CN102885034A - Microemulsion pesticide and preparation method thereof - Google Patents
Microemulsion pesticide and preparation method thereof Download PDFInfo
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- CN102885034A CN102885034A CN 201210367068 CN201210367068A CN102885034A CN 102885034 A CN102885034 A CN 102885034A CN 201210367068 CN201210367068 CN 201210367068 CN 201210367068 A CN201210367068 A CN 201210367068A CN 102885034 A CN102885034 A CN 102885034A
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Abstract
The invention discloses a microemulsion pesticide, comprising the following compositions in percentage by weight: 0.5-5% of technical material, 2-20% of cyclohexanone, 2-20% of dimethyl formamide, 1.5-20% of methanol, 1.5-4.5% of agricultural emulsion 700#, 1.5-4.5% of tristyryl phenol polyoxyethylene polyoxypropylene ether, 1.5-4.5% of agricultural emulsion 602#, 2-6% of nonylphenol polyoxyethylene ether, 2-6% of agricultural emulsion 404#, and the rest amount of water; and the technical material comprises one or two of abamectin, hexaflumuron, fipronil, profenofos, methomyl, carbosulfan monosultap, diafenthiuron, emamectin benzoate and matrine. The microemulsion pesticide and the preparation method thereof have the advantages that the application range is wide, the dosage form is stable, the formula is simple, and the production is convenient.
Description
Technical field
The present invention relates to a kind of insecticide, specifically a kind of microemulsion insecticide and preparation method thereof belongs to the microemulsion insecticide field.
Background technology
A large amount of uses along with agricultural chemicals have brought serious pollution to natural environment, have caused the common concern of the parties concerned.Particularly in today that environmental protection is day by day improved and is strict with, the cry that reduces pesticide pollution more and more adds strongly.The formulations of pesticide such as missible oil, pulvis have been brought into play important function in China's pesticide industry development course, in Pesticidal products, also occupy very large ratio, yet these fall behind formulation and have the fatal defectives such as environmental pollution is large, manufacturing cost is high, can not satisfy the demand of agricultural sustainable development.
Preparation Forms of Modern Pesticide is to water baseization, ultramicronising, without efflorescence and control release aspect development, i.e. the formulations of pesticide take water as matrix replace missible oil etc. to fall behind formulation such as water baseization pesticidal preparations such as suspending agent, microemulsion, aqueous emulsions.Wherein microemulsion be a kind of organic solvent can be less with in addition the novel pesticide formulation of no, good drug efficacy, environmentally-friendly water-basedization, also be the good liquid dosage form that a kind of alternative missible oil etc. falls behind formulation.
Microemulsion is comprised of liquid pesticide, surfactant, water, stabilizing agent etc., belong to thermodynamics through the time stable dispersion, mainly take water as medium, do not contain or contain less organic solvent, thereby do not fire not quick-fried, production operation, storing is safe, low in the pollution of the environment, saves a large amount of organic solvents; The pesticide dispersion degree is high, reaches the miniaturization degree, and the agricultural chemicals particle is generally 0.1～0.01 micron, and outward appearance is similar to transparent or sub-translucent liquid; Good dispersion in water is strong to the target body permeability, adhesive force good.
Yet the problems such as layering, crystallization, muddiness, floccule often appear in present microemulsion product in market, thereby have greatly affected the development of this formulation in technical field of pesticide.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, a kind of microemulsion insecticide and preparation method thereof is provided, after adding cyclohexanone, dimethyl formamide, methyl alcohol, Nongru-700 #, triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, agricultural newborn 602#, polyoxyethylene nonylphenol ether and agricultural newborn 404#, the product forms that obtains is stable, synergy is remarkable, and the preparation method is simple.
For addressing the above problem, the present invention by the following technical solutions:
A kind of microemulsion insecticide is grouped into by the one-tenth of following percetage by weight:
The former medicine of 0.5-5%, 2-20% cyclohexanone, 2-20% dimethyl formamide, 1.5-20% methyl alcohol, 1.5-4.5% Nongru-700 #, 1.5-4.5% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, the newborn 602# of 1.5-4.5% farming, 2-6% polyoxyethylene nonylphenol ether, the newborn 404# of 2-6% farming, water complementary;
Wherein, described former medicine is one or both in Avermectin, HEXAFLUMURON, ethiprole, Profenofos, Methomyl, carbosulfan, desinsection list, diafenthiuron, first dimension salt, the matrine.
Preferably, the one-tenth by following percetage by weight is grouped into:
3% former medicine, 10% cyclohexanone, 10% dimethyl formamide, 10% methyl alcohol, 3% Nongru-700 #, 3% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, 3% agricultural newborn 602#, 3% polyoxyethylene nonylphenol ether, 3% agricultural newborn 404#, water complementary.
Preferably, 3% former medicine is grouped into by the one-tenth of following percetage by weight: 0.5% Avermectin, 2.5% HEXAFLUMURON.
Avermectin is the natural materials from Soil Microorganism grey streptomycin.Wherein the strongest with the Bla composition activity, be that good antibiotic desinsection is hidden agent extremely from.Be characterized in the broad-spectrum high efficacy low-residual and to people and animals and Environmental security, stomach toxicity and the action of contace poison of insect hidden from agent without cross resistance extremely with chemistry commonly used again, thereby become one of present China suitability for industrialized production large-tonnage biopesticide.The desinsection list belongs to nereistoxin pesticide.It is extremely strong interior suction, stomach toxicity, tagging has the good bionical insecticide of stifling ovicidal action, noresidue concurrently.Avermectin mainly shields, and without systemic activity, and the longevity of residure is short, and the desinsection list has systemic action, and the longevity of residure is long.There is greatest differences in both chemical constitutions, and each self-applying rake mark is also different.The Avermectin Main Function suppresses neurotransmission in insect neurotransmitter GABA, and the desinsection list is the second phthalein choline competitive inhibitor of insect, makes the insect paralysis.The two is used with, and good preventive effect can be arranged, and can delay again the generation of insect pest resistance.
HEXAFLUMURON belongs to benzene first phthalein arteries and veins insecticide, is chitin synthesis inhibitor, has very high desinsection and ovicidal activity, and quick-acting, especially prevents and treats cotton bollworm, can be used for cotton, potato and fruit tree and prevents and treats multiple coleoptera, diptera, Homoptera insect.Existing much studies show that, this insecticide can also suppress insect food speed, therefore the power of knocking down is faster arranged when killing off the insect pests by suppressing to cast off a skin.The insecticidal activity of HEXAFLUMURON is high, and insect is difficult for developing immunity to drugs, and noresidue after using to crop safety, has no adverse effects to crop products.
Cyclohexanone, for carbonylic carbon atom is included in saturated cyclic ketones in the hexatomic ring, colourless transparent liquid is industrial main as organic synthesis raw material and solvent;
Dimethyl formamide, namely DMF is a kind of transparency liquid, energy and water and majority of organic solvent dissolve each other; In agricultural chemicals for the synthesis of the higher effective and lower toxic pesticide insecticide;
Methyl alcohol claims again " another name for " or " another name for ", is the colourless volatile liquid of alcohol smell that has, for the manufacture of formaldehyde and agricultural chemicals etc., and as the denaturant of organic extractant and alcohol etc.;
The triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, cas 99734-09-5, molecular formula C
30H
24O
.(C
2H
4O) N, model 1601 in the present invention as emulsifier and stabilizing agent, reduces resolution ratio;
Polyoxyethylene nonylphenol ether has another name called OP-10, and this product has good infiltration, emulsification, dispersion, antiacid, alkali resistant, anti-hard water, anti-reduction, oxidation resistance, in the present invention as emulsifier and stabilizing agent;
The preparation method of above-mentioned microemulsion insecticide may further comprise the steps:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first former medicine is joined in the agitator tank, again cyclohexanone, dimethyl formamide, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, agricultural newborn 602#, polyoxyethylene nonylphenol ether and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The invention has the advantages that:
1, applied widely: former medicine can adopt the materials such as Avermectin, HEXAFLUMURON, ethiprole, Profenofos, Methomyl, carbosulfan, desinsection list, diafenthiuron, first dimension salt, matrine;
2, formulation is stable: after adding cyclohexanone, dimethyl formamide, methyl alcohol, Nongru-700 #, triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, agricultural newborn 602#, polyoxyethylene nonylphenol ether and agricultural newborn 404#, store 60 ℃ of 90 days resolution ratios less than 1% in heat, cold storage-25 ℃ 90 days is not freezed non-crystallizable, and is higher than missible oil stability;
3 prescriptions are simple, convenient for production: only need an agitator tank, working condition requires low.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, is not intended to limit the present invention.
Except as otherwise noted, the percentage that adopts among the present invention is percetage by weight.
Embodiment 1
3% Avermectin HEXAFLUMURON microemulsion
0.5% Avermectin, 2.5% HEXAFLUMURON, 10% cyclohexanone, 10%DMF, 10% methyl alcohol, 3% Nongru-700 #, 3% agricultural newborn 1601#, 3% agricultural newborn 602#, 3% agricultural newborn OP-10,3% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first Avermectin, the former medicine of HEXAFLUMURON are joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 36%.
Embodiment 2
3% avermectin micro-emulsion
One-tenth by following percetage by weight is grouped into:
3% Avermectin, 10% cyclohexanone, 10%DMF, 10% methyl alcohol, 3% Nongru-700 #, 3% agricultural newborn 1601#, 3% agricultural newborn 602#, 3% agricultural newborn OP-10,3% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first the former medicine of Avermectin is joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 30%.
Embodiment 3
3% HEXAFLUMURON microemulsion
3% HEXAFLUMURON, 10% cyclohexanone, 10%DMF, 10% methyl alcohol, 3% Nongru-700 #, 3% agricultural newborn 1601#, 3% agricultural newborn 602#, 3% agricultural newborn OP-10,3% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first the former medicine of HEXAFLUMURON is joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 33%.
Embodiment 4
3% first dimension salt microemulsion
One-tenth by following percetage by weight is grouped into:
3% first dimension salt, 10% cyclohexanone, 10%DMF, 10% methyl alcohol, 3% Nongru-700 #, 3% agricultural newborn 1601#, 3% agricultural newborn 602#, 3% agricultural newborn OP-10,3% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first first is tieed up the former medicine of salt and joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 31%.
Embodiment 5
0.5% ethiprole microemulsion
One-tenth by following percetage by weight is grouped into:
0.5% ethiprole, 2% cyclohexanone, 20% dimethyl formamide, 1.5% methyl alcohol, 1.5% Nongru-700 #, 4.5% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, 1.5% agricultural newborn 602#, 6% polyoxyethylene nonylphenol ether, 2% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first the former medicine of ethiprole is joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 25%.
Embodiment 6
5% desinsection list microemulsion
One-tenth by following percetage by weight is grouped into:
5% desinsection list, 20% cyclohexanone, 2% dimethyl formamide, 20% methyl alcohol, 4.5% Nongru-700 #, 1.5% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, 4.5% agricultural newborn 602#, 2% polyoxyethylene nonylphenol ether, 6% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first the former medicine of desinsection list is joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 23%.
Embodiment 7
2% Methomyl microemulsion
One-tenth by following percetage by weight is grouped into:
2% Methomyl, 8% cyclohexanone, 8% dimethyl formamide, 14% methyl alcohol, 2.5 Nongru-700 #, 2.5% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, 2.5% agricultural newborn 602#, 3% polyoxyethylene nonylphenol ether, 3% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first the former medicine of Methomyl is joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 29%.
Embodiment 8
3.5% carbosulfan microemulsion
One-tenth by following percetage by weight is grouped into:
3.5% carbosulfan, 15% cyclohexanone, 15% dimethyl formamide, 6% methyl alcohol, 3.5 Nongru-700 #, 3.5% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, 3.5% agricultural newborn 602#, 4.5% polyoxyethylene nonylphenol ether, 4.5% agricultural newborn 404#, water complementary.
The preparation method:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first the former medicine of carbosulfan is joined in the agitator tank, again cyclohexanone, DMF, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, agricultural newborn 1601#, agricultural newborn 602#, agricultural newborn OP-10 and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
The result:
Be 0.1% in 60 ℃ of 90 days resolution ratios of heat storage, cold storage-25 ℃ 90 days is not freezed non-crystallizable;
Synergy is remarkable: by comparative trial, preparation of the present invention is compared with the insecticide of former medicine content with formulation with routine, and other condition is identical, and insecticidal effect increases by 27%.
Among each embodiment of the present invention, used chemical industry material is used material in the production of this area, all can obtain from market, and can not exert an influence for the production result; The equipment of using in each operation all adopts conventional equipment used in the current production, there is no special feature.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment the present invention is had been described in detail, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. microemulsion insecticide is grouped into by the one-tenth of following percetage by weight:
The former medicine of 0.5-5%, 2-20% cyclohexanone, 2-20% dimethyl formamide, 1.5-20% methyl alcohol, 1.5-4.5% Nongru-700 #, 1.5-4.5% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, the newborn 602# of 1.5-4.5% farming, 2-6% polyoxyethylene nonylphenol ether, the newborn 404# of 2-6% farming, water complementary;
Wherein, described former medicine is one or both in Avermectin, HEXAFLUMURON, ethiprole, Profenofos, Methomyl, carbosulfan, desinsection list, diafenthiuron, first dimension salt, the matrine.
2. microemulsion insecticide according to claim 1, it is characterized in that: the one-tenth by following percetage by weight is grouped into: 3% former medicine, 10% cyclohexanone, 10% dimethyl formamide, 10% methyl alcohol, 3% Nongru-700 #, 3% triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, 3% agricultural newborn 602#, 3% polyoxyethylene nonylphenol ether, 3% agricultural newborn 404#, water complementary.
3. microemulsion insecticide according to claim 2, it is characterized in that: described 3% former medicine is grouped into by the one-tenth of following percetage by weight: 0.5% Avermectin, 2.5% HEXAFLUMURON.
4. the preparation method of a microemulsion insecticide as claimed in claim 1 is characterized in that, may further comprise the steps:
(1) takes by weighing each raw material according to above-mentioned prescription;
(2) first former medicine is joined in the agitator tank, again cyclohexanone, dimethyl formamide, methyl alcohol are joined in the agitator tank, stirred 15-25 minute;
(3) Nongru-700 #, triphenyl vinyl phenol polyoxyethylene poly-oxygen propylene aether, agricultural newborn 602#, polyoxyethylene nonylphenol ether and agricultural newborn 404# are joined in the agitator tank of above-mentioned steps (2), stirred 20-30 minute, to fully dissolving;
(4) at last water is joined in the agitator tank of above-mentioned steps (3), stirred 25-30 minute, obtain formulation products.
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| CN 201210367068 CN102885034A (en) | 2012-09-28 | 2012-09-28 | Microemulsion pesticide and preparation method thereof |
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| CN 201210367068 CN102885034A (en) | 2012-09-28 | 2012-09-28 | Microemulsion pesticide and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104106565A (en) * | 2013-10-21 | 2014-10-22 | 曾立雄 | Novel water-emulsion type solvent capable of replacing xylene |
| CN107156115A (en) * | 2017-07-14 | 2017-09-15 | 安徽海日生物科技有限公司 | A kind of HEXAFLUMURON and emamectin-benzoate complex microemulsion and preparation method thereof |
| CN109566659A (en) * | 2018-12-21 | 2019-04-05 | 河北省农林科学院石家庄果树研究所 | A kind of pear tree insecticide and preparation method thereof |
-
2012
- 2012-09-28 CN CN 201210367068 patent/CN102885034A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104106565A (en) * | 2013-10-21 | 2014-10-22 | 曾立雄 | Novel water-emulsion type solvent capable of replacing xylene |
| CN107156115A (en) * | 2017-07-14 | 2017-09-15 | 安徽海日生物科技有限公司 | A kind of HEXAFLUMURON and emamectin-benzoate complex microemulsion and preparation method thereof |
| CN109566659A (en) * | 2018-12-21 | 2019-04-05 | 河北省农林科学院石家庄果树研究所 | A kind of pear tree insecticide and preparation method thereof |
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Application publication date: 20130123 |