阅读说明：本技术 一种油酸醇酯类的表面活性剂的应用 (Application of oleic alcohol ester surfactant ) 是由 丑靖宇 周惠中 崔勇 刘昊 崔东亮 于 2020-06-12 设计创作，主要内容包括：本发明涉及一种除草剂组合物,主要是一种含油酸醇酯类的表面活性剂作为稳定及增效剂的除草组合物,按重量百分含量计,活性组分1-95％、稳定及增效剂油酸醇酯类的表面活性剂1-10％,其它组分补至100％；其中活性组分为异噁草松的组合物。本发明含油酸醇酯类的表面活性剂作为稳定及增效剂的异噁草松除草组合物其物理化学性能稳定,在产品保质期内各项检测指标合格,且在零下18度90天无结晶、不结块。该除草组合物的制剂主要用于防治大豆、花生、甘蔗、油菜、马铃薯、水稻作物田的一年生禾本科杂草和阔叶杂草。(The invention relates to a weedicide composition, mainly a weedicide composition taking surface active agent of oleic acid alcohol ester as stabilizing and synergist, according to the weight percent, active component 1-95%, stabilizing and synergist oleic acid alcohol ester surface active agent 1-10%, other components make up to 100%; the active component is clomazone. The clomazone weeding composition taking the oleic acid alcohol ester surfactant as the stabilizing and synergistic agent has stable physical and chemical properties, various detection indexes are qualified in the quality guarantee period of products, and no crystallization or agglomeration occurs at minus 18 ℃ for 90 days. The preparation of the weeding composition is mainly used for preventing and controlling annual gramineous weeds and broadleaf weeds in soybean, peanut, sugarcane, rape, potato and rice crop fields.)

1. An application of the surfactant of oleic alcohol ester in stabilizing and synergistic agent in herbicide.

2. Use according to claim 1, characterized in that: the active component of the herbicide contains clomazone.

3. Use according to claim 1 or 2, characterized in that: the addition amount of the oleic alcohol ester surfactant accounts for 1-10% of the mass of the herbicide.

4. Use according to claim 3, characterized in that: the surfactant of oleic acid alcohol ester is selected from one or more of polyethylene glycol 200 monooleate, polyethylene glycol 200 dioleate, polyethylene glycol 400 monooleate, polyethylene glycol 400 dioleate, sorbitan monooleate, sorbitan sesquioleate, and sorbitan trioleate.

5. A herbicidal formulation characterized by: according to the weight percentage, the active component is 1-90%, the surface active agent of oleic alcohol ester is 1-10%, and other components are supplemented to 100%; wherein the active component contains clomazone.

6. A herbicidal formulation as set forth in claim 5, wherein: according to the weight percentage, the active component is 10-50%, the surfactant of the oleic alcohol ester is 1-5%, and other components are supplemented to 100%.

7. A herbicidal formulation as set forth in claim 5, wherein: the preparation can be missible oil, microemulsion, oil agent or ultra-low volume preparation.

8. Use of a formulation according to claim 5, characterized in that: the herbicide is applied to the prevention and treatment of annual gramineous weeds and broadleaf weeds in crop fields.

9. Use of a formulation according to claim 8, characterized in that: the crops are soybeans, peanuts, sugarcane, rape, potatoes or rice.

Technical Field

The invention relates to a weeding composition, in particular to application of an oleic alcohol ester surfactant.

A herbicidal composition containing clomazone and surfactant containing oleyl ester as stabilizer and synergist and its application are disclosed.

Background

Clomazone is an organic heterocyclic selective pre-emergence herbicide firstly developed by FMC, has an English name clomazone and has a structural formula as follows:

chemical name: 2- (2-chlorobenzyl) -4, 4-dimethylisoxazol-3-one; the molecular formula is as follows: c₁₂H₁₄ClNO₂Molecular weight: 239.7, the crude drug is light brown viscous liquid with relative density of 1.192 and vapor pressure of 19.2MPa at 25 deg.C. The solubility in water is 1.1g/L, and the product is easily dissolved in organic solvents such as acetone, acetonitrile, chloroform, cyclohexanone, dichloromethane, methanol, toluene and the like. Is stable in alkaline and acidic (pH4.5-9.25) medium, and can be stored for one year without loss at room temperature.

PCT patent EP2007104658A (B) filed by aksu corporation, filed concurrently with the chinese invention patent and granted CN102088846A (B), wherein a surfactant blend composition is mentioned, containing at least one nonionic alkoxylate and at least one sugar-based surfactant, to the use of said composition as adjuvant for pesticides. However, several of the formulations described do not solve the problem of not freezing, not crystallizing at low temperatures, while ensuring the stability of the physicochemical characteristics of the product during its shelf life.

The invention content is as follows:

the invention aims to solve the problems of low-temperature crystallization and synergistic interaction of clomazone liquid preparations, and further provides an application of an oleic acid alcohol ester surfactant.

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

an application of the surfactant of oleic alcohol ester in stabilizing and synergistic agent in herbicide.

The active component of the herbicide contains clomazone.

The addition amount of the oleic alcohol ester surfactant accounts for 1-10% of the mass of the herbicide.

The surfactant of oleic acid alcohol ester is selected from one or more of polyethylene glycol 200 monooleate, polyethylene glycol 200 dioleate, polyethylene glycol 400 monooleate, polyethylene glycol 400 dioleate, sorbitan monooleate, sorbitan sesquioleate, and sorbitan trioleate.

Preferably: one or more of polyethylene glycol 200 monooleate, polyethylene glycol 200 dioleate, polyethylene glycol 400 monooleate, sorbitan sesquioleate and sorbitan trioleate;

more preferably one or more of polyethylene glycol 200 monooleate, polyethylene glycol 200 dioleate, sorbitan monooleate, sorbitan sesquioleate and sorbitan trioleate.

A weeding preparation comprises 1-90% of active component, 1-10% of oleic alcohol ester surfactant and 100% of other components in percentage by weight; wherein the active component contains clomazone.

Preferably, the active component accounts for 10 to 50 percent, the surfactant of the oleic alcohol ester accounts for 1 to 5 percent and other components account for 100 percent in weight percentage.

The preparation can be missible oil, microemulsion, oil agent or ultra-low volume preparation.

The other components are an auxiliary agent and a solvent; wherein the auxiliary agent is at least one surfactant; the surfactant is a nonionic surfactant and/or an anionic surfactant;

nonionic surfactant:

1) such as polyethylene glycol type surfactants: for example, polyoxyethylene alkyl (C12-18) ethers, ethylene oxide adducts of alkylnaphthols, polyoxyethylene (mono-or di) alkyl (C8-12) phenyl ethers, formaldehyde condensates of polyoxyethylene (mono-or di) alkyl (C8-12) phenyl ethers, polyoxyethylene (mono-, di-or tri) phenyl ethers, polyoxyethylene (mono-, di-or tri) benzyl phenyl ethers, polyoxypropylene (mono-, di-or tri) benzyl phenyl ethers, polyoxyethylene (mono-, di-or tri) styrylphenyl ethers, polyoxypropylene (mono-, di-or tri) styrylphenyl ethers, polymers of polyoxyethylene (mono-, di-or tri) styrylphenyl ethers, polyoxyethylene polyoxypropylene block polymers, alkyl (C12-18) polyoxyethylene polyoxypropylene block polymer ethers, alkyl (C8-12) phenyl polyoxyethylene polyoxypropylene block polymer ethers, polyoxyethylene bisphenyl ethers, polyoxyethylene resinates, polyoxyethylene glycolates, polyoxyethylene glycolethers, and the like, Polyoxyethylene fatty acid (C12-18) monoesters, polyoxyethylene fatty acid (C12-18) diesters, polyoxyethylene sorbitan fatty acid (C12-18) esters, glycerin fatty acid ester ethylene oxide adducts, polyoxyethylene castor oil ethers, hardened castor oil ethylene oxide adducts, alkyl (C12-18) amine ethylene oxide adducts, fatty acid (C12-18) amide ethylene oxide adducts, and the like;

2) such as polyhydric alcohol type surfactants, for example, glycerin fatty acid esters, polyglycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid (C12-18) esters, sorbitan fatty acid (C12-18) esters, sucrose fatty acid esters, polyhydric alcohol alkyl ethers, fatty acid alkanolamides, and the like;

anionic surfactant:

1) such as carboxylic acid type surfactants: carboxylic acids such as polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of maleic acid and olefins (e.g., isobutylene and diisobutylene), copolymers of acrylic acid and itaconic acid, copolymers of methacrylic acid and itaconic acid, copolymers of maleic acid and styrene, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methyl acrylate, copolymers of acrylic acid and vinyl acetate, copolymers of acrylic acid and maleic acid, sarcosinates of N-methyl-fatty acids (C12-18), resin acids, and fatty acids (C12-18), and salts of these carboxylic acids;

2) such as sulfate ester type surfactants, for example, alkyl (C12-18) sulfates, polyoxyethylene alkyl (C12-18) ether sulfates, polyoxyethylene (mono or di) alkyl (C8-12) phenyl ether sulfates, sulfates of polymers of polyoxyethylene (mono or di) alkyl (C8-12) phenyl ethers, polyoxyethylene (mono, di or tri) phenyl ether sulfates, polyoxyethylene (mono, di or tri) benzyl phenyl ether sulfates, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfates, sulfates of polymers of polyoxyethylene (mono, di or tri) styryl phenyl ethers, sulfates of polyoxyethylene polyoxypropylene block polymers, sulfated oils, sulfated fatty acid esters, sulfated fatty acids and sulfated olefins, and salts of these sulfates;

3) such as sulfonic acid type surfactants, for example, paraffin (C12-22) sulfonic acids, alkyl (C8-12) benzenesulfonic acids, formaldehyde condensates of alkyl (C8-12) benzenesulfonic acids, formaldehyde condensates of cresolsulfonic acids, alpha-olefin (C14-16) sulfonic acids, dialkyl (C8-12) sulfosuccinic acids, lignosulfonic acids, polyoxyethylene (mono-or di) alkyl (C8-12) phenylether sulfonic acids, polyoxyethylene alkyl (C12-18) ether sulfosuccinic acid half esters, sulfonic acids such as naphthalenesulfonic acid, (mono-or di-alkyl (C1-6) naphthalenesulfonic acid, formaldehyde condensate of naphthalenesulfonic acid, (mono-or di-alkyl (C1-6) naphthalenesulfonic acid, formaldehyde condensate of creosote sulfonic acid, alkyl (C8-12) diphenyl ether disulfonic acid, イゲポン T (trade name), polystyrenesulfonic acid, and a copolymer of styrenesulfonic acid and methacrylic acid, and salts of these sulfonic acids.

4) Examples of the phosphate ester-type surfactant include alkyl (C8-12) phosphate esters, polyoxyethylene alkyl (C12-18) ether phosphate esters, polyoxyethylene (mono-or di) -alkyl (C8-12) phenyl ether phosphate esters, phosphate esters of polymers of polyoxyethylene (mono-, di-or tri) -alkyl (C8-12) phenyl ethers, polyoxyethylene (mono-, di-or tri) -phenyl ether phosphate esters, polyoxyethylene (mono-, di-or tri) -benzyl phenyl ether phosphate esters, polyoxyethylene (mono-, di-or tri) -styryl phenyl ether phosphate esters, phosphate esters of polymers of polyoxyethylene (mono-, di-or tri) -styryl phenyl ethers, phosphate esters of polyoxyethylene polyoxypropylene block polymers, phosphate esters of phosphatidylcholine, phosphatidylethanolamine, condensed phosphoric acids (e.g., tripolyphosphate), and salts of these phosphate esters, e.g., alkali metal phosphates (e.g., lithium, sodium, potassium, etc.), alkali metal phosphates, sodium, potassium phosphates, and salts of these phosphate esters, Alkaline earth metals (calcium, magnesium, etc.), ammonium, and various amines (e.g., alkylamines, cycloalkylamines, alkanolamines, etc.), and the like. The above surfactants may be used alone or in combination of 2 or more,

the proportion in the case of mixing can be freely selected, and the total content of the surfactants is usually 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the present invention. The solvent is an organic solvent, and includes, but is not limited to, alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and isopropyl alcohol, ethers such as butyl cellosolve, ketones such as cyclohexanone, esters such as γ -butyrolactone, polar solvents such as amides such as N-methylpyrrolidone, and N-octylpyrrolidone, aromatic hydrocarbons such as xylene, alkyl (C9, C10, etc.) benzene, phenylxylylethane, and alkyl (C1, C3, etc.) naphthalene, aliphatic hydrocarbons such as engine oil, N-paraffin, isoparaffin, and naphthene, mixtures of aromatic hydrocarbons such as kerosene and aliphatic hydrocarbons, and nonpolar solvents such as soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil, and castor oil.

The application of the preparation is to be used as a herbicide for preventing and controlling annual gramineous weeds and broadleaf weeds in crop fields.

The crops are soybeans, peanuts, sugarcane, rape, potatoes or rice.

The preparation method of the present invention is not particularly limited; the preparation can be applied by foliar treatment, soil treatment, paddy field water surface treatment, or a general method generally used by those skilled in the art, thereby controlling weeds. In the case of foliage treatment or soil treatment, it is usually diluted to about 10 to 5000 times with water and spread on crops, trees, or soil where they grow using a sprayer or the like, or spread from the air using an airplane or the like as a stock solution or diluted to about 2 to 100 times with water. In the case of surface treatment of paddy fields, it is common to directly spread the raw material solution to the paddy field.

The invention has the advantages that:

the surfactant containing the oleic acid alcohol ester is used in a clomazone weeding liquid preparation, so that the formed clomazone weeding composition has no crystallization and no agglomeration at 18 ℃ below zero for 90 days at low temperature, the physical and chemical properties of the weeding preparation taking the clomazone as an active ingredient are stable in the shelf life of the product, and the composition containing the clomazone and the oleic acid alcohol ester surfactant has good weeding activity and has no phytotoxicity to target crops.

Furthermore, the invention uses the surfactant without containing oleic acid alcohol ester as the stabilizer and the synergist, is applied to a weeding preparation taking clomazone as an active ingredient, generates crystallization and caking phenomena at 18 ℃ below zero, further solves the phenomena of low-temperature crystallization and caking of clomazone missible oil, and has stable physical and chemical properties in the product quality guarantee period, good weeding activity and no phytotoxicity to target crops.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The following examples serve to describe the invention in further detail, but are not to be construed as limiting the invention, the compositions of the invention being in no way limited to these examples. The raw materials involved in the formulation examples are commercially available. The content of clomazone is 95-98%, and the clomazone is added after being folded. The materials were added in amounts by weight.

Example 1

Clomazone original drug (96.8%)	48％
		Isopropanol (I-propanol)	5％
Calcium dodecyl benzene sulfonate	5％
		Phenethyl phenol polyoxyethylene ether	5％
Sorbitan trioleate	2％
		Solvent oil 150	The content is supplemented to 100%

Comparative example 1

Clomazone original drug (96.8%)	48％
		Isopropanol (I-propanol)	5％
Calcium dodecyl benzene sulfonate	5％
		Phenethyl phenol polyoxyethylene ether	5％
Solvent oil 150	The content is supplemented to 100%

Example 2

Comparative example 2

Clomazone original drug (96.8%)	25％
		Isopropanol (I-propanol)	5％
Sodium di-n-butyl sulfosuccinate	5％
		Phosphoric acid esters of polyoxyethylene polyoxypropylene block polymers	5％
Fatty acid methyl ester	The content is supplemented to 100%

Example 3

Clomazone original drug (96.8%)	30％
		Isomeric tridecanol phosphates	5％
Calcium dodecyl benzene sulfonate	5％
		Polyether	10％
Polyethylene glycol 400 dioleate	2％
		Isopropanol (I-propanol)	The content is supplemented to 100%

Comparative example 3

Clomazone original drug (96.8%)	30％
		Isomeric tridecanol phosphates	5％
Calcium dodecyl benzene sulfonate	5％
		Polyether	10％
Isopropanol (I-propanol)	The content is supplemented to 100%

Example 4

Clomazone missible oil (commercially available)	46％
		Polyethylene glycol 200 monooleate	2％

Comparative example 4

Clomazone missible oil (commercially available)

46％

The processing method of each of the above examples and comparative examples is briefly described as follows: according to the formula requirement, the raw medicine, the auxiliary agent and the like are metered and then added into a preparation kettle, the stirring is started for 60 minutes, and the mixture is guided into a storage tank after being analyzed to be qualified, so that the product is obtained.

Stability test of examples and comparative examples

The stability of the formulations obtained in the above examples and comparative examples was tested under the following conditions: storing for 14 days in a constant temperature oven at 54 plus or minus 2 ℃. Analyzing the content after storage by liquid chromatography, and calculating the decomposition rate of the active component by using the following formula:

calculating the formula: the decomposition rate X of the active component is calculated according to the following formula:

in the formula:

M₀┄ percent sample before heat storage;

M₁┄ percent of the sample after heat storage.

The results are shown in Table 1.

Table 1 comparative stability tests of examples and comparative examples

Serial number	Storage conditions	Active ingredient	Appearance of the product	Decomposition Rate (%)
					Example 1	(54±2)℃，14d	Clomazone	Homogeneous phase flowable	0.25
Comparative example 1	(54±2)℃，14d	Clomazone	Homogeneous phase flowable	5.11
					Example 2	(54±2)℃，14d	Clomazone	Homogeneous phase flowable	0.31
Comparative example 2	(54±2)℃，14d	Clomazone	Homogeneous phase flowable	5.51
					EXAMPLE 3	(54±2)℃，14d	Clomazone	Homogeneous liquid	0.33
Comparative example 3	(54±2)℃，14d	Clomazone	Homogeneous liquid	6.32
					Example 4	(54±2)℃，14d	Clomazone	Homogeneous liquid	0.21
Comparative example 4	(54±2)℃，14d	Clomazone	Homogeneous liquid	4.88

As can be seen from comparison between the examples and the comparative examples in table 1, the herbicidal preparation comprising the clomazone composition containing the oleyl ester surfactant had good physical and chemical stability, and the tendency of increasing the decomposition rate of the active ingredient clomazone original drug in the preparation was effectively controlled.

Table 2 comparative stability tests of examples and comparative examples

Serial number	Storage conditions	Active ingredient	Appearance of the product	Decomposition Rate (%)
					Example 1	At 18 ℃ below zero and 90d	Clomazone	Homogeneous phase flowable	0.25
Comparative example 1	At 18 ℃ below zero and 90d	Clomazone	Crystallization and agglomeration	1.51
					Example 2	At 18 ℃ below zero and 90d	Clomazone	Homogeneous phase flowable	0.35
Comparative example 2	At 18 ℃ below zero and 90d	Clomazone	Crystallization and agglomeration	1.55
					EXAMPLE 3	At 18 ℃ below zero and 90d	Clomazone	Homogeneous liquid	0.33
Comparative example 3	At 18 ℃ below zero and 90d	Clomazone	Crystallization and agglomeration	2.65
					EXAMPLE 4	At 18 ℃ below zero and 90d	Clomazone	Homogeneous liquid	0.22
Comparative example 4	At 18 ℃ below zero and 90d	Clomazone	Crystallization and agglomeration	3.1

It can be seen from table 2 that the comparison between the examples and the comparative examples shows that the physical and chemical stability of the active ingredients of the formulation containing the combination of clomazone and the oleate surfactant composition is good, and the problems of crystallization, caking and the like of the herbicidal formulation using clomazone as the active ingredient at low temperature (18 ℃ below zero) can be effectively controlled.

Examples of biological activity: has herbicidal effect on soybean

1. Test target

Weed target: abutilon (Abutilo theohrasti medicinal.), and Echinochloa crus-galli (L.) Beauv.

Crop: soybean Glycine max (Linn.) Merr.

2. Test method

Quantitative Abutilon and Echinochloa crusgalli seeds were sown in disposable paper cups having a height of 9cm, and soil was sprayed with a crawler-type crop sprayer (designed by Engineer Research Ltd. in England) at a test design dose 24 hours after sowing (spray pressure 1.95 kg/cm)²The amount of the liquid spray is 500L/hm²Track speed 1.48km/h), the test was repeated 3 times. After the test material is treated, the treated test material is placed in an operation hall, after the liquid medicine is naturally dried in the air, the test material is placed in a greenhouse for management according to a conventional method, the emergence of piemarker and cockspur grass and the reaction to the agent are observed and recorded, the control effect of the agent to the piemarker and the cockspur grass is periodically checked by eyes, and the weeding activity of the test agent is evaluated.

TABLE 3 results of visual weed control with different formulations of clomazone (15 days after treatment)

As seen from table 3, the herbicidal activity of all the examples is higher than that of the comparative examples for barnyard grass and abutilon, higher than that of the original herbicide, and no phytotoxicity to soybean, indicating that the clomazone composition added with the oleic acid alcohol ester-containing surfactant has a synergistic effect on the herbicidal activity of clomazone and is safe for soybean as a target crop.