CN105532656A - Environment-friendly dinotefuran microemulsion and preparation method thereof - Google Patents
Environment-friendly dinotefuran microemulsion and preparation method thereof Download PDFInfo
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- CN105532656A CN105532656A CN201610061491.XA CN201610061491A CN105532656A CN 105532656 A CN105532656 A CN 105532656A CN 201610061491 A CN201610061491 A CN 201610061491A CN 105532656 A CN105532656 A CN 105532656A
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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
- A01N25/30—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 characterised by the surfactants
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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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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Abstract
The invention provides an environment-friendly dinotefuran microemulsion which is prepared from the following components in percentage by weight: 1 to 20 percent of dinotefuran , 4 to 10 percent of anionic surface active agent, 2 to 12 percent of non-ionic surface active agent, 5 to 12 percent of ketone solvents with a boiling point above 150 DEG C, 0.01 to 0.04 percent of defoaming agent, and the balance of water, wherein the anionic surface active agent is selected from one or more of anionic surface active agents, wherein the hydrophobic group of the anionic surface active agents is vegetable oil hydrolyzed or pyrolysed linear chain alkyl or alkenyl, and the hydrophilic group of the anionic surface active agents is selected from carboxyl, acidophobe or sulfonic acid group; the non-ionic surface active agent is selected from one or more of polyethoxylated non-ionic surface active agents, wherein the hydrophobic group of the non-ionic surface active agent is vegetable oil or vegetable oil hydrolyzed or pyrolysed linear chain alkyl or alkenyl. The invention also provides a preparation method of the environment-friendly dinotefuran microemulsion.
Description
Technical field
The invention belongs to pesticides new formulation field, particularly a kind of environmental friendliness dinotefuran micron-emulsion and preparation method thereof of use plant source wedding agent newly.
Background technology
Agricultural chemicals (referring to pesticidal preparations in this specification) is the specialty goods controlling farm-forestry crop disease, worm, crop smothering, is the indispensable means of production of modern agriculture.But it is again one " double-edged sword ", on the one hand, by applying pesticides, the whole nation can retrieve the grain loss of about 30,000,000,000 kilograms every year.On the other hand, also day shows protrusion for the food security caused thus and problem of environmental pollution.The pollution that agricultural chemicals brings, has the reason of active component self, also has the solvent in preparation and auxiliary agent reason.Consumption due to solvent and auxiliary agent is general comparatively large, therefore, is sometimes more far more than active component itself by endangering the secondary of people, animal and environment of bringing of solvent and/or auxiliary agent improperly.
In August, 2010, four ministries and commissions of country combine " the agricultural chemicals industrial policy " of appearance, explicitly point out: " country is by measure such as science and technology supports, technological transformation, economic policy guiding etc.; support efficient, safety, economy, the development of eco-friendly pesticide new product; accelerate high pollution, the substituting and eliminating of excessive risk product, promotion breed structure is continued to optimize "; " promote agricultural formulation energetically to efficient, the safe future development such as water baseization, dustlessization, Co ntrolled release ... the strict use controlling poisonous and harmful solvent and auxiliary agent." Ministry of Industry and Information's " pesticide industry " 12 " development plan " of putting into effect also emphasizes: " the strict use controlled containing the poisonous and harmful such as toluene, dimethylbenzene solvent and auxiliary agent, develops and promotes the formulations such as water baseization ".Therefore, the pesticidal preparations of development environment close friend, especially water baseization pesticidal preparations is the requirement in epoch.When the active component synthesized and screen high-efficiency low-toxicity more day by day difficulty, improve existing pesticidal preparations with the auxiliary agent of environmental protection and/or solvent, become the mainstream development direction of the friendly formulations of pesticide of development environment.
The water baseization formulations of pesticide of all or part of replacement organic solvent of water are used to comprise: aqua, microemulsion, aqueous emulsion, suspending agent and suspension emulsion.Because most pesticide activity component is all fat-soluble, or unstable in water, and therefore, the aqueous pesticide solution kind not comprising any organic solvent is little.
Microemulsion and aqueous emulsion are all active component is dissolved in a certain amount of organic solvent to form solution, then are dispersed in water in the mode of fine droplet.Drop size in microemulsion is generally a few nanometer to tens nanometer, is less than 1/4th of visible wavelength.The drop size of aqueous emulsion is greater than visible wavelength, generally more than hundreds of nanometer or to micron order.Indissoluble or insoluble active component are then normally ground into particulate (general≤5 μm) by mechanical force by suspending agent, then make its dispersion suspension in water.Suspension emulsion is then the combining form of suspending agent and aqueous emulsion.Obviously, in above-mentioned four kinds of water base chemical preparations, the agricultural chemicals particulate in microemulsion is minimum, has obvious advantage.Reason is:
1) drug effect of pesticidal preparations is relevant with size with preparation Pesticides particulate form.Particle size is less, and particle number is more, and its surface area is larger, larger with the contact area of target organisms, and the drug effect of performance is larger.Therefore, the usefulness of microemulsion is higher than other three kinds of preparations; Under the prerequisite of identical drug effect, consumption can reduce relatively.
2) particulate of microemulsion is at nano-scale, is in fact exactly a kind of nanometer formulation.Therefore, microemulsion belongs to thermodynamic stable system, and preparation is transparent, excellent storage stability.And aqueous emulsion, suspending agent and suspension emulsion are all thermodynamic unstable systems, preparation is opaque, and storage may exist the problems such as flocculation, layering.
3) microemulsion preparation method is simple, and do not need high speed shear emulsification (aqueous emulsion) and Mechanical Crushing (suspending agent), suitable formula system only needs gentle agitation.
Organic solvent contained by microemulsion and emulsifier performance difference are very large, have impact on the environmental friendliness performance of microemulsion all to some extent.
MTI-446 (dinotefuran), chemical name is (RS)-1-methyl-2-nitro-3-(3-tetrahydrofuran methyl) guanidine, be the third generation anabasine insecticide of Mitsui chemical company exploitation, listing in 2002, chemical structural formula as indicated with 1.MTI-446 has excellent preventive effect to sucking insect, not only have tag, stomach toxicity and root systemic activity, and have that interior absorption is strong, consumption is few, quick-acting good, the feature such as activity is high, the lasting period is long, insecticidal spectrum is wide.Do not have cross resistance with common insecticides, thus antagonism insect has special efficacy.Be mainly used in preventing and treating the sucking insect in the various crop such as paddy rice, cotton, wheat, vegetables, fruit tree, tea tree, flowers, ornamental plants, as stinkbug, aphid, plant hopper, thrips, leafhopper class Hemipteran pest, diamond-back moth, beetle order and total wing order insect, and the difficulty beans peach of preventing and kill off is dived the Diptera pests such as fly; Also just like the brown planthopper of paddy rice, white-backed planthopper, rice leafhopper, striped rice borer, the aphid, aleyrodid class, a red-spotted lizard class diamond-back moth etc. of Vegetables and fruits.In addition, MTI-446 also has efficiently sanitary insect pests such as blattaria, termite, houseflies.
Different from the structure of existing nicotinic insecticide, MTI-446 instead of chloro-pyridine ring, chloro-thiazole ring with oxolane ring, and not halogen-containing.The solvability of MTI-446 is 4g/100gH
2o (20 DEG C), belongs to water microsolubility material, is insoluble in the non-polar organic solvent such as cyclohexane, dimethylbenzene.Obviously, the MTI-446 aqua preparing high concentration is more difficult.
Also occurred in prior art that some take MTI-446 as the technical scheme of the microemulsion of pesticide original medicine.
As, publication number CN102415405A (publication date on April 18th, 2012), name are called the Chinese invention patent application of " a kind of dinotefuran micron-emulsion and preparation method thereof ", disclose a kind of dinotefuran micron-emulsion.By MTI-446, solvent (is selected from cyclohexanone, toluene, dimethylbenzene, DMSO or DMF), surfactant (is selected from the compound of anion and non-ionic surface active agent, the compound of anion and non-ionic surface active agent and solvent, calcium dodecyl benzene sulfonate, styrylphenol formaldehyde resin PULLRONIC F68 block type polyethers, the polyoxyethylene nonylphenol ether of nonionic or the OPEO of nonionic), cosolvent (is selected from ethanol, propyl alcohol, isopropyl alcohol or the tert-butyl alcohol) and water composition.Wherein, percentage by weight shared by each component is MTI-446 1-40%, solvent 10-30%, surfactant 10-25%, cosolvent 5-15%, and surplus is water.This microemulsion can also comprise stabilizing agent and bleeding agent.Technique scheme Problems existing is: 1. consumption of organic solvent is large.The consumption of solvent and cosolvent is up to 14-45%, if counted by the solvent in agriculture breast 2201, then the consumption of organic solvent is larger; 2. the toxicity of solvent for use is comparatively large, as toluene, dimethylbenzene, DMSO or DMF; 3. emulsifier not environmentally, the nonyl phenol (NP) that the degraded of its polyoxyethylene nonylphenol ether adopted (OP-10) produces is a kind of generally acknowledged environmental hormone, it can simulate oestrogenic hormone, the sexual development of biology is had an impact, and the internal secretion that interference is biological, to genital system, there is toxicity.Even if nonyl phenol and precursor compound content thereof are seldom, also have harmfulness, disabled in the world.
And for example, publication number is CN1951193A (publication date on April 18th, 2007), name is called the Chinese invention patent application of " rotenone and MTI-446 complex microemulsion and preparation method thereof ", discloses a kind of MTI-446 complex microemulsion.Complex microemulsion is made up of rotenone and MTI-446, emulsifier (being selected from nonyl phenol, phenethyl phenol, xenol and Ben-zylphenol Polyoxyethyl Ether), bleeding agent (being selected from sulfosuccinate di-sec-octyl sodium salt, Sodium Octylphosphate and azone), stabilizing agent (being selected from butyl glycidyl ether, phenyl glycidyl ether or acrylic glycidol ether), cosolvent (being selected from isoamyl alcohol, acetone, ethyl acetate or phenol) and water.Percentage by weight shared by each component is rotenone 0.5-25%, MTI-446 1.5-45%, emulsifier 3-22%, bleeding agent 2-16%, stabilizing agent 1-15%, cosolvent 2-20%, and surplus is water.Technique scheme Problems existing is: 1. auxiliary dosage is large, and the total amount of the auxiliary agents such as emulsifier, bleeding agent, stabilizing agent and cosolvent can up to 36%; 2. emulsifier not environmentally, uses polyoxyethylene nonylphenol ether equally.
Also have, publication number is CN104186527A (publication date on December 10th, 2014), name is called that the Chinese invention patent application of " a kind of Pesticidal combination containing four chlorantraniliproles and MTI-446 " discloses a kind of agricultural insecticide composition containing MTI-446, it is disclosed that the microemulsion (embodiment 5) of a kind of four chlorantraniliproles and MTI-446, wherein four chlorantraniliproles 10%, MTI-446 5%, emulsifier (agriculture breast 500#) 5%, emulsifier (agriculture breast 1601#) 5%, antifreezing agent (ethylene glycol) 10%, surplus is water.In this scenario, auxiliary dosage is large: total consumption of emulsifier and the consumption of antifreezing agent are 2 times of MTI-446 all respectively.In addition, in said preparation, the content of MTI-446 is low, and only 5%.
At present, domestic MTI-446 registration and the water base agent type of MTI-446 registered are all suspending agents, there are no microemulsion.Address before relevant suspending agent Problems existing.This also reflects from another side, prepares to meet agriculture chemical registration requirement, the dinotefuran micron-emulsion of list marketing can there is very large technical difficulty.
Summary of the invention
One object of the present invention is to overcome the deficiencies in the prior art, provides a kind of new environmental friendliness dinotefuran micron-emulsion.Dinotefuran micron-emulsion of the present invention has the advantages that obviously be better than prior art: 1. surfactant (emulsifier) is all be derived from vegetable fat, easily biological-degradable, and environmental friendliness performance is given prominence to; 2. not containing alkylphenol polyoxyethylene, the emulsifier components such as the polyoxyethylene nonylphenol ether especially forbidden, nonyl phenol poly-oxypropylene ether, without environmental hazard; 3. strong polarity or polar latent solvent, antifreezing agent is not used, without environment hidden danger; 4. use the ketones solvent of low toxicity or micro-poison, boiling point is more than 150 DEG C, and when MTI-446 content is 20%, solvent is only 0.62:1 with the ratio of former medicine; 5. described microemulsion outward appearance is the solution of faint yellow clear, and long-term placement is stablized, and physical properties meets state specified standards index.
A further object of the invention, is the preparation method providing described environmental friendliness dinotefuran micron-emulsion.
In order to realize foregoing invention object, present invention employs following technical scheme:
A kind of environmental friendliness dinotefuran micron-emulsion, according to weight percent meter, comprising:
1%-20% MTI-446,4%-10% anion surfactant, 2%-12% non-ionic surface active agent, the ketones solvent of 5%-12% boiling point more than 150 DEG C, 0.01%-0.04% defoamer, surplus is water;
Wherein, it is come from vegetable oil hydrolysis or the straight chained alkyl of cracking or thiazolinyl that described anionic surfactant is selected from hydrophobic grouping, hydrophilic radical be selected from carboxyl, sulfate or sulfonic anion surfactant one or more; Described non-ionic surface active agent be selected from hydrophobic grouping be come from vegetable oil or vegetable oil hydrolysis or the straight chained alkyl of cracking or the polyethenoxy ether class non-ionic surface active agent of thiazolinyl one or more.
Preferably, environmental friendliness dinotefuran micron-emulsion, according to weight percent meter, comprising:
10%-20% MTI-446,4%-8% anion surfactant, 6%-12% non-ionic surface active agent, the ketones solvent of 6%-12% boiling point more than 150 DEG C, 0.01%-0.04% defoamer, surplus is water.
Preferably, the gross mass of described anion surfactant and non-ionic surface active agent, the ketones solvent quality of boiling point more than 150 DEG C, and the mass ratio of MTI-446 is 0.9 ~ 0.95: 0.6 ~ 0.7: 1 respectively.
Preferred, the gross mass of described anion surfactant and non-ionic surface active agent, the ketones solvent quality of boiling point more than 150 DEG C, and the mass ratio of MTI-446 is 0.93 ~ 0.95: 0.62 ~ 0.66: 1 respectively.
Preferably, the hydrophobic grouping of described anionic surfactant and non-ionic surface active agent is straight chained alkyl or the thiazolinyl with 7-17 carbon atom.
Preferred, described anion surfactant be selected from enuatrol or potassium, linoleic acid sodium or potassium, linolenic acid sodium or potassium, sodium ricinoleate or potassium, myristyl carboxylic acid sodium or potassium, sodium tetradecyl sulfate or potassium, myristyl ether sodium sulfate or potassium, sodium laurate or potassium, lauryl sodium sulfate or potassium, sodium lauryl tri(oxyethyl) sulfate or potassium and undecenoic acid sodium or potassium one or more.
Most preferred, described non-ionic surface active agent is selected from one or more of 10 two to tetradecyl alchohol APEOs (AEO), 10 six to polyoxyethylene octadecanols (peregal), cocounut oil acid ester polyoxyethylene ether, oleate APEO, fatty acid esters of sorbitan APEO (tween) and castor oil polyoxyethylene ether (EL).
Preferably, the ketones solvent of described boiling point more than 150 DEG C is selected from one or more in cyclohexanone, methyl cyclohexanone and methyln-hexyl ketone.
Preferably, described defoamer is selected from tributyl phosphate, 6 ~ 8 carbon alcohol or silicone defoaming agents.
Another object of the present invention, is the preparation method providing described environmental friendliness dinotefuran micron-emulsion, comprises the steps:
I. various raw material is prepared according to formula;
II. except ketones solvent more than 150 DEG C of MTI-446, boiling point and defoamer, water in formula and other raw material are added stirred tank, stir, make it dissolve, obtain solution A;
III. the ketones solvent of boiling point more than 150 DEG C is added another container, then add MTI-446, stir, make it dissolve, obtain solution B;
IV. solution B is joined in solution A, stir, become clear solution, then add defoamer, gentle agitation, static, filter, obtain dinotefuran micron-emulsion.
Environmental friendliness dinotefuran micron-emulsion of the present invention, without the need to high speed shear process, uses common stirring and filter, carries out under normal temperature condition, produce workable, facilitate simple and easy.
Environmental friendliness dinotefuran micron-emulsion of the present invention, be mainly used in preventing and treating the sucking insect in the various crop such as paddy rice, cotton, wheat, vegetables, fruit tree, tea tree, flowers, ornamental plants, as stinkbug, aphid, plant hopper, thrips, leafhopper class Hemipteran pest, diamond-back moth, beetle order and total wing order insect, and the difficulty beans peach of preventing and kill off is dived the Diptera pests such as fly; Also just like the brown planthopper of paddy rice, white-backed planthopper, rice leafhopper, striped rice borer, the aphid, aleyrodid class, a red-spotted lizard class diamond-back moth etc. of Vegetables and fruits.In addition, environmental friendliness dinotefuran micron-emulsion of the present invention also has efficiently sanitary insect pests such as blattaria, termite, houseflies.
After testing, the environmental friendliness dinotefuran micron-emulsion of variable concentrations provided by the invention, property indices reaches state specified standards:
1. microemulsion outward appearance is faint yellow clear shape, and stable storing any ratio can disperse rapidly, dilutes in water, without precipitation, muddy, lamination.
2. in microemulsion, the most high-load of the active ingredient of MTI-446 can reach 20%, maintains an equal level with the content of current domestic common suspending agent.
3. microemulsion stability in hard water can be qualified, in the hard water of normal concentration, muddiness, precipitation do not occur.
4. microemulsion high-and low-temperature resistance performance is qualified, and storage and serviceability temperature scope are-6 DEG C ~ 90 DEG C.
Dinotefuran micron-emulsion of the present invention has excellent environmental friendliness performance, bin stability and drug effect.The most outstanding feature is, 1. formulation environment is friendly.The auxiliary agent used is all plant resource surfactant, biodegradable, not containing polyoxyethylene nonylphenol ether material, not containing strong polarity or polar latent solvent.2. the consumption of surfactant and organic solvent in preparation is decreased as far as possible.The mass ratio of preferred surfactant (comprising anion and nonionic), solvent and former medicine is respectively 0.93 ~ 0.95: 0.62 ~ 0.66: 1, reduces the impact on environment to greatest extent.3. formulation storage is stablized, and breakdown of emulsion or precipitation gathering do not occur.4. drug effect is remarkable.2 times of Imidacloprid to the indoor virulence MTI-446 of tea lesser leafhopper; The killing action of dinotefuran micron-emulsion of the present invention to tea lesser leafhopper 3 nymph in age is remarkable.The LC of 10% microemulsion
50for 1.44mg/L, and 20% suspending agent is in contrast 2.21mg/L.When identical drug effect, use microemulsion of the present invention can reduce the amount of application of MTI-446.Therefore, dinotefuran micron-emulsion of the present invention improves the environmental friendliness performance of preparation to greatest extent from many aspects.
Compare with dinotefuran micron-emulsion disclosed in prior art, the present invention also has outstanding advantage:
1) microemulsion disclosed in publication number CN102415405A, CN1951193A and CN104186527A, all have employed the surfactant containing aromatic group, the later product of such surfactant degradation enters in human or animal body and is not only difficult to metabolism, and have hormone-like effect, harmfulness is large.And the surfactant that microemulsion of the present invention adopts, its hydrophobic grouping is straight chained alkyl or thiazolinyl, derives from hydrolysis or the cracking of vegetable oil, can not produce poison the environment sprayed or contact humans and animals.
2) although publication number preparation name disclosed in CN1951193A is called microemulsion, be the use of high-speed shearing machine and mix, actual is a kind of aqueous emulsion, belongs to thermodynamic unstable system, not shelf-stable.
In addition, dinotefuran micron-emulsion provided by the invention, compared with MTI-446 suspending agent, making equipment needed thereby and manufacture craft simply, have Industry Promotion and are worth.Described dinotefuran micron-emulsion, can use the normally used mixing apparatus of insecticide factory, as stirred tank makes, do not need the Jet Mill adding high price, and the technique of whole manufacturing process is simple, flow process is short, easy operation, can carry out automation after completing filling.Therefore, along with applying of dinotefuran micron-emulsion of the present invention, significant economic benefit and social benefit will be produced.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is explained.
Fig. 1 photo display be embodiment 1 ~ 3 prepare environmental friendliness dinotefuran micron-emulsion sample photo, the outward appearance of three samples is faint yellow as clear as crystal liquid.
Embodiment
Below, by preferred embodiment, the present invention is described in detail.But the present invention is not restricted to following embodiment.
Various raw materials used in embodiment all can be obtained by commercial channel.
embodiment 1a kind of 10% environmental friendliness dinotefuran micron-emulsion
Pulp furnish:
Prepare by the following method:
I. according to formulation weight proportioning, the various raw materials of preparation 1000kg microemulsion are prepared;
II. respectively lauryl sodium sulfate, tween-30, linolenic acid sodium are joined in stirred tank, add deionized water, stir, make dissolving, obtain solution A;
III. MTI-446 is added in solvent cyclohexanone, stir, make dissolving, obtain solution B;
IV. join in solution A by solution B, stir, then add tributyl phosphate defoamer, gentle agitation, static, filter, obtain the target product of the transparent shape of outward appearance, sample photo is see Fig. 1.
The test item of 10% dinotefuran micron-emulsion prepared by the present embodiment, method and quality standard list in table 1.
The test item of table 110% dinotefuran micron-emulsion, detection method and testing result
embodiment 2a kind of 15% environmental friendliness dinotefuran micron-emulsion
Pulp furnish:
Adopt the preparation method similar to embodiment 1 and step, obtain 1000kg target product, sample photo is see Fig. 1.
15% environmental friendliness dinotefuran micron-emulsion prepared by the present embodiment detects according to project described in table 1, except content is except 15%, every result all with embodiment 1 come to the same thing or close.
embodiment 3a kind of 20% environmental friendliness dinotefuran micron-emulsion
Pulp furnish:
Adopt the preparation method similar to embodiment 1 and step, obtain 1000kg target product, sample photo is see Fig. 1.
20% environmental friendliness dinotefuran micron-emulsion prepared by the present embodiment detects according to project described in table 1, except content is except 20%, every result all with embodiment 1 come to the same thing or close.
test example 1environmental friendliness 10% dinotefuran micron-emulsion insecticidal test of the present invention
1.1 test names: dinotefuran micron-emulsion is to the Toxicity Determination of tea lesser leafhopper
1.2 controlling objects: tea lesser leafhopper (Empoascavitis (Gothe)) gathers and tea place, Yingde, Guangdong area, with cylindrical glass tube dress collection.Gather tea slightly, for raising and raw survey simultaneously.
1.3 test medicines:
1) 10% dinotefuran micron-emulsion of embodiment 1 preparation;
2) 20% MTI-446 suspending agent, prepared by Shan Si bio tech ltd, Hebei.
1.4 medicament preparations
Accurately take test medicine, directly add deionized water and dilute, be mixed with the mother liquor of 10000mg/L.
According to the concentration range that preliminary experiment is determined, often kind of medicament designs 5 concentration gradients (by active ingredient), sets clear water contrast simultaneously.
1.5 test method
With reference to agricultural industry criteria NY/T1154.14-2008, leaf dipping method is adopted to carry out.Specific as follows:
Choose clean, healthy tea leaf, be trimmed to suitable size.In variable concentrations liquid, flood 15s, after taking-up is put into and dries in the culture dish being covered with clean filter paper, then tea leaf is put into the test tube of base diameter 2.5cm, high 7.5cm, put into a wet cotton balls moisturizing simultaneously.Then often pipe accesses close tea lesser leafhopper 3 nymph in age of 30 individualities, with gauze sealing, in case examination worm escapes.If blank, often process repetition 4 times.After process, examination worm being placed in temperature is 25 ± 1 DEG C, and humidity is about 70%, the photoperiod is raising and observation in the insectary of L:D=16:8h.The situation of 48h " Invest, Then Investigate " tea lesser leafhopper death.
1.6 data processing
Calculate lethality and corrected mortality according to formula I and formula II respectively, carry out network analysis with POLO software, obtain independent regression equation, LC
50, LC
90with 95% confidence limit, the virulence effect of com-parison and analysis medicament.
Lethality (%)=death toll/total borer population × 100%I,
Corrected mortality (%)=(process lethality-corrected mortality)/(1-contrasts lethality) × 100%II.
1.7 result of the test
After the dinotefuran micron-emulsion of variable concentrations and MTI-446 suspending agent process tea lesser leafhopper, the initial data such as its death condition are in table 2.
The death condition (48h) of tea lesser leafhopper after the process of table 2 different MTI-446 preparation
Convert concentration to logarithm value, corrected mortality converts probability value to, carries out linear regression.The different preparation of MTI-446 to tea lesser leafhopper, LC
50, LC
90with numerical value such as 95% confidence limits in table 3.
Table 3 different furan worm preparation is to the indoor virulence (48h) of tea lesser leafhopper
As can be seen from Table 3, after leaf dipping method process 48h, two kinds of MTI-446 preparations all show good biologically active to tea lesser leafhopper, but the LC of 10% dinotefuran micron-emulsion and 20% MTI-446 suspending agent
50being respectively 1.44mg/L and 2.21mg/L, there is significant difference in both.
1.8 conclusions:
The activity of 10% dinotefuran micron-emulsion is better than 20% MTI-446 suspending agent, and both there are differences significance.
test example 2the safety evaluatio of 10% dinotefuran micron-emulsion of the present invention
2.1 test names: 10% dinotefuran micron-emulsion is to the safety evaluatio of tea tree
2.2 subjects: tea tree, kind is red No. 1 of English, narcissus, white hair; Tea tree does not use other any medicaments, is not plucked yet.Test site is on tea plantation, teaching and scientific research base, Agricultural University Of South China Zengcheng.
2.3 test medicines: 10% dinotefuran micron-emulsion prepared by the embodiment of the present invention 1
2.4 dosage are arranged
By active ingredient, test setting 120ga.i./ha, 240ga.i./ha, 480ga.i./ha tri-dosage, are directly watered and carry out cauline leaf spraying.Contrast spray equivalent clear water.
2.5 test method
With reference to People's Republic of China (PRC) agricultural industry criteria NY/T1965.1-2010, carry out cauline leaf spraying process in the growth of tea plant phase.Concrete grammar is as follows:
Adopt sprayer according to above-mentioned setting dosage, process to the order of high dose from contrast, low dosage.According to the planting density of every mu of 3000 strain tea trees, after conversion, calculate dosage, by liquid even spraying to tea tree stem and leave dual sides.The strain of each dosage spray tea tree 10, often processes and repeats for 4 times.If blank.The normal water and fertilizer management of duration of test.
Because tea tree plant exists bending, therefore the growth rate measurment of plant is undertaken by the growing height measuring the tender tip in top.In each dosage process community, choose 5 points for investigation before medicine, fasten red rope and carry out mark, measure top height of shoot.After medicine 21 days, measure the height of shoot of marker site, calculate the growth rate of plant with this.
2.6 poisoning are observed
1d, 3d, 7d, 10d, 14d, 21d after medicine, observe plant forms and color change, judge whether medicament produces poisoning to plant, and record type and the extent of injury of poisoning.
2.7 symptom of chemical damage describe
Variable color: comprise chlorisis, chrysanthemum, albefaction, floral leaf, rust staining, brownization, greening etc.
Downright bad: spot, withered spot, leaf margin are downright bad, growing point or climbing stem is withered, fallen leaves, fallen flowers, shedding, unfilled gtains etc.
Grow and delay: dwarfing, shortened internodes, vane extension be suppressed, it is uneven to emerge, the maturing stage changes, stagnation of growing.
Wilt: plant dehydration is wilted, green grass or young crops is withered.
Deformity: hang contracting, Hua Sui of tiller abnormal, growth adventive root, lateral growth, excessive growth, leaf rolling or torsional deformation, stem is out of shape.
2.8 poisoning extent descriptions
2.8.1 variable color
Dispenser ensuing crop is very safe without any visible symptom of chemical damage;
There is the crop leaf being less than 10% to have light discolouration after dispenser, or can safety be reverted in 3d ~ 4d;
There is the crop leaf of 11% ~ 20% to have obvious variable color after dispenser, or slight poisoning can be reverted in 7d ~ 10d;
There is the obvious variable color of the crop leaf of 21% ~ 50% after dispenser, or moderate poisoning can not be reverted in 10d;
There is the obvious variable color of the blade of more than 50% after dispenser, and serious poisoning can not be reverted to.
2.8.2 downright bad
Dispenser ensuing crop is very safe without any visible symptom of chemical damage;
Have the crop organ within 10% to occur minority spot or necrosis, account for crop organ's area less than 1%, or the fallen leaves of increase by less than 1%, fallen flowers, shedding or unfilled gtains are safety;
Have the crop organ of 11% ~ 20% to occur spot or necrosis, account for crop organ's area less than 3%, or the fallen leaves of increase by less than 3%, fallen flowers, shedding or unfilled gtains are slight poisoning;
Have the crop organ of 21% ~ 50% to occur spot or necrosis, account for crop organ's area less than 10%, or the fallen leaves of increase by less than 10%, fallen flowers, shedding or unfilled gtains are moderate poisoning;
Have the crop organ of more than 50% to occur spot or necrosis, account for crop organ's area more than 10%, or the fallen leaves of increase by more than 10%, fallen flowers, shedding or unfilled gtains are serious poisoning;
2.8.3 growth retardation
Dispenser ensuing crop is very safe without any visible symptom of chemical damage;
After dispenser, in 21d, growth rate inhibiting rate 10% thinks safety;
After dispenser, in 21d, growth rate inhibiting rate 11% ~ 20% is slight poisoning;
After dispenser, in 21d, growth rate inhibiting rate 21% ~ 50% is moderate poisoning;
After dispenser, in 21d, growth rate inhibiting rate more than 50% is serious poisoning.
2.8.4 wilt
Dispenser ensuing crop is very safe without any visible symptom of chemical damage;
After dispenser, within 3d, crop leaf has the of short duration dehydration of 1h ~ 2h to wilt at noon, then reverts to safety;
After dispenser, within 3d, crop leaf has 3h ~ 5h dehydration at noon, sooner or later reverts to slight poisoning;
After dispenser, within 3d ~ 5d, crop leaf had more than 5h dehydration to wilt in one day, sooner or later reverted to moderate poisoning;
Dispenser ensuing crop is wilted, and can not recover and wither for serious poisoning after 5d.
2.8.5 lopsided
Dispenser ensuing crop is very safe without any visible symptom of chemical damage;
21d after dispenser, have that plant tillering within 5% is abnormal, growth adventive root, lateral growth, excessive growth, leaf rolling or torsional deformation, hang contracting, Hua Sui of stem is deformed into safety;
Have that plant tillering within 6% ~ 25% is abnormal, growth adventive root, lateral growth, excessive growth, leaf rolling or torsional deformation, hang contracting, Hua Sui of stem is deformed into slight poisoning;
Have that plant tillering within 26% ~ 50% is abnormal, growth adventive root, lateral growth, excessive growth, leaf rolling or torsional deformation, hang contracting, Hua Sui of stem is deformed into moderate poisoning;
Have that the plant tillering of more than 50% is abnormal, growth adventive root, lateral growth, excessive growth, leaf rolling or torsional deformation, hang contracting, Hua Sui of stem is deformed into serious poisoning.
The calculating of 2.9 poisoning degree
Evaluate with growth rate inhibiting rate.After dispenser, 21d measures each process plant height, evaluates the safety of medicament to plant by formula III and formula IV calculating growth rate and growth rate inhibiting rate.
The newborn height of growth rate=plant (mm)/time (d) III, growth rate inhibiting rate (%)=(contrast growth rate-process growth rate)/contrast growth rate × 100IV.Wherein, growth rate inhibiting rate=0, for very safe;
Growth rate inhibiting rate≤10% is safety;
11%≤growth rate inhibiting rate≤20% is slight poisoning;
21%≤growth rate inhibiting rate≤50% is moderate poisoning;
Growth rate inhibiting rate >50% is serious poisoning.
2.10 safety evaluatio result of the test
After 10% dinotefuran micron-emulsion spraying process, 3 kinds of form growth change for examination tea tree breed the results are shown in Table 4.
Table 410% dinotefuran micron-emulsion is observed tea tree symptom of chemical damage
Table 4 result shows, after the process of various dose 10% dinotefuran micron-emulsion not to producing variable color, necrosis for examination tea tree plant, growing delays, wilts and the symptom of chemical damage of deformity.Determine said preparation further to the poisoning degree of tea tree and growth rate inhibiting rate, the results are shown in Table 5.
Table 510% dinotefuran micron-emulsion is to the Security test result of tea tree
As can be seen from Table 5, after spraying process, 10% dinotefuran micron-emulsion does not cause tea tree to produce the phenomenon of variable color, necrosis, growth retardation, wilting and deformity under the dosage of 120ga.i./ha, 240ga.i./ha and 480ga.i./ha.After maximum dose level 480ga.i./ha process, it has all exceeded 10% to 3 growth rate inhibiting rates for examination tea tree breed, is up to 15.64%, illustrates that high dose process has slight poisoning.Meanwhile, the consumption of 240ga.i./ha also dialogue hair kind produces slight poisoning, and inhibiting rate is 10.61%.All the other dosage all show as safety.
2.11 conclusion
Measurement result shows, with 10% dinotefuran micron-emulsion with after 120ga.i./ha, 240ga.i./ha and 480ga.i./ha spraying process, does not produce symptom of chemical damage to red No. 1 of English, narcissus, white hair 3 tea tree breeds.
By statistics and the calculating of poisoning degree, after pressing red No. 1 of setting dosage spray process English, narcissus, white hair 3 tea tree breeds, the growth rate of dosage to the dosage dialogue hair of red No. 1 of English, narcissus, Bai Mao and 240ga.i./ha of 4 only 80ga.i./ha presents slight poisoning, and all the other dosage all show as safety to for examination tea tree.
In a word, the invention provides a kind of environmental friendliness dinotefuran micron-emulsion, its surfactant used is all plant origin, and solvent is also low toxicity; And total consumption of auxiliary agent is little.Environmentally friendly dinotefuran micron-emulsion of the present invention also has efficient, stable advantage.
Specific description of embodiments of the present invention does not above limit the present invention, and those skilled in the art can make various change or distortion according to the present invention, only otherwise depart from spirit of the present invention, all should belong to the scope of claims of the present invention.
Claims (10)
1. an environmental friendliness dinotefuran micron-emulsion, according to weight percent meter, comprising:
1%-20% MTI-446,4%-10% anion surfactant, 2%-12% non-ionic surface active agent, the ketones solvent of 5%-12% boiling point more than 150 DEG C, 0.01%-0.04% defoamer, surplus is water;
Wherein, it is come from vegetable oil hydrolysis or the straight chained alkyl of cracking or thiazolinyl that described anionic surfactant is selected from hydrophobic grouping, hydrophilic radical be selected from carboxyl, sulfate or sulfonic anion surfactant one or more; Described non-ionic surface active agent be selected from hydrophobic grouping be come from vegetable oil or vegetable oil hydrolysis or the straight chained alkyl of cracking or the polyethenoxy ether class non-ionic surface active agent of thiazolinyl one or more.
2. environmental friendliness dinotefuran micron-emulsion according to claim 1, is characterized in that, described environmental friendliness dinotefuran micron-emulsion, according to weight percent meter, comprising:
10%-20% MTI-446,4%-8% anion surfactant, 6%-12% non-ionic surface active agent, the ketones solvent of 6%-12% boiling point more than 150 DEG C, 0.01%-0.04% defoamer, surplus is water.
3. environmental friendliness dinotefuran micron-emulsion according to claim 1 and 2, it is characterized in that, the gross mass of described anion surfactant and non-ionic surface active agent, the ketones solvent quality of boiling point more than 150 DEG C, and the mass ratio of MTI-446 is 0.9 ~ 0.95: 0.6 ~ 0.7: 1 respectively.
4. environmental friendliness dinotefuran micron-emulsion according to claim 3, it is characterized in that, the gross mass of described anion surfactant and non-ionic surface active agent, the ketones solvent quality of boiling point more than 150 DEG C, and the mass ratio of MTI-446 is 0.93 ~ 0.95: 0.62 ~ 0.66: 1 respectively.
5. environmental friendliness dinotefuran micron-emulsion according to any one of claim 1 to 4, is characterized in that, the hydrophobic grouping of described anionic surfactant and non-ionic surface active agent is straight chain or the alkyl or alkenyl with 7-17 carbon atom.
6. environmental friendliness dinotefuran micron-emulsion according to any one of claim 1 to 5, it is characterized in that, described anion surfactant be selected from enuatrol or potassium, linoleic acid sodium or potassium, linolenic acid sodium or potassium, sodium ricinoleate or potassium, myristyl carboxylic acid sodium or potassium, sodium tetradecyl sulfate or potassium, myristyl ether sodium sulfate or potassium, sodium laurate or potassium, lauryl sodium sulfate or potassium, sodium lauryl tri(oxyethyl) sulfate or potassium and undecenoic acid sodium or potassium one or more.
7. environmental friendliness dinotefuran micron-emulsion according to any one of claim 1 to 6, it is characterized in that, described non-ionic surface active agent is selected from one or more of 10 two to tetradecyl alchohol APEOs, 10 six to polyoxyethylene octadecanols, cocounut oil acid ester polyoxyethylene ether, oleate APEO, fatty acid esters of sorbitan APEO and castor oil polyoxyethylene ether.
8. environmental friendliness dinotefuran micron-emulsion according to any one of claim 1 to 7, is characterized in that, the ketones solvent of described boiling point more than 150 DEG C be selected from cyclohexanone, methyl cyclohexanone and methyln-hexyl ketone one or more.
9. environmental friendliness dinotefuran micron-emulsion according to any one of claim 1 to 8, is characterized in that, described defoamer is selected from tributyl phosphate, 6 ~ 8 carbon alcohol or silicone defoaming agents.
10. the preparation method of environmental friendliness dinotefuran micron-emulsion according to any one of claim 1 to 9, comprises the steps:
I. various raw material is prepared according to formula;
II. except ketones solvent more than 150 DEG C of MTI-446, boiling point and defoamer, water in formula and other raw material are added stirred tank, stir, make it dissolve, obtain solution A;
III. the ketones solvent of boiling point more than 150 DEG C is added another container, then add MTI-446, stir, make it dissolve, obtain solution B;
IV. solution B is joined in solution A, stir, become clear solution, then add defoamer, gentle agitation, static, filter, obtain dinotefuran micron-emulsion.
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| CN111513063A (en) * | 2020-05-14 | 2020-08-11 | 广东省科学院产业技术育成中心 | Insecticide additive and preparation method and application thereof |
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