CN101019530A - Azacycle containing pesticide microemulsion and its prepn - Google Patents
Azacycle containing pesticide microemulsion and its prepn Download PDFInfo
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Abstract
The azacycle containing pesticide microemulsion and its preparation process relates to many sorts of new water emulsion pesticide preparations. The present invention features that some azacycle containing pesticides may be dissolved temporarily in the mixed solution system of inorganic acid with or without organic acid and the solution may be maintained by using surfactant with or without antifreezing thickener, so as to prepare azacycle containing pesticide microemulsion of 2-60 % concentration and containing no harmful solvent. The present invention opens one new way for preparing water emulsion pesticide preparations.
Description
One, technical field
Nitrogen heterocyclic ring microemulsion and preparation method thereof relates to Water-borne modification novel form, novel formulation and the new preparation method thereof of a big class agricultural chemicals.
Two, background technology
For safety, economy, effectively utilize agricultural chemicals, nearly all pesticide original medicine all need be made multiple processing formulation and the preparation thereof of being convenient to use and can give full play to drug effect with maximizing favourable factors and minimizing unfavourable ones.At present in the world surplus in the of 80 in kind of the formulations of pesticide, missible oil still accounts for 26%.Because missible oil disperses the back emulsion droplet trickle in water, drug effect is good, makes simple and easy, be suitable for the processing of liquid such as most organic phosphor and pyrethroid and low melting point agricultural chemicals, thereby the ratio of missible oil in the nearly 70 kinds of formulations of China competes to account for 45%, exceeds one times approximately than international average value.
The required organic solvent of preparation missible oil, as benzene,toluene,xylene, mix a large amount of polar solvents in aromatic solvent such as benzene and solvent naphtha and the soluble liquid, not only consume the petrochemical materials that appreciates day by day, give the pesticidal preparations processing enterprise cost pressure that the band fork-like farm tool used in ancient China is difficult to bear, the more important thing is, nearly 400,000 tons of hazardous solvents that are difficult to degrade in annual China missible oil, crops, soil, waters and environment etc. are caused severe contamination and potential threat, especially increased the poisoning of crops and residual, had influence on human safety with healthy.Therefore,, replace expensive harmful organic solvent, be referred to as the research of meaning " pesticidal preparations Water-borne modification ", become the most important thing in the Environmental Protection in China dosage form research with the natural water that safety is easy to get.And the microemulsion in the Water-borne modification formulation, aqueous emulsion and aqua, than suspending agent, the outstanding agent of breast, micro-capsule suspension, at aspects such as equipment input, preparation technique, production efficiency, packing uses more advantage is arranged, and can directly utilize existing missible oil device to produce.But the suitable pesticide species of making aqua is very limited, thereby drug effect is better than or is bordering on the microemulsion and the aqueous emulsion of missible oil, has become the focus of nearly 20 years fork-like farm tool used in ancient China agricultural chemicals Water-borne modification research naturally.
Nineteen twenty-eight G.Rodawall is with Brazil wax (100), oleic acid (12), KOH (4). borax (7), water (600) made first type microemulsion (northern original text hero etc.: " and disperse. emulsion type
Chemistry " engineering figure book Co., Ltd.).Nineteen fifty-nine Schulman etc. can form the microemulsion of transparent system behind the discovery adding higher alcohol in oil/water/surfactant ternary system, Xiao field .Friebery etc. propose multiple hypothesis to the formation mechanism of microemulsion, aqueous emulsion in succession.Year surplus in the of nearly ten, learn the related content of " pesticide processing book series " (" pesticides new formulation ", " formulations of pesticide add worker's skill Intraoperative. ", " liquid preparation ") of publishing from Chinese Chemical Industry Press, the making of microemulsion such as pyrethroid, organic phosphates, aqueous emulsion receives much attention, and have commercial variety to go on the market in succession, now formed the research boom (seeing the agriculture chemical registration bulletin) of pesticidal preparations Water-borne modification.Microemulsion (ME) and aqueous emulsion (EW) belong to emulsion dispersed structure both persons together in the difficulty that all has aspect the maintenance system stability separately, and the little transparency of seeing to the naked eyes difficulty of the emulsion droplet of ME, in dispersity, stability, coverage rate. adhesive force. aspects such as penetration are better than EW, and drug effect is better than EW, therefore studies microemulsion emphatically.
The inventor has concluded the preparation method of both knowing microemulsion and aqueous emulsion, mainly has following scarce limit:
1, still uses the conditioning agent of a considerable amount of organic solvents, emulsifier at double, a large amount of deionized water or distilled water and stabilizing agent, PH and proportion;
2, need complicated procedures of forming such as strong agitation, heating phase inversion and filtration in the making;
3, be applicable to the former medicine of liquid stable in the water more, powerless to the former medicine of the nitrogenous heterocyclic solid of majority, be difficult to adapt to the demand that the nitrogen heterocyclic ring pesticide species increases severely;
4, existing microemulsion content is many in 20%, and the performance of high-load microemulsion and cost are difficult to reach a standard;
5, product transparency temperature scope is narrow, is subject to multifactor impact, often causes irreversible phenomenon of phase separation.
Because the limitation of above-mentioned problems, it is fast-developing comprehensively to hamper microemulsion.In August, 2003, the inventor has proposed " preparation method that imidacloprid emulsion is new " (application number: 2003101140025), disclose the preparation method of 30% imidacloprid emulsion first and dropped into suitability for industrialized production the sixth of the twelve Earthly Branches, overcome the drawback of above-mentioned microemulsion method for making comprehensively.But raw materials used kind in the method for making. the consumption measuring and calculating. the scope of application etc. lack the statement of scientific system, further in-depth and expansion.
Three, summary of the invention
The present invention is on the basis of simplification and system summary " preparation method that imidacloprid emulsion is new ", enlarge the application of new preparation method in multiple nitrogen heterocyclic ring microemulsion, thereby successfully opened up the universal method that a nitrogen heterocyclic ring agricultural chemicals height (low) concentration microemulsion is made.
In recent years fork-like farm tool used in ancient China, the nitrogen heterocyclic ring of highly effective and safe (pyridine. pyrimidine. imidazoles. pyrazoles etc.) agricultural chemicals continues to bring out, the inventor is according to existing the N atom of not using duplet more than one in the azacyclo-chemistry of pesticide structure, they have and positive charge affinity abilities in various degree such as H+.The inventor tests discovery, Imidacloprid is partly dissolved in 4NHCL or HNO3, but separate out precipitation after depositing certain hour, and at certain density phosphoric acid. also minimal amounts of dissolved is arranged in the solution such as citric acid and do not separate out precipitation; after again both kinds acid being mixed by a certain percentage, and to the dissolving multiplication and the quite stable of Imidacloprid.But drop in the water again,, separate out the flakes crystallization that is insoluble to HCL subsequently though can not disperse through strong agitation.But if add some non-ionic surface active agent (or and thickener) again in Imidacloprid mixing acid after, then mixed liquor can fully disperse and keep stable in water.2%～50% the imidacloprid emulsion of making, its appearance transparent, spontaneous emulsification rapidly then becomes clear solution in water, and other physics and chemical stability that preparation requires are good, the biological effect excellence.
By above-mentioned principle, make up different types of acid and surfactant, can be made into the microemulsion of different types of structure nitrogen heterocyclic ring agricultural chemicals, thereby invented the nitrogen heterocyclic ring microemulsion that do not contain any hazardous solvent and new preparation method thereof.
1, the present invention's subject matter that will solve is:
(1) at the nitrogen heterocyclic ring pesticide species and the content of different types of structure, by theory calculating and physics and chemical stability test, determine kind, consumption and the portfolio ratio of acid, making for different structure nitrogen heterocyclic ring microemulsion provides basic components to instruct;
(2) according to different structure nitrogen heterocyclic ring agricultural chemicals and mixed acid system, select different surface words property agent and thickener for use, make it to make performance qualified microemulsion comprehensively;
(3) enumerated the example of making of representing different types of structure and variable concentrations nitrogen heterocyclic ring microemulsion.
2. Ji Intraoperative scheme
Nitrogen heterocyclic ring microemulsion basic composition (%) pattern is as follows:
Nitrogen heterocyclic ring pesticide effective component content 2%～60%
The molal quantity that inorganic acid is identical with active ingredient * activated nitrogen atom number * 0.3～1.0
The molal quantity that organic acid is identical with active ingredient * activated nitrogen atom number * 0～0.7
Surfactant 5%～25%
Antifreeze thickener 0～5%
From the fork-like farm tool used in ancient China water surplus
The inorganic acid of indication is among the present invention: in the water-soluble inorganic acid such as hydrobromic acid, hydroiodic acid, acid iodide, hydrochloric acid, perchloric acid, hypochlorous acid, nitric acid, Asia nitric acid, thiocyanic acid, molybdic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, pyrophosphoric acid one or more, its usage amount is, with 30%～100% (i.e. identical molal quantity * activated nitrogen atom number * 0.3～1.0 with working substance) of the identical molal quantity of working substance.
The organic acid of indication is among the present invention: formic acid, acetate, dichloroacetic acid, propionic acid, malonic acid, butyric acid, succinic acid, lactic acid, citric acid, malic acid, tartaric acid, oxalic acid, pyruvic acid, pantothenic acid, salicylic acid, sulfosalicylic acid, alkyl benzene sulphonate, sulfanilic acid, maleic acid, naphthenic acid, gluconic acid, the DL-alanine, glycine, glutamic acid L-cystine, aminotriacetic acid, in the water-soluble organic acids such as ethylenediamine tetra-acetic acid (and its esters) one or more, its usage amount is, with 0～70% (i.e. identical molal quantity * activated nitrogen atom number * 0～0.7 with working substance) of the identical molal quantity of working substance.
The concrete ratio of both classes acid can be determined by the physics and the chemical stability complex experiment of different structure nitrogen heterocyclic ring microemulsion.Organic acid or multi-element, inorganic acid and salt play an important role to chemical stability, and often the agricultural chemicals that can make some this fork-like farm tool used in ancient China be easy to decompose under acid condition is stablized at this.
The surfactant of indication is among the present invention: (different) OPEO and phosphate (OPE thereof, SOPE and OPEPO4, SOPEPO4 series), polyoxyethylene nonylphenol ether and phosphate thereof and sulphosuccinates (NPE and NPEPO4 and MAPM series), ethoxylated dodecyl alcohol and phosphate thereof and sulphosuccinates (AEO and AEPO4 and AEM series), fatty alcohol-polyoxyethylene ether and phosphate (JFC thereof, peregal and phosphate MAP series thereof), phenethyl phenol polyethenoxy ether and phosphate thereof (601#-～606# and SPEnPO4 series), alkylphenol polyoxyethylene formaldehyde condensation products (agricultural breast-700# series) and phosphate thereof, phenethyl phenol polyethenoxy ether formaldehyde condensation products (agricultural breast-700-1#, peaceful breast-36#, SPF series) and phosphate, cumylphenol APEO formaldehyde condensation products (agricultural breast-700-2#, peaceful breast-37# series) and phosphate, phenethyl phenol polyethenoxy polyethenoxy ether (agricultural breast-1601#, peaceful breast-33# series) and phosphate, phenethyl phenol polyoxyethylene polyoxypropylene ether (agricultural breast-1602#, peaceful breast-34# series) and phosphate, polyoxyethylene sorbitan carboxylic ester (TW series) and phosphate thereof, castor oil polyoxyethylene ether (EL series) and phosphate thereof, aliphatic amine polyoxyethylene ether series and phosphate thereof, APG organic acid esters (salt) and ethylene oxide adduct series and phosphate thereof, organosilicon non-(the moon) ionic surface active agent and Dodecyl trimethyl ammonium chloride such as (fluorine), DDAO, dodecyl dimethyl benzyl ammonium bromide, in cationic surfactant such as imidazoline cationic compound series and the polymeric carboxylic polymer one or more, its usage amount is formed the 5%-25% of gross mass for prescription.Carry out the consumption adjustment according to preparation working substance content and dilution surface tension size.
The antifreeze thickener of indication is among the present invention: in water-soluble height (low) molecular compounds such as ethylene glycol, propane diols, glycerine, PEG400 #, polyvinyl alcohol, sorbierite, cellosolve and carboxymethyl cellulose, starch derivatives, xanthans, carragheen, alginic acid, polyacrylic acid, carboxylic ethylene polymer one or more.Its usage amount is formed 0～5% of gross mass for prescription, adds according to preparation physically stable implementations and special applications demand.
Also can add prescription as required and forming 0.5%～15% bleeding agent of gross mass, spreader-sticker, stabilizing agent, synergist, process promoter etc.
The inventor to the understanding of microemulsion shaping mechanism among the present invention is, the mixing acid of different degrees of ionization, respectively with nitrogenous pesticide molecule in loose combination of activated nitrogen atom of one or more varying strength negative electrical charges, form unsettled compound or molecular compound.This compound or molecular compound are difficult to dissolving or dispersion in water, even there is the minimal amounts of dissolved thing also to dissociate because of the polarization of big water gaging.Because the poly-effect of the anti-freezing of hydration, hydrotropy, emulsification and the antifreeze thickener of surfactant just makes the compound of loose combination be able to disperse more enduringly in water.The formulation of similar water solution among the present invention, test by analysis, both do not formed the noval chemical compound of combining closely, again but salting liquid or soluble liquid like that can with any ratio and water be miscible and stable character when keeping long, but by the acting in conjunction that mixes acid and surfactant, be formed in the water the transparent rapidly and system that keeps relative stability after can spontaneous emulsification, thereby more near the characteristic of microemulsion, so tentative is the novel microemulsion made from specific process, dispersed structure that it is definite and appellation, remain to be decided after the scientific observation, can not influence its practical value before this.
3, beneficial effect
The new Ka-Wing uniqueness of nitrogen heterocyclic ring microemulsion of the present invention and preparation method thereof has following skill Intraoperative characteristics and industrial advantages:
(1) compare with microemulsion method for making in the past, additive types, emulsifier consumption, manufacturing conditions etc. greatly reduce, thereby have reduced production cost and use cost significantly, can obtain remarkable economic efficiency;
(2) owing to do not contain harmful solvent, ensured in production, accumulating and the use people and animals, crop and environmentAL safety are met the requirement of environment friendly agricultural, can enlarge the scope of application of its microemulsion simultaneously to Different Crop, different growing and different occasions and method;
(3) because the electropositive of new compound and interim polarization, neither change the former medicine permeability existing to controlling object, help the absorption of medicament on the elecrtonegativity blade face again, opening up and permeate, in addition in the soup salicylic acid, citric acid, lactic acid, phosphoric acid etc. degeneration-resistant, lure anti-and encourage function, thereby drug effect is better than other formulation with dosage;
(4) transparency temperature wide ranges, physics and chemical stability are good, and the shelf-life reached more than 3 years, also corresponding prolongation of the longevity of residure;
(5) raw material is easy to get, production equipment. and technology and method for making are simple and easy, help generally promoting, and can make the nitrogen heterocyclic ring agricultural chemicals high concentration microemulsion that other method for making can't be made, thereby have more distinctive feature.
Four, concrete implementation example
1, triazole type microemulsion method for making is applicable to propiconazole, nitrile bacterium azoles, Difenoconazole, Flusilazole, fluorine ring azoles, Tebuconazole, the sixth of the twelve Earthly Branches azoles alcohol, Triadimenol, alkene azoles alcohol, triazolone, uniconazole P, paclobutrazol, MBAMT (diazole), presses down mould azoles triazole (pyrazoles, imidazoles) class agricultural chemicals such as (imidazoles).
Embodiment 1,50% propiconazole microemulsion method for making
In the reactor of 2000 liters, input is from fork-like farm tool used in ancient China water 100KG, propionic acid 32KG, hydrochloric acid 37KG slowly adds 96% propiconazole 521KG behind the mixing, continue to be stirred to transparent, add agricultural breast-1601# (or 1602#, the phosphate 130KG of peaceful breast-33#, peaceful breast-34#), AEO-7 20KG, add again from fork-like farm tool used in ancient China water 160KG, promptly get product behind the mixing.
Table 1 different content propiconazole microemulsion primary raw material input ratio (%)
Embodiment 2.25% myclobutanil micro-emulsion method for making
In the reactor of 2000 liters, input is from fork-like farm tool used in ancient China water 215.5KG, propionic acid 19.5KG, hydrochloric acid 22KG slowly adds 96% nitrile bacterium azoles 261KG behind the mixing, continue to be stirred to transparent, add 600# (601#-～606# and homologous series) phosphate 100KG, NP-10 20KG adds from fork-like farm tool used in ancient China water 362KG again, promptly gets product behind the mixing.
Table 2 different content myclobutanil micro-emulsion primary raw material input ratio (%)
Embodiment 3.20% (with 40%) micro-emulsion of phenyl ether methyl cyclic-azole method for making
In the reactor of 2000 liters, input is from fork-like farm tool used in ancient China water 200KG, lactic acid 19KG (34KG), hydrochloric acid 30KG (49KG) slowly adds 95% Difenoconazole 210KG (421KG) behind the mixing, salicylic acid 1KG, continue to be stirred to transparent, add TW-80 100KG (120KG), MAP-10 20KG, add again from fork-like farm tool used in ancient China water 420KG (155KG), promptly get product behind the mixing.
2, intend nicotinoids microemulsion method for making: be applicable to Imidacloprid. Acetamiprid. plan such as thiophene worm piperazine nicotine (pyridine. pyrimidine) the class agricultural chemicals.
Embodiment 4 50% Imidacloprid (m/v) microemulsion method for makings
In the reactor of 2000 liters, drop into from fork-like farm tool used in ancient China water 100KG, hydrochloric acid 90KG, phosphoric acid 240KG slowly adds 98% Imidacloprid 363KG behind the mixing, continue to be stirred to transparent, (140KG of or peaceful breast-34#), JFC40KG adds behind fork-like farm tool used in ancient China water 57KG mixing again and promptly gets product to add peaceful breast-33#.
Table 3 different content imidacloprid emulsion primary raw material input ratio (%)
Embodiment 5 30% Acetamiprid (m/v) microemulsion method for makings
In the reactor of 2000 liters, input is from fork-like farm tool used in ancient China water 160KG, hydrochloric acid 75.5KG, phosphatase 11 44.5KG slowly adds 95% Acetamiprid 270KG behind the mixing, continue to be stirred to transparent, add TW-20 120KG, agricultural breast-700-II#20KG adds from fork-like farm tool used in ancient China water 190KG again, PEG400 #20KG promptly gets product behind the mixing.
The different acetamiprid micro emulsion agent of table 4 primary raw material input ratio (%)
3, other nitrogen heterocyclic ring microemulsion method for making be applicable to phonetic mould amine, fly eradication amine, fluorine worm nitrile, tebufenpyrad,, Nitenpyram, alkene oxime amine, niclosamide,, the nitrogen heterocyclic ring agricultural chemicals of amino-contained such as Buprofezin, dimethomorph, procymidone, the fast quinoline of 6-benzyl gland, Acetochlor, isopropyl methoxalamine, atrazine, prometryn or amide groups structure type.
The phonetic mould amine microemulsion method for making of embodiment 6 40% (with 20%)
In the reactor of 2000 liters, input is from fork-like farm tool used in ancient China water 160KG, lactic acid 15KG (7KG), hydrochloric acid 73KG (43KG) slowly adds 96% phonetic mould amine 420KG (210KG) behind the mixing, citric acid 1KG, continue to be stirred to transparent, add bromogeramine 80KG (70KG), EL-80 30KG, add again from fork-like farm tool used in ancient China water 221KG (479KG), promptly get product behind the mixing.
Embodiment 7 18% Imidacloprid (2) Buprofezin (16) microemulsion (m/v) method for makings
In the reactor of 2000 liters, input is from fork-like farm tool used in ancient China water 100KG, phosphoric acid 300KG, acetate 20KG, process promoter 150KG, slowly add 95% Imidacloprid 18KG behind the mixing, 95% Buprofezin 140KG continues to be stirred to transparent, add peaceful newborn 36# phosphate 25KG, OPE-10 75KG adds from fork-like farm tool used in ancient China water 172KG again, promptly gets product behind the mixing.
Embodiment 8 20% fluorine worm nitrile microemulsion method for makings
In the reactor of 2000 liters, input is from fork-like farm tool used in ancient China water 100KG, butyric acid 5KG, hydrobromic acid 22KG, process promoter 150KG, slowly add 96% fluorine worm nitrile 210KG behind the mixing, continue to be stirred to transparent, add agricultural breast-700#85KG, aliphatic amine polyoxyethylene ether phosphate 25KG, add again from fork-like farm tool used in ancient China water 403KG, promptly get product behind the mixing.
Test example 9 is an example with 45% Imidacloprid and 50% propiconazole microemulsion, is compared as follows with the physics of both knowing preparation and chemical property:
Table 5
| Test specimen | Outward appearance | Spontaneous dispersiveness (30 ℃, in the 342ppm hard water) | Dispersion and emulsion stability (in 30 ℃ of hard water) | Cold storage (15 ℃, 24h) result of the test | Heat storage (54 ± 2 ℃ 14 days) resolution ratio, % | Transparency temperature (℃) |
| 45% imidacloprid emulsion | Transparent | Thirty | Thirty | Transparent | 1.3 | -20～ +85 |
| 20% imidacloprid soluble liquor | Transparent | ± | Thirty | Muddy | 4.7 | 0～+65 |
| 50% propiconazole microemulsion | Transparent | Thirty | Thirty | Transparent | 1.6 | -20～ +85 |
| 25% propiconazole emulsifiable concentrate | Transparent | ± | ± | Little muddiness | 3.4 | 0～+55 |
Test example 10 is an example with 45% Imidacloprid and 50% propiconazole microemulsion, is compared as follows with the biological effect of both knowing preparation (* annotates table down) and economic effect:
Table 6
| Test specimen | The working substance consumption, g/hm2 | Preventive effect after 1 day, % | Preventive effect after 3 days, % | Preventive effect after 7 days, % | Preventive effect after 14 days, % | The ton cost, (ten thousand yuan) | Use cost (unit/mu) |
| 45% imidacloprid emulsion | 20 | 95.3 | 98.7 | 99.2 | 97.6 | 5 | 2.4 |
| 20% imidacloprid soluble liquor | 25 | 94.5 | 95.2 | 87.3 | 84.7 | 4.3 | 5.0 |
| 10% imidacloprid wettable powder | 30 | 92.6 | 93.6 | 82.1 | 73.2 | 2.1 | 3.6 |
| 50% propiconazole microemulsion | 100 | 76.8 | 83.9 | 88.6 | 94.1 | 10 | 12 |
| 25% propiconazole emulsifiable concentrate | 100 | 77.2 | 84.2 | 85.3 | 86.4 | 7 | 15 |
* Imidacloprid is prevented and treated Jie Gua Thistle horse, and propiconazole is prevented and treated sigatoka.
Claims (6)
1, nitrogen heterocyclic ring microemulsion and preparation method thereof, feature of the present invention is: the nitrogen heterocyclic ring agricultural chemicals is slowly joined contain in certain density inorganic acid and (or nothing) organic acid mixed system, impel its dissolving, add suitable surfactant and (or nothing) antifreeze thickener then, can be made into the nitrogen heterocyclic ring microemulsion that does not contain any hazardous solvent.This method is applicable to the making of nitrogen heterocyclic ring agricultural chemicals 2%～60% microemulsion of multiple structure type.
2,, it is characterized in that referring to according to the described inorganic acid of nitrogen heterocyclic ring microemulsion and preparation method thereof claim 1: in the water-soluble inorganic acid such as hydrobromic acid, hydroiodic acid, acid iodide, hydrochloric acid, perchloric acid, hypochlorous acid, nitric acid, Asia nitric acid, thiocyanic acid, molybdic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, pyrophosphoric acid one or more.The usage amount of its indication inorganic acid is, with 30%～100% (i.e. identical molal quantity * activated nitrogen atom number * 0.3～1.0 with working substance) of the identical molal quantity of working substance.
3,, it is characterized in that referring to: formic acid, acetate, dichloroacetic acid, propionic acid, malonic acid, butyric acid, succinic acid according to the described organic acid of nitrogen heterocyclic ring agricultural chemicals micro emulsion and preparation method thereof claim 1. in the water-soluble organic acids such as lactic acid, citric acid, malic acid, tartaric acid, oxalic acid, pyruvic acid, pantothenic acid, sulfosalicylic acid, alkyl benzene sulphonate, sulfanilic acid, maleic acid, naphthenic acid, gluconic acid, DL-alanine, glycine, glutamic acid L-cystine, aminotriacetic acid, ethylenediamine tetra-acetic acid (and its esters) one or more.Its indication organic acid usage amount is, with 0～70% (i.e. identical molal quantity * activated nitrogen atom number * 0～0.7 with working substance) of the identical molal quantity of working substance.
4, according to the described appropriate surfactant of nitrogen heterocyclic ring microemulsion and preparation method thereof claim 1, it is characterized in that referring to: (different) OPEO and phosphate (OPE thereof, SOPE and OPEPO4, SOPEPO4 series), polyoxyethylene nonylphenol ether and phosphate thereof and sulphosuccinates (NPE and NPEPO4 and MAPM series), ethoxylated dodecyl alcohol and phosphate thereof and sulphosuccinates (AEO and AEPO4 and AEM series), fatty alcohol-polyoxyethylene ether and phosphate (JFC thereof, peregal and phosphate MAP series thereof), phenethyl phenol polyethenoxy ether and phosphate thereof (601#-～606# and SPEnPO4 series), alkylphenol polyoxyethylene formaldehyde condensation products (agricultural breast-700# series) and phosphate thereof, phenethyl phenol polyethenoxy ether formaldehyde condensation products (agricultural breast-700-1#, peaceful breast-36#, SPF series) and phosphate, cumylphenol APEO formaldehyde condensation products (agricultural breast-700-2#, peaceful breast-37# series) and phosphate, phenethyl phenol polyethenoxy polyethenoxy ether (agricultural breast-1601#, peaceful breast-33# series) and phosphate, phenethyl phenol polyoxyethylene polyoxypropylene ether (agricultural breast-1602#, peaceful breast-34# series) and phosphate, polyoxyethylene sorbitan carboxylic ester (TW series) and phosphate thereof, castor oil polyoxyethylene ether (EL series) and phosphate thereof, aliphatic amine polyoxyethylene ether series and phosphate thereof, APG organic acid esters (salt) and ethylene oxide adduct series and phosphate thereof, organosilicon non-(the moon) ionic surface active agent and Dodecyl trimethyl ammonium chloride such as (fluorine), DDAO, dodecyl dimethyl benzyl ammonium bromide, in cationic surfactants such as imidazoline cationic compound series and the polymeric carboxylic polymer one or more.The usage amount of its indication surfactant is the 5%-25% of prescription composition gross mass.
5, according to the described antifreeze thickener of nitrogen heterocyclic ring microemulsion and preparation method thereof claim 1, it is characterized in that referring to: in water-soluble height (low) molecular compounds such as ethylene glycol, propane diols, glycerine, PEG400 #, polyvinyl alcohol, sorbierite, cellosolve and carboxymethyl cellulose, starch derivatives, xanthans, carragheen, alginic acid, polyacrylic acid, carboxylic ethylene polymer one or more, the usage amount of the antifreeze thickener of its indication is for prescription is formed 0～5% of gross mass.
6,, it is characterized in that referring to according to the nitrogen heterocyclic ring agricultural chemicals of the described suitable multiple structure type of nitrogen heterocyclic ring microemulsion and preparation method thereof claim 1: (1) propiconazole, nitrile bacterium azoles, Difenoconazole, Flusilazole, fluorine ring azoles, Tebuconazole, the sixth of the twelve Earthly Branches azoles alcohol, Triadimenol, alkene azoles alcohol, triazolone, uniconazole P, paclobutrazol, MBAMT (diazole), press down mould azoles triazole (pyrazoles, imidazoles) class agricultural chemicals such as (imidazoles); (2) Imidacloprid. Acetamiprid. plan such as thiophene worm piperazine nicotine (pyridine. pyrimidine) the class agricultural chemicals; (3) in other nitrogen heterocyclic ring agricultural chemicals of above-mentioned identical chemical structure type such as amino-contained such as phonetic mould amine, fly eradication amine, tebufenpyrad, Nitenpyram, alkene oxime amine, niclosamide, fluorine worm nitrile, Buprofezin, dimethomorph, procymidone, the fast quinoline of 6-benzyl gland, Acetochlor, isopropyl methoxalamine, atrazine, prometryn or amide groups one or more.The content of its indication chemical constitution type nitrogen heterocyclic ring microemulsion is 2%～60%.
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| CN102365957A (en) * | 2011-09-13 | 2012-03-07 | 辽宁师范大学 | Uniconazole microemulsion as well as preparation method and application thereof |
| CN103621497A (en) * | 2013-11-13 | 2014-03-12 | 江西巴菲特化工有限公司 | Method for processing preparation from raw pesticide structure |
| CN104982460A (en) * | 2015-07-20 | 2015-10-21 | 国家林业局泡桐研究开发中心 | Anti-freezing liquid for resisting late frost for kernel-apricots and preparation method and application thereof |
| CN107843659A (en) * | 2017-09-30 | 2018-03-27 | 安徽华星化工有限公司 | A kind of solution positive liquid chromatographic detection pyrethrin pesticide aqueous emulsion and aqueous suspension agent and the immiscible method of solvent |
| CN111187204A (en) * | 2020-01-13 | 2020-05-22 | 海利尔药业集团股份有限公司 | Acetamiprid eutectic crystal and preparation method and application thereof |
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| CN101984822B (en) * | 2010-08-06 | 2012-12-12 | 东莞市瑞德丰生物科技有限公司 | Germicide composition |
| CN102365957A (en) * | 2011-09-13 | 2012-03-07 | 辽宁师范大学 | Uniconazole microemulsion as well as preparation method and application thereof |
| CN103621497A (en) * | 2013-11-13 | 2014-03-12 | 江西巴菲特化工有限公司 | Method for processing preparation from raw pesticide structure |
| CN104982460A (en) * | 2015-07-20 | 2015-10-21 | 国家林业局泡桐研究开发中心 | Anti-freezing liquid for resisting late frost for kernel-apricots and preparation method and application thereof |
| CN104982460B (en) * | 2015-07-20 | 2017-12-22 | 国家林业局泡桐研究开发中心 | A kind of anti frozen liquid and preparation method and application of Armeniaca vulgaris resistance late frost |
| CN107843659A (en) * | 2017-09-30 | 2018-03-27 | 安徽华星化工有限公司 | A kind of solution positive liquid chromatographic detection pyrethrin pesticide aqueous emulsion and aqueous suspension agent and the immiscible method of solvent |
| CN111187204A (en) * | 2020-01-13 | 2020-05-22 | 海利尔药业集团股份有限公司 | Acetamiprid eutectic crystal and preparation method and application thereof |
| CN111187204B (en) * | 2020-01-13 | 2022-11-08 | 海利尔药业集团股份有限公司 | Acetamiprid eutectic crystal and preparation method and application thereof |
| CN114600881A (en) * | 2022-04-22 | 2022-06-10 | 广西田园生化股份有限公司 | Pesticide liquid preparation and preparation method thereof |
| CN114600881B (en) * | 2022-04-22 | 2023-09-12 | 广西田园生化股份有限公司 | Pesticide liquid preparation and preparation method thereof |
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