农药液体制剂产品的质量稳定。(The invention discloses a sulfonylurea herbicide stabilizer and a preparation method thereof, wherein the total weight of the stabilizer for sulfonylurea herbicides is 100%, and the stabilizer for sulfonylurea herbicides comprises the following components in parts by weight: 10-50% of metal soap stabilizer; 5 to 30 percent of auxiliary stabilizer; 5 to 30 percent of antioxidant; the solvent is complemented to 100%; wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer. The stabilizer of the invention is suitable for various liquid formulations of sulfonylurea herbicides such as mesosulfuron, bensulfuron-methyl, pyrazosulfuron-ethyl, halosulfuron-methyl, flucarbazone-methyl and the like, and the better formulations are missible oil, dispersible oil suspending agent or film spreading oil agent. The stabilizing agent can obviously reduce the decomposition of the active ingredients of the sulfonylurea herbicide in the processing of pesticide preparations and keep the quality of pesticide liquid preparation products stable.)

1. A stabilizer for sulfonylurea herbicides, which comprises the following components in percentage by weight, based on 100% by weight of the total weight of the stabilizer for sulfonylurea herbicides:

wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer.

2. The stabilizer for sulfonylurea herbicides according to claim 1, wherein the calcium salt stabilizer is at least one selected from the group consisting of calcium stearate, calcium ricinoleate, calcium hydroxide and calcium phosphite.

3. A stabilizer for sulfonylurea herbicides according to claim 1, wherein the zinc salt stabilizer is at least one selected from the group consisting of zinc stearate, zinc ricinoleate, zinc 2-ethylhexanoate, zinc laurate, zinc naphthenate, zinc neodecanoate, zinc oxide, benzoic acid and substituted zinc benzoate.

4. A stabilizer for sulfonylurea herbicides according to any one of claims 1 to 3, wherein the auxiliary stabilizer is at least one selected from the group consisting of epoxidized soybean oil, epichlorohydrin, diphenylmonooctyl phosphite, diphenylmonodecyl phosphite, trisnonylphenyl phosphite, dibenzoylmethane, pentaerythritol, distearylpentaerythritol diphosphite and aminouracil.

5. A stabilizer for sulfonylurea herbicides according to any one of claims 1 to 3, wherein the antioxidant is at least one selected from the group consisting of 2, 6-ditert-butyl-p-cresol, bisphenol A and nonylphenol.

6. A stabilizer for sulfonylurea herbicides according to any one of claims 1 to 3, wherein the solvent is at least one selected from the group consisting of liquid paraffin, white oil, diesel oil, mineral oil and oxidized soybean oil.

7. A preparation method of a stabilizing agent for sulfonylurea herbicides is characterized by comprising the following steps:

weighing the components according to the stabilizing agent for sulfonylurea herbicides according to any one of claims 1 to 6;

uniformly stirring the solvent, adding a metal soap stabilizer, an auxiliary stabilizer and an antioxidant, and heating and stirring for 2-3 hours to obtain a first mixture;

and (3) carrying out pressure filtration on the first mixture to obtain a light yellow filtrate, wherein the light yellow filtrate is a stabilizer for the sulfonylurea herbicide.

8. The method for producing a stabilizer for sulfonylurea herbicides according to claim 7, wherein the heating temperature in the step of heating and stirring is 107 to 120 ℃.

9. The sulfonylurea herbicide is characterized in that the sulfonylurea herbicide comprises 5-10% of stabilizer by taking the total weight of the sulfonylurea herbicide as 100%, and the stabilizer comprises the following components in percentage by weight by taking the total weight of the stabilizer as 100%: 10-50% of metal soap stabilizer; 5 to 30 percent of auxiliary stabilizer; 5 to 30 percent of antioxidant; make up to 100% solvent; wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer.

10. The sulfonylurea herbicide according to claim 9, characterized in that the pesticidal active ingredient of the sulfonylurea herbicide is any one selected from the group consisting of mesosulfuron, bensulfuron, pyrazosulfuron, halosulfuron-methyl and flucarbazone-methyl.

Technical Field

The invention relates to the technical field of pesticides, in particular to a stabilizing agent for sulfonylurea herbicides and a preparation method and application thereof.

Background

The sulfonylurea herbicide has wide herbicidal spectrum and high activity, and may be used widely in dry land and paddy field. Through research, the vegetable oil, the mineral oil and the methyl esterified vegetable oil can promote the drug effect of the herbicide to be exerted, so that the emulsifiable solution, the dispersible oil suspending agent, the film-spreading oil agent and other liquid formulations are better formulations of the herbicide. However, in the processing of such oil preparations, sulfonylurea herbicides have a problem of decomposition of active ingredients. For example, under the condition that the mesosulfuron-methyl dispersible oil suspending agent is not added with a stabilizer, the decomposition rate of the thermal storage 14d is more than 15%, the thermal storage 14d is compounded with other herbicides and is decomposed more seriously, and the decomposition rate can reach more than 20%, and the application of the herbicides is severely restricted. The stability of the preparation is an important index for the pesticide standard and the quality measurement of products, and also guarantees that the pesticide can fully exert the pesticide effect in the using process. Therefore, the research on the stabilizer aiming at the active ingredients of the pesticide has great significance for improving the quality and ensuring the pesticide effect of the pesticide preparation.

Aiming at the problem that the active ingredients of the sulfonylurea herbicides are easy to decompose, the prior art adopts a stabilizing method comprising water regulation, pH value control, preparation system regulation and the like. In the aspect of using the stabilizer, a pH value regulator such as citric acid, triethanolamine and the like is common; moisture regulators such as anhydrous sodium carbonate, lignin, etc., but the stabilizing effect and the applicable range are not ideal. Meanwhile, sulfonylurea herbicide stabilizers have been disclosed in some patent documents. Patent CN 103960234B discloses that the high-efficiency stabilizer of sulfonylurea herbicides such as bensulfuron-methyl and metsulfuron-methyl is triphenyl phosphite and diphenyl sulfoxide, and the stabilizer can make the decomposition rate of the pesticide film-spreading oil agent stored at normal temperature for two years less than 5%, but the influence of the diversity of the preparation system on the stabilizing effect of the stabilizer is not involved. Patent CN 108041033a discloses a composite stabilizer for sulfonylurea herbicides, comprising a pH adjuster, a desiccant and urotropine, which can reduce the decomposition problem of sulfonylurea herbicide dispersible oil suspension. However, the invention is not concerned with the flexibility of a wider range of formulation systems.

The above invention can well control the decomposition of sulfonylurea herbicides under proper conditions, but the chemical stability effect is limited under certain preparation conditions, so that a stabilizer or a stabilizing technology capable of effectively controlling the decomposition of the active ingredients of sulfonylurea herbicides and adapting to more preparation systems is needed.

PVC heat stabilizer is a kind of existing, long-developing additives in the plastic industry, and can prevent or reduce the degradation or crosslinking of polymers caused by heating in the processing and using processes, and prolong the service life of composite materials. The common stabilizer comprises a composite calcium zinc stabilizer, a composite barium cadmium zinc stabilizer and the like, and can better solve the problems of oxidation discoloration and the like of PVC products. However, in the field of pesticides, the chemical stability of similar types of compounds for pesticides has not been reported, particularly in liquid formulations of herbicides.

Disclosure of Invention

The invention aims to provide a stabilizing agent for sulfonylurea herbicides, and aims to solve the problem that active ingredients of the sulfonylurea herbicides are easy to decompose in the using process in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

a stabilizer for sulfonylurea herbicides comprising the following components in parts by weight, based on 100% by weight of the stabilizer for sulfonylurea herbicides:

wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer.

And, a method for preparing a stabilizer for sulfonylurea herbicides, comprising the steps of:

weighing the components according to the stabilizing agent for the sulfonylurea herbicide;

uniformly stirring the solvent, adding a metal soap stabilizer, an auxiliary stabilizer and an antioxidant, and heating and stirring for 2-3 hours to obtain a first mixture;

and (3) carrying out pressure filtration on the first mixture to obtain a light yellow filtrate, wherein the light yellow filtrate is a stabilizer for the sulfonylurea herbicide.

And a sulfonylurea herbicide, wherein the sulfonylurea herbicide comprises 5-10% of a stabilizer by taking the total weight of the sulfonylurea herbicide as 100%, and the stabilizer comprises the following components in percentage by weight by taking the total weight of the stabilizer as 100%: 10-50% of metal soap stabilizer; 5 to 30 percent of auxiliary stabilizer; 5 to 30 percent of antioxidant; make up to 100% solvent; wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer.

Compared with the prior art, the stabilizing agent for the sulfonylurea herbicide provided by the invention comprises 10-50% of metal soap stabilizing agent; 5 to 30 percent of auxiliary stabilizer; 5 to 30 percent of antioxidant and solvent which is complemented to 100 percent, wherein the metal soap stabilizer is a mixture of calcium salt stabilizer and zinc salt stabilizer. The stabilizer provided by the invention can reduce the decomposition rate of the effective components in the sulfonylurea herbicide, so that the decomposition rate of the effective components in the pesticide during thermal storage is lower than 5%, and the utilization rate of the active components of the pesticide is favorably improved. And the stabilizer has good stabilizing effect, low cost and good practical value.

The preparation method of the stabilizing agent for the sulfonylurea herbicide provided by the invention only needs to mix the components according to the proportion, and the preparation method can uniformly disperse the components, thereby endowing the stabilizing agent for the sulfonylurea herbicide with excellent stability while realizing the beneficial effect of the stabilizing agent for the sulfonylurea herbicide. In addition, the preparation method has simple process, controllable conditions and low equipment requirement, and can be used for industrial production.

The sulfonylurea herbicide provided by the invention comprises 5-10% of stabilizer by taking the total weight of the sulfonylurea herbicide as 100%, and the stabilizer comprises the following components by weight percent by taking the total weight of the stabilizer as 100%: 10-50% of metal soap stabilizer; 5 to 30 percent of auxiliary stabilizer; 5 to 30 percent of antioxidant; make up to 100% solvent; wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer. The addition of 5-10% of the stabilizing agent for the sulfonylurea herbicide can ensure the stability of the sulfonylurea herbicide, reduce the decomposition rate of the effective components in the sulfonylurea herbicide, ensure that the decomposition rate of the effective components of the pesticide in hot storage is lower than 5%, facilitate the improvement of the utilization rate of the active components of the pesticide, and ensure that the sulfonylurea herbicide is wider in use and better in effect.

Detailed Description

In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.

In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.

The embodiment of the invention provides a stabilizing agent for sulfonylurea herbicides, which comprises the following components in parts by weight based on 100% of the weight of the stabilizing agent for sulfonylurea herbicides:

wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer.

Specifically, the stabilizer for sulfonylurea herbicides comprises 10 to 50% of a metallic soap stabilizer, based on 100% by weight of the stabilizer for sulfonylurea herbicides. Wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer. Specifically, the addition amount of the metal soap stabilizer is 10% to 50%, and in the specific embodiment of the invention, the addition amount of the metal soap stabilizer is 25%, 30%, 40% or 50%.

Preferably, the calcium salt stabilizer is at least one selected from the group consisting of calcium stearate, calcium ricinoleate, calcium hydroxide, and calcium phosphite. Preferably, the zinc salt stabilizer is at least one selected from the group consisting of zinc stearate, zinc ricinoleate, zinc 2-ethylhexanoate, zinc laurate, zinc naphthenate, zinc neodecanoate, zinc oxide, benzoic acid, and substituted zinc benzoate.

Specifically, the stabilizing agent for sulfonylurea herbicides comprises 5 to 30 percent of auxiliary stabilizing agent, based on 100 percent of the weight of the stabilizing agent for sulfonylurea herbicides. In the specific embodiment of the present invention, the addition amount of the auxiliary stabilizer is 5%, 10%, 16%, 25%.

Preferably, the auxiliary stabilizer is at least one selected from the group consisting of epoxidized soybean oil, epichlorohydrin, diphenyl monooctyl phosphite, diphenyl monodecanyl phosphite, trisnonylphenyl phosphite, dibenzoyl methane, pentaerythritol, distearyl pentaerythritol diphosphite and aminouracil.

Specifically, the stabilizer for sulfonylurea herbicides comprises 5 to 30% of an antioxidant, based on 100% by weight of the stabilizer for sulfonylurea herbicides. In the specific embodiment of the invention, the addition amount of the antioxidant is 5%, 6%, 7% or 10%.

Preferably, the antioxidant is at least one selected from the group consisting of 2, 6-di-tert-butyl-p-cresol, bisphenol A and nonylphenol.

Specifically, the solvent is made up to 100% by weight of the stabilizer for sulfonylurea herbicides of 100%. The water of the sulfonylurea herbicide is favorable for the decomposition of the active ingredients, so the added solvent is an organic solvent, on one hand, the similar compatible effect can be achieved, and the uniform mixing of the components is promoted; on the other hand, the sulfonylurea herbicide can be kept unfavorable for decomposition, and the beneficial effect is kept. In a specific embodiment of the present invention, the solvent is added in an amount of 30%, 34%, 45%, 49%, 63%.

Preferably, the solvent is at least one selected from the group consisting of liquid paraffin, white oil, diesel oil, mineral oil, and oxidized soybean oil.

Preferably, the stabilizing agent is suitable for sulfonylurea herbicides in the dosage forms of missible oil, dispersible oil suspending agents or film-spreading oil agents.

Compared with the stabilizing effect of other sulfonylurea stabilizers, the experimental results in the 30g/L mesosulfuron-methyl dispersible oil suspending agent are shown in the following table 1:

TABLE 1

As can be seen from Table 1, the stabilizer of the invention has good stabilizing effect on sulfonylurea herbicides in a wider pesticide preparation system range, has a decomposition rate of less than 5 percent after being stored for 14 days, and is superior to the prior conventional stabilizer in stabilizing effect and application range.

The stabilizer for sulfonylurea herbicide provided by the invention comprises 10-50% of metal soap stabilizer; 5 to 30 percent of auxiliary stabilizer; 5 to 30 percent of antioxidant and solvent which is complemented to 100 percent, wherein the metal soap stabilizer is a mixture of calcium salt stabilizer and zinc salt stabilizer. The stabilizer provided by the invention can reduce the decomposition rate of the effective components in the sulfonylurea herbicide, so that the decomposition rate of the effective components in the pesticide during thermal storage is lower than 5%, and the utilization rate of the active components of the pesticide is favorably improved. And the stabilizer has good stabilizing effect, low cost and good practical value.

The above-mentioned stabilizer for sulfonylurea herbicides is prepared by the following method for preparing a stabilizer for sulfonylurea herbicides.

Correspondingly, the embodiment of the invention also provides a preparation method of the stabilizing agent for the sulfonylurea herbicide. The method comprises the following steps:

s01, weighing each component according to the stabilizing agent for the sulfonylurea herbicide;

s02, uniformly stirring the solvent, adding a metal soap stabilizer, an auxiliary stabilizer and an antioxidant, and heating and stirring for 2-3 hours to obtain a first mixture;

s03, carrying out pressure filtration on the first mixture to obtain a light yellow filtrate, wherein the light yellow filtrate is a stabilizer for the sulfonylurea herbicide.

Specifically, in the step S01, the components are weighed according to the stabilizer for sulfonylurea herbicides, which is consistent with the above discussion and will not be described herein again.

Specifically, in the step S02, the solvent is uniformly stirred, the metal soap stabilizer, the auxiliary stabilizer, and the antioxidant are added, and the mixture is heated and stirred for 2 to 3 hours to obtain the first mixture. Preferably, in the step of heating and stirring, the heating temperature is 107-120 ℃.

Specifically, in the above step S03, the first mixture is filter-pressed to obtain a pale yellow filtrate, which is a stabilizer for the sulfonylurea herbicide. The stabilizing agent for sulfonylurea herbicides is treated by a filter pressing method to remove insoluble impurities, and the stabilizing agent for sulfonylurea herbicides, which can be used as the sulfonylurea herbicides in the dosage forms of missible oil, dispersible oil suspending agents or film-spreading oil agents, is obtained.

The preparation method of the stabilizing agent for the sulfonylurea herbicide provided by the invention only needs to mix the components according to the proportion, and the preparation method can uniformly disperse the components, thereby endowing the stabilizing agent for the sulfonylurea herbicide with excellent stability while realizing the beneficial effect of the stabilizing agent for the sulfonylurea herbicide. In addition, the preparation method has simple process, controllable conditions and low equipment requirement, and can be used for industrial production.

Correspondingly, the embodiment of the invention also provides a sulfonylurea herbicide, and the sulfonylurea herbicide comprises 5-10% of a stabilizing agent for the sulfonylurea herbicide, based on 100% of the weight of the sulfonylurea herbicide.

Preferably, the sulfonylurea herbicide is selected from emulsifiable concentrate, dispersible oil suspending agent or film-spreading oil agent. Further preferably, the pesticide active ingredient of the sulfonylurea herbicide is any one selected from the group consisting of mesosulfuron, bensulfuron, pyrazosulfuron-ethyl, halosulfuron-methyl and flucarbazone-methyl.

The sulfonylurea herbicide provided by the invention comprises 5-10% of stabilizer by taking the total weight of the sulfonylurea herbicide as 100%, and the stabilizer comprises the following components by weight percent by taking the total weight of the stabilizer as 100%: 10-50% of metal soap stabilizer; 5 to 30 percent of auxiliary stabilizer; 5 to 30 percent of antioxidant; make up to 100% solvent; wherein the metal soap stabilizer is a mixture of a calcium salt stabilizer and a zinc salt stabilizer. The addition of 5-10% of the stabilizing agent for the sulfonylurea herbicide can ensure the stability of the sulfonylurea herbicide, reduce the decomposition rate of the effective components in the sulfonylurea herbicide, ensure that the decomposition rate of the effective components of the pesticide in hot storage is lower than 5%, facilitate the improvement of the utilization rate of the active components of the pesticide, and ensure that the sulfonylurea herbicide is wider in use and better in effect.

The present invention will now be described in further detail by taking as an example a stabilizer for sulfonylurea herbicides and a method for preparing the same.

The stabilizers for sulfonylurea herbicides were subjected to stability test:

a stability test method of a stabilizing agent for sulfonylurea herbicides and the steps thereof: adding a certain proportion of stabilizer into the pesticide liquid preparation, stirring and mixing or preparing and sanding together, after the sample is prepared, immediately measuring the content of effective components of the sample and carrying out a stability storage test at normal temperature over time; and then carrying out a heat storage test, namely placing the sample in an oven at 54 +/-2 ℃, measuring the content of the effective components in the sample after the sample is placed for 14 days (14d), and calculating the decomposition rate of the effective components.

The decomposition rate is calculated by taking the content of the effective components measured before storage as a reference, and the decomposition rate is less than or equal to 5 percent after the storage with heat storage for 14d (54 +/-2 ℃) and the storage with the stability at normal temperature is qualified.

Decomposition rate calculation formula: the decomposition rate (%) - (content of active ingredient in sample before storage-content of active ingredient in sample after heat storage)/content of active ingredient in sample before storage × 100%.