CN114766478A - Compound emulsifier for clethodim preparation and preparation method thereof - Google Patents
Compound emulsifier for clethodim preparation and preparation method thereof Download PDFInfo
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- CN114766478A CN114766478A CN202210527391.7A CN202210527391A CN114766478A CN 114766478 A CN114766478 A CN 114766478A CN 202210527391 A CN202210527391 A CN 202210527391A CN 114766478 A CN114766478 A CN 114766478A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/06—Sulfonic acid amides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Agronomy & Crop Science (AREA)
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Abstract
The invention discloses a compound emulsifier for clethodim preparations and a preparation method thereof. The agricultural compound emulsifier comprises, by mass, 20-50% of an emulsifier A with an average HLB value of 6-9, 10-40% of an emulsifier B with an average HLB value of 12.5-16, 20-25% of an anionic emulsifier C and the balance of S-150# solvent oil. The invention adopts the matching of the nonionic emulsifier with a specific HLB value range and the anionic emulsifier, thus solving the problem of high decomposition rate of the clethodim preparation after thermal storage; the monomer raw materials used by the emulsifier are green, environment-friendly, safe and low-toxic, and meet the development requirements of pesticide industry; compared with the conventional emulsifier sold in the market (8-12% of missible oil and 15-20% of dispersible oil suspending agent), the dosage of the compound emulsifier is lower, so that the resource is saved, and the production cost of enterprises is reduced.
Description
Technical Field
The invention relates to a compound emulsifier, and in particular relates to a preparation method of a compound emulsifier for a clethodim emulsifiable concentrate and dispersible oil suspending agent product.
Background
Clethodim (Clethodim) is an internal absorption conduction type stem and leaf treatment herbicide of cyclohexenone type developed by Chevron chemical company in the United states and Sumitomo chemical company in Japan, is mainly used for preventing and killing annual and perennial gramineous weeds such as barnyard grass, wild oat, crab grass, green bristlegrass, goosegrass, aloes, bluegrass and hard grass in broad-leaved fields such as soybean, rape, cotton and peanut, and is ineffective to broad-leaved families and sedges.
Due to low residue and low use cost, clethodim becomes the best choice for compounding a plurality of herbicides (such as haloxyfop-R-methyl, fluoroglycofen-ethyl, fomesafen, clopyralid, picloram and the like), and the market demand is continuously increased. Moreover, with the continuous generation of the resistance of weeds to glufosinate-ammonium, clethodim and glyphosate or glufosinate-ammonium are compounded for use, so that the clethodim can be used as a means for coping with and resisting the resistance of glufosinate-ammonium glyphosate, a good market prospect is developed for clethodim, and the clethodim is one of the reasons for the rapid development of clethodim in recent years.
The clethodim molecules contain functional groups such as hydroxyl, double bonds, oxime and the like, and are easy to decompose under the conditions of oxygen, moisture, ultraviolet rays, temperature and the like in daily environment. Due to the characteristic that the original drug is easy to decompose, the preparation stability is not good enough. At present, clethodim single agent is mainly missible oil, and a compound preparation formulation mainly comprises missible oil and dispersible oil suspending agent. These formulations are very unstable, the actual decomposition rate of clethodim at normal temperature for two years is generally greater than 10%, and according to the documents of the european union, the decomposition rate of formulations of foreign enterprises is also greater than 5%, and in international trade, the problem that clethodim-containing formulation products decompose over a long period of time at high temperature during cross-sea transportation is a very difficult problem to solve.
At present, as the solvent of the emulsion-type products generally adopts solvent oil, and the dispersion medium of the dispersible oil suspending agent is generally selected from vegetable oil or derivatives of vegetable oil, the emulsifier becomes an intrinsic key factor influencing the decomposition of the clethodim preparation.
However, the preparation samples processed by adopting the emulsifying agents of different manufacturers have obvious performance difference, and the prepared samples have a series of problems of poor emulsion stability, high decomposition rate and the like.
Disclosure of Invention
Aiming at the problems and the defects in the prior agricultural technology, the invention aims to provide a compound emulsifier for clethodim preparations and a preparation method thereof, and aims to improve the stability of a product system containing clethodim preparations so as to reduce the decomposition rate of active ingredients of the clethodim preparations.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
the invention discloses an agricultural compound emulsifier, which comprises 20-50 wt% of emulsifier A with an average HLB value of 6-9, 10-40 wt% of emulsifier B with an average HLB value of 12.5-16, 20-25 wt% of anionic emulsifier C and the balance of S-150# solvent oil.
Preferably, the agricultural compound emulsifier comprises, by mass, 35-45% of emulsifier A with an average HLB value of 6-9, 20-25% of emulsifier B with an average HLB value of 12.5-16, 20-25% of anionic emulsifier C and the balance S-150# solvent oil.
Specifically, the agricultural compound emulsifier is any one of the following 1) to 7):
1) the emulsifier is prepared from 35-40 wt% of emulsifier A with an average HLB value of 6-9, 20-25 wt% of emulsifier B with an average HLB value of 12.5-16, 25 wt% of anionic emulsifier C and the balance S-150# solvent oil;
2) the emulsifier is prepared from 40-45 wt% of an emulsifier A with an average HLB value of 6-9, 20-25 wt% of an emulsifier B with an average HLB value of 12.5-16, 20-25 wt% of an anionic emulsifier C and the balance of S-150# solvent oil;
3) the emulsifier is prepared from 45 mass percent of emulsifier A with the average HLB value of 6-9, 20 mass percent of emulsifier B with the average HLB value of 12.5-16, 25 mass percent of anionic emulsifier C and the balance of S-150# solvent oil;
4) the emulsifier is prepared from 45 mass percent of emulsifier A with the average HLB value of 6-9, 25 mass percent of emulsifier B with the average HLB value of 12.5-16, 20 mass percent of anionic emulsifier C and the balance of S-150# solvent oil;
5) the emulsifier is prepared from 40% of emulsifier A with an average HLB value of 6-9, 25% of emulsifier B with an average HLB value of 12.5-16, 25% of anionic emulsifier C and the balance of S-150# solvent oil in percentage by mass;
6) the emulsifier is prepared from 35% of an emulsifier A with an average HLB value of 6-9, 20% of an emulsifier B with an average HLB value of 12.5-16, 25% of an anionic emulsifier C and the balance of S-150# solvent oil in percentage by mass;
7) the emulsifier is prepared from 45% of emulsifier A with the average HLB value of 6-9, 25% of emulsifier B with the average HLB value of 12.5-16, 25% of anionic emulsifier C and the balance of S-150# solvent oil in percentage by mass.
In the agricultural compound emulsifier, the emulsifier A with the average HLB value of 6-9 can be an emulsifier A with an HLB value of 6.7-9, such as 6.8, 8.6, 8, 7.8, 7.9, 6.7 and 9, and can be at least one selected from castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, sorbitan fatty acid ester, propylene glycol block polyether and polyethylene glycol fatty acid ester;
the emulsifier B with the average HLB value of 12.5-16 can be emulsifier B with the HLB value of 13-16, such as 15, 13, 15.2, 13.5, 13.8, 16 and 13.3, and can be specifically selected from at least one of castor oil polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, tristyrylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, alkylphenol polyoxyethylene ether polyoxypropylene ether, fatty acid polyoxyethylene ester and tristyrylphenol polyoxyethylene polyoxypropylene ether;
the anionic emulsifier C can be at least one selected from sodium dibutyl succinate, sodium dihexyl succinate, dicyclohexyl sulfosuccinate sodium, alkyl polyoxyethylene ether sulfosuccinate monoester sulfonate disodium, lauryl alcohol sulfosuccinate disodium, dodecylbenzene sulfonic acid triethanolamine salt, C16-18 fatty acid methyl ester sodium sulfonate, nonylphenol polyoxyethylene ether sulfosuccinate monoester sulfonate disodium, and coconut monoethanolamide sulfosuccinate monoester disodium.
In a second aspect, the invention provides a preparation method of the agricultural compound emulsifier, comprising the following steps: the agricultural compound emulsifier is prepared by mixing the components in proportion, stirring for 10-15 minutes (such as 10 minutes and 15 minutes) at 40-55 ℃ (45 ℃, 40 ℃, 50 ℃ or 55 ℃) until the mixture is transparent and uniform, cooling to room temperature and filtering.
In a third aspect, the invention protects the application of the agricultural compound emulsifier in at least one of the following A1) -A2):
A1) improving the dispersion stability of the clethodim-containing preparation;
A2) improving the heat storage stability of the clethodim-containing formulation.
In the above application, the clethodim-containing preparation can be a clethodim preparation or a clethodim-containing compound preparation;
the clethodim-containing compound preparation is any one of the following compound preparations:
a compound preparation of fluoroglycofen-ethyl and clethodim, a compound preparation of haloxyfop-methyl and clethodim, a compound preparation of fomesafen and clethodim, and a compound preparation of glufosinate-ammonium and clethodim;
the clethodim-containing preparation can be missible oil or dispersible oil suspending agent.
In a fourth aspect, the invention provides a clethodim-containing preparation, which contains the agricultural compound emulsifier described in any one of the above.
In the clethodim-containing preparation, the clethodim-containing preparation is missible oil, and the agricultural compound emulsifier accounts for 5-8% of the clethodim-containing preparation, such as 8%.
In the clethodim-containing preparation, the clethodim-containing preparation is a dispersible oil suspending agent, and the agricultural compound emulsifier accounts for 10-12% of the mass of the clethodim-containing preparation, such as 12%.
In the clethodim-containing preparation, the clethodim-containing preparation can be a clethodim preparation or a clethodim-containing compound preparation;
the clethodim-containing compound preparation is any one of the following compound preparations:
a compound preparation of fluoroglycofen-ethyl and clethodim, a compound preparation of haloxyfop-methyl and clethodim, a compound preparation of fomesafen and clethodim, and a compound preparation of glufosinate-ammonium and clethodim.
By way of example, the clethodim preparation can specifically consist of 24% of clethodim, 8% of an emulsifier and the balance of solvent oil (such as S-1200#) in percentage by mass.
By way of example, the compound preparation of the fluoroglycofen-ethyl and the clethodim specifically comprises 5% of fluoroglycofen-ethyl, 12% of clethodim, 8% of an emulsifier and the balance of solvent oil (such as S-150 #).
By way of example, the compound preparation of the haloxyfop-methyl and the clethodim specifically comprises 7.5% of haloxyfop-methyl, 15.5% of clethodim, 8% of emulsifier and the balance of solvent oil (such as S-200 #).
By way of example, the compound preparation of fomesafen and clethodim specifically comprises, by mass percentage, 17% of fomesafen, 4% of clethodim, 12% of an emulsifier, 2% of a thickener (such as white carbon R-974), 35% of methyl oleate and the balance solvent oil (such as 330 #).
By way of example, the compound preparation of glufosinate-ammonium and clethodim specifically comprises, by mass percentage, 15% of glufosinate-ammonium, 5% of clethodim, 12% of an emulsifier, 2% of a thickener (such as white carbon R-974), 25% of soybean oil and the balance solvent oil (such as 330 #).
Compared with the prior art, the stabilizing emulsifier has the following outstanding advantages: firstly, the invention adopts the matching of the nonionic emulsifier with a specific HLB value range and the anionic emulsifier, thus solving the problem of high decomposition rate of the clethodim preparation after thermal storage; secondly, the monomer raw materials used by the emulsifier are green, environment-friendly, safe and low-toxic, and accord with the development requirements of the pesticide industry; the dosage of the compound emulsifier is lower than that of the conventional emulsifier sold in the market (the dosage of missible oil is 8-12%, and the dosage of the dispersible oil suspending agent is 15-20%), so that the resource is saved, and the production cost of enterprises is reduced.
Detailed Description
Aiming at the problems that the performance difference of preparation samples processed by adopting emulsifiers of different manufacturers in the existing clethodim preparation is obvious, and the prepared samples have a series of problems of poor emulsion stability, high decomposition rate and the like. This is related to the source of the raw materials, the formulation composition, etc., and more importantly, to the properties of the emulsifier itself.
Through a great deal of research, the inventor screens out a proper emulsifier combination by compounding the monomer emulsifiers with different HLB values, ensures the good emulsion stability of the clethodim preparation, and also ensures that the clethodim preparation has lower decomposition rate (missible oil preparation is less than or equal to 5%, 54 ℃ and 14 d; dispersible oil suspending agent preparation is less than or equal to 10%, 54 ℃ and 14d), and has significant progress compared with the thermal storage decomposition rate (less than or equal to 10%, 35 ℃ and 12 weeks) of clethodim specified in the national standard GB/T22615-2008, and the invention is completed through deep research.
The present invention is described in further detail below with reference to specific embodiments, and the examples are given only for illustrating the present invention and not for limiting the scope of the present invention. The examples provided below serve as a guide for further modifications by a person skilled in the art and do not constitute a limitation of the invention in any way.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
Example 1
This example illustrates the preparation of the compound emulsifier provided by the present invention.
According to the mass percentage, 45 percent of emulsifier EL-10(HLB value is 6.8, castor oil polyoxyethylene ether, Jiangsu Xinde biological science and technology limited), 20 percent of emulsifier T-80(HLB value is 15, polyoxyethylene sorbitan fatty acid ester, Swallow Chengdai chemical auxiliary agent limited company in Pechant), 25 percent of nonylphenol polyoxyethylene ether succinic acid monoester disodium sulfonate (gas chemical industry limited company in Fushan City), and 100 percent of solvent oil S-150# (Jiangsu Hualun chemical industry limited company) are weighed and supplemented. The raw materials are mixed according to a proportion, heated to 45 ℃, stirred for 10 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 2
This example illustrates the preparation of the compound emulsifier provided by the present invention.
Weighing 45% of emulsifier S-80(HLB value of 8.6, sorbitan fatty acid ester, Haian petrochemical plant of Jiangsu province), 25% of emulsifier EL-36(HLB value of 13.0, castor oil polyoxyethylene ether, Jiangsu Xinde biological science and technology limited company), 20% of dibutyl succinate sodium sulfonate (Qing Xin county Han Ke chemical technology limited company) and 100% of solvent oil S-150 (Jiangsu Hualun chemical technology limited company). The raw materials are mixed according to a proportion, heated to 40 ℃, stirred for 10 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 3
This example illustrates the preparation of the compound emulsifier provided by the present invention.
40% of emulsifier PEG-200DL (HLB value of 8, polyethylene glycol fatty acid ester, Haian petrochemical plant of Jiangsu province), 25% of emulsifier 602# (HLB value of 15.2, tristyrylphenol polyoxyethylene ether, Swallow Corne chemical auxiliary agent Co., Ltd., Peettable), 25% of sodium dihexyl succinate sulfonate (Shandong Cuihua Biotech Co., Ltd.), and 100% of solvent oil S-150# (Jiangsu Hualun chemical Co., Ltd.). The raw materials are mixed according to a proportion, heated to 45 ℃, stirred for 15 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 4
This example illustrates the preparation of the compound emulsifier provided by the present invention.
Weighing 35% of emulsifier S-80(HLB value is 8.6, sorbitan fatty acid ester, Jiangsu province Haian petrochemical plant), 20% of emulsifier SG-12(HLB value is 13.5, polyoxyethylene fatty acid ester, Jiangsu province Haian petrochemical plant), 25% of sodium dihexyl succinate sulfonate (Shandong Tuihua Biotech limited) and 100% of solvent oil S-150 (Jiangsu Hualun chemical limited). The raw materials are mixed according to a certain proportion, heated to 45 ℃, stirred for 15 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 5
This example illustrates the preparation of the compound emulsifier provided by the present invention.
According to the mass percentage, 45 percent of emulsifier PEG-400DO (HLB value is 7.8, polyethylene glycol fatty acid ester, Jiangsu province Haian petrochemical plant), 25 percent of emulsifier LAE-9(HLB value is 13.8, fatty acid polyoxyethylene ester, Jiangsu province Haian petrochemical plant), 25 percent of dicyclohexyl sulfosuccinate (Shanghai Han science and technology Co., Ltd.) and 100 percent of solvent oil S-150# (Jiangsu Hualun chemical Co., Ltd.) are weighed and supplemented. The raw materials are mixed according to a proportion, heated to 50 ℃, stirred for 10 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 6
This example illustrates the preparation of the compound emulsifier provided by the present invention.
According to the mass percentage, 45 percent of emulsifier PEG-400DS (HLB value is 7.9, polyethylene glycol fatty acid ester, Jiangsu province, Haian petrochemical plant), 20 percent of emulsifier EL-60(HLB value is 15, castor oil polyoxyethylene ether, Swine chemical auxiliary agent Co., Ltd. of the Chaettai city), 25 percent of lauryl alcohol sulfosuccinate disodium (Kandis chemical industry (Hubei) Co., Ltd.), and 100 percent of solvent oil S-150# (Jiangsu Hualun chemical Co., Ltd.) are weighed and supplemented. The raw materials are mixed according to a certain proportion, heated to 55 ℃, stirred for 10 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 7
This example illustrates the preparation of the compound emulsifier provided by the present invention.
By mass percentage, 45% of emulsifier S-40(HLB value of 6.7, sorbitan fatty acid ester, Haian petrochemical plant of Jiangsu province), 25% of emulsifier 1602# (HLB value of 16, tristyrylphenol polyoxyethylene polyoxypropylene ether, Nantonne chemical industry Co., Ltd.), 25% of lauryl alcohol sulfosuccinate disodium (Kangdus chemical industry (Hubei) Co., Ltd.), and 100% of solvent oil S-150# (Jiangsu Hualun chemical industry Co., Ltd.) are weighed. The raw materials are mixed according to a proportion, heated to 45 ℃, stirred for 10 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 8
This example illustrates the preparation of the compound emulsifier provided by the present invention.
According to the mass percentage, 45% of an emulsifier EL-10(HLB value is 6.8, castor oil polyoxyethylene ether, Jiangsu New Germany Biotechnology Co., Ltd.), 20% of an emulsifier 34# (HLB value is 16, triphenethyl phenol polyoxyethylene polyoxypropylene ether, Swine Corne chemical auxiliary agent Co., Ltd., Shentai), 25% of dodecylbenzene sulfonic acid triethanolamine (Jiangsu province, Haian petrochemical plant) and 100% of solvent oil S-150# (Jiangsu Hualun chemical Co., Ltd.). The raw materials are mixed according to a proportion, heated to 40 ℃, stirred for 10 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 9
This example illustrates the preparation of the compound emulsifier provided by the present invention.
Weighing 40% of emulsifier A-105(HLB value is 9, polyoxyethylene fatty acid ester, Nantong Chen Rui chemical Co., Ltd.), 25% of emulsifier 701# (HLB value is 13.3, alkylphenol formaldehyde resin polyoxyethylene ether, Swine chemical auxiliary Co., Ltd. from Chentai city), 25% of alkyl polyoxyethylene ether succinic acid monoester disodium sulfonate (Subei Chengshi science and technology Co., Ltd.), and 100% of solvent oil S-150# (Jiangsu Hualun chemical Co., Ltd.). The raw materials are mixed according to a proportion, heated to 45 ℃, stirred for 15 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 10
This example illustrates the preparation of the compound emulsifier provided by the present invention.
According to the mass percentage, 45 percent of emulsifier PEG-200DL (HLB value is 8, polyethylene glycol fatty acid ester, Jiangsu province Haian petrochemical plant), 25 percent of emulsifier T-80(HLB value is 15, polyoxyethylene sorbitan fatty acid ester, Swine chemical auxiliary agent Co., Ltd. of Schott city), 25 percent of coconut monoethanolamide sulfosuccinic acid monoester disodium (Suzhou sailing biological science and technology Co., Ltd.), and 100 percent of solvent oil S-150# (Jiangsu Hualun chemical Co., Ltd.). The raw materials are mixed according to a certain proportion, heated to 50 ℃, stirred for 10 minutes until the mixture is transparent and uniform, cooled to room temperature, and filtered to obtain the compound emulsifier.
Example 11 application example (I)
This example illustrates the preparation of clethodim emulsifiable concentrate provided by the present invention
The formula of 240g/L clethodim emulsifiable concentrate (in percentage by mass):
clethodim active compound (active ingredient, calculated by 100%) 24%
Emulsifier 8%
The solvent oil S-150# (solvent) is supplemented to 100 percent
According to the formula, 240g/L clethodim emulsifiable concentrate is prepared from the compound emulsifying agent prepared in the embodiment 1-10 respectively, wherein the clethodim technical material is purchased from Wuqiao pesticide Co., Ltd (content 95%), and the solvent oil S-150# is purchased from Jiangsu Hualun chemical Co., Ltd, and the emulsion stability and the heat storage decomposition rate index of the prepared sample are determined by referring to the method shown in GB/T22615-. The emulsion stability is carried out according to GB/T1603-2001, no floating oil exists on the upper part, no precipitate exists on the lower part, and the emulsion is judged to be qualified; heat storage stability is carried out according to the "liquid formulations" of GB/T19136-2003. The results are shown in Table 1.
TABLE 1240 g/L clethodim missible oil clethodim heat storage decomposition rate and emulsion stability detection result
Example 12 application example (two)
This example illustrates the preparation of clethodim emulsifiable concentrate provided by the present invention
5% of fluoroglycofen-ethyl and 12% of clethodim emulsifiable concentrate (in percentage by mass):
according to the formula, 5% of fluoroglycofen-ethyl and 12% of clethodim emulsifiable solution are respectively prepared from the compound emulsifier prepared in the embodiments 1-10, wherein the fluoroglycofen-ethyl technical raw material is purchased from Shandongbin agricultural technology limited company (content 95%), the clethodim technical raw material is purchased from Hebei Lansheng biological technology limited company (content 90%), and the solvent oil S-150# is purchased from Jiangsu Hualun chemical limited company, and the emulsion stability and the thermal storage decomposition rate index of the prepared sample are determined by referring to the method shown in GB/T22615 ion 2008. The emulsion stability is carried out according to GB/T1603-2001, no floating oil exists on the upper part, no precipitate exists on the lower part, and the emulsion is judged to be qualified; heat storage stability is carried out according to the "liquid formulations" of GB/T19136-2003. The results are shown in Table 2.
In Table 25%, fluoroglycofen and 12% clethodim emulsifiable solution, clethodim heat storage decomposition rate and emulsion stability detection results
Example 13 application example (III)
This example illustrates the preparation of clethodim emulsifiable concentrate provided by the present invention
7.5 percent of haloxyfop-R-methyl and 15.5 percent of clethodim missible oil (in percentage by mass):
according to the formula, the compound emulsifier prepared in the embodiment 1-10 is respectively prepared into 7.5% of haloxyfop-methyl and 15.5% of clethodim emulsifiable concentrate, wherein the haloxyfop-methyl raw pesticide is purchased from Shandong Lvba chemical engineering Co., Ltd (content of 97%), the clethodim raw pesticide is purchased from Hebei Lansheng Biotech Co., Ltd (content of 94%), and the solvent oil S-200# is purchased from Jiangsu Hualun chemical engineering Co., Ltd, and the emulsion stability and the heat storage decomposition rate index of the prepared sample are determined by referring to the method shown in GB/T22615-. The emulsion stability is carried out according to GB/T1603-2001, and the emulsion is judged to be qualified if no floating oil exists on the upper part and no precipitate exists on the lower part; heat storage stability is carried out according to the "liquid formulations" of GB/T19136-2003. The results are shown in Table 3.
TABLE 37.5% haloxyfop-R + 15.5% clethodim emulsifiable solution clethodim heat storage decomposition rate and emulsion stability detection result
Example 14 application example (IV)
This example illustrates the preparation of a dispersible clethodim oil-based suspension concentrate provided by the present invention
17% fomesafen and 4% clethodim dispersible oil suspending agent (in percentage by mass):
according to the formula, 17% of fomesafen and 4% of clethodim dispersible oil suspending agent are respectively prepared from the compound emulsifier prepared in the embodiments 1-10, wherein the fomesafen raw drug is purchased from the national institute of Vanda Biotechnology Limited company (content 95%), the clethodim raw drug is purchased from the Wuqiao pesticide Limited company (content 90%), the white carbon R-974 is purchased from the Yingchuang Germany Gusai (China) investment Limited company, the fumed silica,
r-974 and solvent oil 330# are purchased from Jiangsu Hualun chemical Co., Ltd, and the dispersion stability and the thermal storage decomposition rate index of the prepared sample are detected.Dispersion stability was carried out according to "4.11" in HG/T2467.11-2003, initial dispersibility: the initial dispersion is complete; certain time dispersion (30 min): the sediment is less than or equal to 1mL, and floating oil or floating paste does not exist; redispersion (24 h): the re-dispersion is complete; redispersion (24.5 h): the sediment is less than or equal to 1mL, and the oil slick or ointment slick is less than or equal to 2mL, namely the product is judged to be qualified. The thermal storage stability was carried out according to "liquid formulations" in GB/T19136-2003. The results are shown in Table 4.
Table 417% fomesafen and 4% clethodim heat storage decomposition rate and dispersion stability detection result in clethodim dispersible oil suspending agent
Example 15 application example (five)
This example illustrates the preparation of a dispersible clethodim oil suspension concentrate provided by the present invention
15% of glufosinate-ammonium + 5% of clethodim dispersible oil suspending agent (in percentage by mass):
according to the formula, 15% of glufosinate-ammonium and 5% of clethodim dispersible oil suspending agent are respectively prepared from the compound emulsifying agent prepared in the examples 1-10, wherein a glufosinate-ammonium salt raw drug is purchased from Shandong green tyrant chemical industry Co., Ltd (content 95%), a clethodim raw drug is purchased from Wuqiao pesticide Co., Ltd (content 90%), white carbon black R-974 is purchased from Yingchuang Degusai (China) investment Co., fumed silica,
r-974, Soybean oil is obtained from Suzhou Fengbang Biotechnology Ltd (methyl esterified Soybean oil, freezing point-3-0 deg.C), and solvent oil 330# was purchased from Hualun chemical Co., Ltd, Jiangsu, and the dispersion stability and the thermal storage decomposition rate index of the prepared sample were examined. Dispersion stability was carried out according to "4.11" in HG/T2467.11-2003, initial dispersibility: the initial dispersion is complete; dispersibility for a certain time (30 min): the sediment is less than or equal to 1mL, and floating oil or floating paste does not exist; redispersion (24 h): the re-dispersion is complete; redispersion (24.5 h): the sediment is less than or equal to 1mL, and the oil slick or ointment slick is less than or equal to 1mL, namely the product is judged to be qualified. The thermal storage stability was carried out according to the "liquid formulation" of GB/T19136-2003. The results are shown in Table 5.
Detection results of clethodim heat storage decomposition rate and dispersion stability in 515% glufosinate-ammonium + 5% clethodim dispersible oil suspending agent
The experiment results show that the compound emulsifier composition has a remarkable stabilizing effect on clethodim-containing missible oil and dispersible oil suspending agent products, the clethodim decomposition rate in the missible oil can be controlled to be below 5% and the clethodim decomposition rate in the dispersible oil suspending agent can be controlled to be below 10% under the condition of heat storage at 54 ℃ for 14 days, and the compound emulsifier composition has remarkable progress compared with the clethodim heat storage decomposition rate (less than or equal to 10%, 35 ℃ and 12 weeks) specified by the national standard GB/T22615 plus 2008, is beneficial to iteration and innovation of a clethodim preparation technology, and meanwhile, the emulsifier is green and environment-friendly in raw materials, low in consumption after compounding, greatly reduces the production cost of enterprises, and is an ideal choice for green prevention and control.
The present invention has been described in detail above. It will be apparent to those skilled in the art that the invention can be practiced within a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with reference to specific embodiments, it will be appreciated that the invention can be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. The use of some of the essential features is possible within the scope of the appended claims.
Claims (10)
1. An agricultural compound emulsifier is characterized in that: the emulsifier comprises, by mass, 20-50% of an emulsifier A with an average HLB value of 6-9, 10-40% of an emulsifier B with an average HLB value of 12.5-16, 20-25% of an anionic emulsifier C and the balance of S-150# solvent oil.
2. The agricultural compound emulsifier of claim 1, which is characterized in that: the agricultural compound emulsifier comprises, by mass, 35-45% of an emulsifier A with an average HLB value of 6-9, 20-25% of an emulsifier B with an average HLB value of 12.5-16, 20-25% of an anionic emulsifier C and the balance of S-150# solvent oil.
3. The agricultural compound emulsifier of claim 1 or 2, which is characterized in that: the emulsifier A with the average HLB value of 6-9 is selected from at least one of castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, sorbitan fatty acid ester, propylene glycol block polyether and polyethylene glycol fatty acid ester;
the emulsifier B with the average HLB value of 12.5-16 is selected from at least one of castor oil polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, tristyrylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, alkylphenol polyoxyethylene ether polyoxypropylene ether, fatty acid polyoxyethylene ester and tristyrylphenol polyoxyethylene polyoxypropylene ether;
the anionic emulsifier C is at least one selected from sodium dibutyl succinate, sodium dihexyl succinate, dicyclohexyl sulfosuccinate sodium, alkyl polyoxyethylene ether succinic acid monoester sulfonate disodium, lauryl alcohol sulfosuccinate disodium, dodecyl benzene sulfonic acid triethanolamine salt, C16-18 fatty acid methyl ester sodium sulfonate, nonylphenol polyoxyethylene ether succinic acid monoester sulfonate disodium and coconut acid monoethanolamide sulfosuccinic acid monoester disodium.
4. The preparation method of the agricultural compound emulsifier of any one of claims 1 to 3, which comprises the following steps: the agricultural compound emulsifier is prepared by mixing the components in proportion, stirring for 10-15 minutes at 40-55 ℃ until the mixture is transparent and uniform, cooling to room temperature and filtering.
5. The use of the agricultural compound emulsifier of any one of claims 1 to 3 in at least one of the following A1) -A2):
A1) improving the dispersion stability of the clethodim-containing preparation;
A2) improving the heat storage stability of the clethodim-containing formulation.
6. Use according to claim 5, characterized in that: the clethodim-containing preparation is a clethodim preparation or a compound preparation containing clethodim;
the clethodim-containing compound preparation is selected from any one of the following compound preparations:
a compound preparation of fluoroglycofen-ethyl and clethodim, a compound preparation of haloxyfop-methyl and clethodim, a compound preparation of fomesafen and clethodim, and a compound preparation of glufosinate-ammonium and clethodim;
the clethodim-containing preparation is missible oil or dispersible oil suspending agent.
7. A clethodim-containing formulation comprising the agricultural compound emulsifier of any one of claims 1-3.
8. The clethodim-containing formulation according to claim 7, characterized in that: the clethodim-containing preparation is missible oil, and the agricultural compound emulsifier accounts for 5-8% of the mass of the clethodim-containing preparation.
9. The clethodim-containing formulation according to claim 7, wherein: the clethodim-containing preparation is a dispersible oil suspending agent, and the agricultural compound emulsifier accounts for 10-12% of the mass of the clethodim-containing preparation.
10. The clethodim-containing formulation according to any one of claims 7-9, characterized in that: the clethodim-containing preparation is a clethodim preparation or a compound preparation containing clethodim;
the clethodim-containing compound preparation is selected from any one of the following compound preparations:
a compound preparation of fluoroglycofen-ethyl and clethodim, a compound preparation of haloxyfop-methyl and clethodim, a compound preparation of fomesafen and clethodim, and a compound preparation of glufosinate-ammonium and clethodim.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024067094A1 (en) * | 2022-09-30 | 2024-04-04 | 兰升生物科技集团股份有限公司 | Clethodim composition, and emulsifiable concentrate and technical concentrate comprising same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102318602A (en) * | 2011-07-13 | 2012-01-18 | 南京扬子鸿利源化学品有限责任公司 | Emulsifying agent having stabilizing effect in clethodim emulsifiable concentrates and preparation method thereof |
| CN104920443A (en) * | 2015-06-12 | 2015-09-23 | 中国日用化学工业研究院 | Environment-friendly beta-cypermethrin emulsion in water and preparing method thereof |
| JP2018024739A (en) * | 2016-08-09 | 2018-02-15 | 東ソー株式会社 | Method for producing vinyl chloride-based resin seed |
-
2022
- 2022-05-16 CN CN202210527391.7A patent/CN114766478B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102318602A (en) * | 2011-07-13 | 2012-01-18 | 南京扬子鸿利源化学品有限责任公司 | Emulsifying agent having stabilizing effect in clethodim emulsifiable concentrates and preparation method thereof |
| CN104920443A (en) * | 2015-06-12 | 2015-09-23 | 中国日用化学工业研究院 | Environment-friendly beta-cypermethrin emulsion in water and preparing method thereof |
| JP2018024739A (en) * | 2016-08-09 | 2018-02-15 | 東ソー株式会社 | Method for producing vinyl chloride-based resin seed |
Non-Patent Citations (2)
| Title |
|---|
| 李彦飞等: "17%烯草酮•乙羧氟草醚乳油配方与田间药效研究", 《现代农药》 * |
| 李彦飞等: "23.5%草铵膦·烯草酮可分散油悬浮剂的配方研制", 《农药》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024067094A1 (en) * | 2022-09-30 | 2024-04-04 | 兰升生物科技集团股份有限公司 | Clethodim composition, and emulsifiable concentrate and technical concentrate comprising same |
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