CN101971802B - Chlorantraniliprole pesticidal microemulsion and preparation method thereof - Google Patents
Chlorantraniliprole pesticidal microemulsion and preparation method thereof Download PDFInfo
- Publication number
- CN101971802B CN101971802B CN 201010513752 CN201010513752A CN101971802B CN 101971802 B CN101971802 B CN 101971802B CN 201010513752 CN201010513752 CN 201010513752 CN 201010513752 A CN201010513752 A CN 201010513752A CN 101971802 B CN101971802 B CN 101971802B
- Authority
- CN
- China
- Prior art keywords
- rynaxypyr
- days
- microemulsion
- chlorantraniliprole
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000005886 Chlorantraniliprole Substances 0.000 title abstract description 11
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 title abstract description 11
- 230000000361 pesticidal Effects 0.000 title abstract description 8
- 238000000593 microemulsion method Methods 0.000 title description 3
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000010008 shearing Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 32
- -1 polyoxyethylene phosphate Polymers 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- ULUAUXLGCMPNKK-UHFFFAOYSA-L 2-sulfobutanedioate Chemical compound OS(=O)(=O)C(C([O-])=O)CC([O-])=O ULUAUXLGCMPNKK-UHFFFAOYSA-L 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- AXTGDCSMTYGJND-UHFFFAOYSA-N 1-dodecylazepan-2-one Chemical compound CCCCCCCCCCCCN1CCCCCC1=O AXTGDCSMTYGJND-UHFFFAOYSA-N 0.000 claims description 8
- LROWVYNUWKVTCU-STWYSWDKSA-M Sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 claims description 8
- 239000004283 Sodium sorbate Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 235000019250 sodium sorbate Nutrition 0.000 claims description 8
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 claims description 7
- GNSKLFRGEWLPPA-UHFFFAOYSA-M Monopotassium phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 7
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 7
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 7
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N Cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 206010018987 Haemorrhage Diseases 0.000 claims description 6
- 230000000740 bleeding Effects 0.000 claims description 6
- 231100000319 bleeding Toxicity 0.000 claims description 6
- WUIJQWLICXXNNE-UHFFFAOYSA-L disodium;octyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCOP([O-])([O-])=O WUIJQWLICXXNNE-UHFFFAOYSA-L 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 claims description 4
- 229940005550 Sodium alginate Drugs 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 4
- MSXHSNHNTORCAW-UHFFFAOYSA-M sodium 3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].OC1OC(C([O-])=O)C(O)C(O)C1O MSXHSNHNTORCAW-UHFFFAOYSA-M 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 3
- 150000007949 saponins Chemical class 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 19
- 239000000575 pesticide Substances 0.000 abstract description 11
- 241000238631 Hexapoda Species 0.000 abstract description 4
- 241000607479 Yersinia pestis Species 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 235000016068 Berberis vulgaris Nutrition 0.000 abstract description 2
- 241000335053 Beta vulgaris Species 0.000 abstract description 2
- 229920000742 Cotton Polymers 0.000 abstract description 2
- 235000013311 vegetables Nutrition 0.000 abstract description 2
- 230000000149 penetrating Effects 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 244000144972 livestock Species 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 47
- 241000500437 Plutella xylostella Species 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
- 241000982105 Brevicoryne brassicae Species 0.000 description 22
- 238000005303 weighing Methods 0.000 description 21
- 230000000749 insecticidal Effects 0.000 description 11
- 239000002917 insecticide Substances 0.000 description 9
- 239000003905 agrochemical Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- KWKXNDCHNDYVRT-UHFFFAOYSA-N Dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 5
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XXKHDSGLCLCFSC-UHFFFAOYSA-N 2,3-diphenylphenol Chemical compound C=1C=CC=CC=1C=1C(O)=CC=CC=1C1=CC=CC=C1 XXKHDSGLCLCFSC-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 230000000607 poisoning Effects 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 241000907661 Pieris rapae Species 0.000 description 2
- 241000256247 Spodoptera exigua Species 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 102000037170 ryanodine receptor (TC 1.A.3.1) family Human genes 0.000 description 2
- 108091006220 ryanodine receptor (TC 1.A.3.1) family Proteins 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241001147381 Helicoverpa armigera Species 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- 241001325860 Lacanobia oleracea Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- FJYTWSATJDPRNY-UHFFFAOYSA-N N-benzamidoformamide Chemical compound O=CNNC(=O)C1=CC=CC=C1 FJYTWSATJDPRNY-UHFFFAOYSA-N 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241000721451 Pectinophora gossypiella Species 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- 241000985245 Spodoptera litura Species 0.000 description 1
- 210000002784 Stomach Anatomy 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004920 integrated pest control Methods 0.000 description 1
- 230000003834 intracellular Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000003449 preventive Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Abstract
The invention discloses chlorantraniliprole pesticidal microemulsion and a preparation method thereof. The chlorantraniliprole pesticidal microemulsion comprises the following components in percentage by weight: 0.1 to 60 percent of chlorantraniliprole, 3 to 27 percent of emulsifier, 2 to 15 percent of penetrating agent, 1 to 10 percent of stabilizing agent, 2 to 40 percent of cosolvent and the balance of water. The preparation method comprises the following steps of: uniformly stirring and mixing the chlorantraniliprole and the emulsifier, the penetrating agent, the cosolvent and the stabilizing agent in a high-speed shearing machine, and adding deionized water, and uniformly stirring and mixing; standing for 5 to 13 hours, heating to the temperature of between 45 and 65 DEG C, and fully stirring to prepare the chlorantraniliprole pesticidal microemulsion. The chlorantraniliprole pesticidal microemulsion has obvious effect of controlling various insect pests of vegetables, beets, cotton and other crops. The microemulsion pesticide is safe to environment, people, livestock and other beneficial organisms, is hard to produce pesticide damage, has low cost, and is easy to prepare and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of agricultural chemical insecticide chlorantraniliprole pesticidal microemulsion and preparation method thereof, belong to technical field of pesticide.
Background technology
Chemical pesticide is that agricultural foison has been made very large contribution, yet has also brought more serious pollution to natural environment, and this has caused people's common concern.Particularly in today that environmental regulation becomes better and approaching perfection day by day and is strict with, the cry that reduces pesticide pollution more and more adds strongly.In recent years, in countries such as the U.S., to an organic solvent restriction increasingly stringent, some national dimethylbenzene has disabled trend in the pesticidal preparations.Therefore, develop high safety, environmental protection and cheap novel liquid formulation have become the trend of the times of Agrochemicals to reduce or eliminate these harmful organic solvents.Wherein, Water-borne modification is exactly one of dominant direction of formulations of pesticide development, and pesticides new formulation also can increase New Characteristics to agricultural chemicals, more can give full play to the function Characteristics of former medicine self, overcome and remedy the deficiency of the original formulation of agricultural chemicals, all lower to people and animals' toxicity and excitant, and can alleviate poisoning to crop, improve physico chemistry and biological property, enlarge range of application, prolong the service life of medicament etc.
Microemulsion is a kind of environmentally friendly novel form in the formulations of pesticide, it is by the solubilization of surfactant, the organic solvent solution of liquid or solid agricultural chemicals is dispersed in formation optical clear or translucent dispersion in the water, have physics, chemical stability is good, absorption ratio is high, preventive effect is good, the active ingredient dispersity is high, produce store and use safety, environmental pollution is little, cost is low, the drug effect high.This formulation oil bead diameter is 10～100nm, uses no or little organic solvent, not only saves a large amount of organic solvents, and has greatly alleviated the pressure to environment, and is significant for protection Agro-ecology balance, more is conducive to the sustainable development of agricultural.
Rynaxypyr (chlorantraniliprole), chemical name is for being 3-bromo-N-{4-chloro-2-methyl-6-[(methylamino) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, be a kind of Novel ortho formamido benzamide insecticides that du pont company develops.This insecticide is insect ryanodine receptor inhibitor, mainly discharges by the intracellular calcium ion of inducing the regulation and control of insect ryanodine receptor to show insecticidal action [" world pesticide ", 2007,29 (5): 6～10].Rynaxypyr has tags and stomach poison function, show efficient, wide spectrum, the characteristics such as holding effect and mechanism of action novelty, can be used for preventing and treating multiple lepidoptera pest, other commercialization insecticide varieties that its control efficiency obviously is better than using in the current production, there is not cross resistance in other insecticides, and to natural enemy insect safety, can be used for integrated pest management and resistance management, be used in vegetables, beet, the crops such as cotton prevent and treat various pests, such as beet armyworm (Spodoptera exigua), tomato moth (Spodoptera litura), diamond-back moth (Plutella xylostella), imported cabbageworm (Pieris rapae), cotton bollworm (Heliothis armigera), pink bollworm (Peatinophora gossypiella) etc. has good control efficiency to each instar larvae.Rynaxypyr is described as efficient pesticides of new generation in the world.The Rynaxypyr product is mainly suspending agent in the market.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of have desinsection wide spectrum, high-efficiency low-toxicity are provided, can satisfy the field and use needs, and the novel agrochemical insecticide Rynaxypyr microemulsion with environmental friendliness characteristics.
Another object of the present invention provides the preparation method of the Rynaxypyr microemulsion of the advantages such as former medicine availability is high, preparation technology is simple, production cost is relatively low.
The present invention is take Rynaxypyr as former medicine, and research and development are efficient, the novel Rynaxypyr microemulsion insecticide of low toxicity, cheap, environmental protection.
To achieve these objectives, the technical solution used in the present invention is:
A kind of Rynaxypyr microemulsion, the percentage by weight of each component is in the prescription: Rynaxypyr 0.1-60%, emulsifier 3-27%, bleeding agent 2-15%, stabilizing agent 1-10%, cosolvent 2-40%, deionized water 15-79%.
Described emulsifier is one or more in alkylbenzene naphthalene sulfonate, alkylphenol polyoxyethylene phosphate, diphenyl phenol polyethenoxy polyethenoxy ether, styrenated phenol APEO, sodium dodecyl aminopropionitrile, sodium alginate, natural carboxylates, polyoxyethylene groups styrene phenolic group ether and the Tea Saponin.
Described bleeding agent is one or more in sulfosuccinate di-sec-octyl sodium salt, octyl phosphate sodium salt and the azone.
Described cosolvent is one or more in ethanol, n-butanol, ethylene glycol, propane diols, glycerine, acetone, cyclohexanone, pyrrolidones and the ethyl acetate.
Described stabilizing agent is urea, potassium dihydrogen phosphate, sodium sorbate, 3-chloro-1, one or more in 2-expoxy propane, benzinum and the cresyl glycidyl ether.
The compound method of described insecticide Rynaxypyr microemulsion, after comprising the steps: first Rynaxypyr and emulsifier, bleeding agent, cosolvent, stabilizing agent mixed in high-speed shearing machine, add again deionized water, mix, then left standstill 5-13 hour, be heated to 45-65 ℃, after fully stirring, namely can be made into the Rynaxypyr microemulsion.
The present invention becomes a kind of new Rynaxypyr microemulsion with the former medicine preparation of Rynaxypyr, for pesticide field provides a kind of agricultural chemical insecticide with higher insecticidal activity and better environment compatibility.Compared with prior art, the Rynaxypyr microemulsion has following outstanding advantages: nano level emulsion particle, and utilization rate of active components is high; The organic solvent usage amount reduces, and is environmentally friendly, and flash-point is high, produces, stores, uses safety; To environment, people and animals and other beneficial organism safety, be difficult for producing poisoning; Have good stability, with low cost, preparation technology is simpler, is appropriate to the scale of chemical production.
Embodiment
For a better understanding of the present invention, the invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1: take by weighing Rynaxypyr 0.1kg, then after mixing in high-speed shearing machine with alkylphenol polyoxyethylene phosphate 4.0kg, sulfosuccinate di-sec-octyl sodium salt 4.5kg, ethyl acetate 14.0kg and urea 2.0kg, add deionized water 75.4kg, mix, left standstill 5 hours, be heated to 45 ℃, after fully stirring, namely can be made into 0.1% Rynaxypyr microemulsion.Use 500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 90.8%, 91.7% and 88.1%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 91.1%, 92.9% and 90.3%.
Embodiment 2: take by weighing Rynaxypyr 60.0kg, then after mixing in high-speed shearing machine with natural carboxylates 3.0kg, alkylphenol polyoxyethylene phosphate 2.0kg, sodium dodecyl aminopropionitrile 4.5kg, sulfosuccinate di-sec-octyl sodium salt 3.5kg, ethylene glycol 5.0kg and potassium dihydrogen phosphate 2.0kg, add deionized water 20.0kg, mix, left standstill 9 hours, be heated to 55 ℃, after fully stirring, namely can be made into 60% Rynaxypyr microemulsion.Use 4000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 95.8%, 96.7% and 89.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 97.1%, 97.9% and 96.3%.
Embodiment 3: take by weighing Rynaxypyr 15.0kg, then after mixing in high-speed shearing machine with sodium dodecyl aminopropionitrile 4.5kg, sulfosuccinate di-sec-octyl sodium salt 4.0kg, octyl phosphate sodium salt 2.5kg, ethyl acetate 4.0kg and sodium sorbate 3.0kg, add deionized water 67.0kg, mix, left standstill 5 hours, be heated to 47 ℃, after fully stirring, namely can be made into 15% Rynaxypyr microemulsion.Use 1500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 92.8%, 93.7% and 89.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 94.1%, 95.9% and 93.3%.
Embodiment 4: take by weighing Rynaxypyr 20.0kg, then after mixing in high-speed shearing machine with polyoxyethylene groups styrene phenolic group ether 6.0kg, sodium dodecyl aminopropionitrile 5.0kg, azone 4.5kg, ethyl acetate 4.0kg and sodium sorbate 3.5kg, add at last deionized water 57.0kg, mix, left standstill 8 hours, be heated to 49 ℃, after fully stirring, namely can be made into 20% Rynaxypyr microemulsion.Use 2000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 93.5%, 94.6% and 90.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 94.8%, 95.6% and 93.5%.
Embodiment 5: take by weighing Rynaxypyr 25.0kg, then after mixing in high-speed shearing machine with alkylbenzene naphthalene sulfonate 2.0kg, polyoxyethylene groups styrene phenolic group ether 7.0kg, sodium dodecyl aminopropionitrile 4.0kg, octyl phosphate sodium salt 3.5kg, ethyl acetate 3.0kg and benzinum 3.5kg, add at last deionized water 52.0kg, mix, left standstill 7 hours, be heated to 51 ℃, after fully stirring, namely can be made into 25% Rynaxypyr microemulsion.Use 2000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 93.9%, 95.5% and 91.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 95.8%, 96.6% and 94.5%.
Embodiment 6: take by weighing Rynaxypyr 32.0kg, then with polyoxyethylene groups styrene phenolic group ether 5.5kg, styrenated phenol APEO 5.0kg, sulfosuccinate di-sec-octyl sodium salt 3.0kg, ethyl acetate 3.0kg, ethylene glycol 3.0kg and 3-chloro-1, after 2-expoxy propane 2.5kg mixes in high-speed shearing machine, add at last deionized water 46.0kg, mix, left standstill 9 hours, be heated to 47 ℃, after fully stirring, namely can be made into 32% Rynaxypyr microemulsion.Use 2500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 92.9%, 94.5% and 91.5%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 94.8%, 95.6% and 94.0%.
Embodiment 7: take by weighing Rynaxypyr 45.0kg, then after mixing in high-speed shearing machine with castor oil ethylene oxide adduct 2.0kg, alkylbenzene naphthalene sulfonate 2.0kg, sodium dodecyl aminopropionitrile 3.0kg, sulfosuccinate di-sec-octyl sodium salt 2.5kg, cyclohexanone 2.5kg and cresyl glycidyl ether 1.5kg, add at last deionized water 41.5kg, mix, left standstill 8 hours, be heated to 57 ℃, after fully stirring, namely can be made into 45% Rynaxypyr microemulsion.Use 3000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 94.9%, 95.8% and 91.0%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 95.2%, 96.0% and 94.1%.
Embodiment 8: take by weighing Rynaxypyr 48.5kg, then after mixing in high-speed shearing machine with alkylbenzene naphthalene sulfonate 2.0kg, sodium dodecyl aminopropionitrile 2.5kg, cyclohexanone 2.0kg, azone 4.0kg, ethylene glycol 2.5kg and cresyl glycidyl ether 2.5kg, add at last deionized water 36.0kg, mix, left standstill 10 hours, be heated to 58 ℃, after fully stirring, namely can be made into 48.5% Rynaxypyr microemulsion.Use 3000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 95.1%, 96.7% and 94.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 96.9%, 97.8% and 94.6%.
Embodiment 9: take by weighing Rynaxypyr 39.0kg, then with polyoxyethylene groups styrene phenolic group ether 4.5kg, sodium dodecyl aminopropionitrile 3.0kg, sulfosuccinate di-sec-octyl sodium salt 3.0kg, ethyl acetate 3.0kg, glycerine 2.0kg and 3-chloro-1, after 2-expoxy propane 2.5kg mixes in high-speed shearing machine, add at last deionized water 43.0kg, mix, left standstill 13 hours, be heated to 51 ℃, after fully stirring, namely can be made into 39% Rynaxypyr microemulsion.Use 3000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 90.9%, 92.5% and 89.5%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 92.6%, 93.4% and 93.0%.
Embodiment 10: take by weighing Rynaxypyr 10.0kg, then after mixing in high-speed shearing machine with sodium alginate 4.5kg, sulfosuccinate di-sec-octyl sodium salt 3.5kg, ethyl acetate 9.0kg and cresyl glycidyl ether 3.0kg, add at last deionized water 70.0kg, mix, left standstill 9 hours, be heated to 65 ℃, after fully stirring, namely can be made into 10% Rynaxypyr microemulsion.Use 1000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 95.8%, 96.7% and 90.1%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 96.7%, 97.5% and 96.3%.
Embodiment 11: take by weighing Rynaxypyr 22.5kg, then after mixing in high-speed shearing machine with styrenated phenol APEO 4.0kg, sodium dodecyl aminopropionitrile 4.5kg, sulfosuccinate di-sec-octyl sodium salt 3.5kg, ethanol 2.0kg, n-butanol 2.5kg and potassium dihydrogen phosphate 2.5kg, add at last deionized water 58.5kg, mix, left standstill 10 hours, be heated to 61 ℃, after fully stirring, namely can be made into 22.5% Rynaxypyr microemulsion.Use 2000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 95.8%, 96.7% and 89.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 97.1%, 97.9% and 96.3%.
Embodiment 12: take by weighing Rynaxypyr 30.0kg, then after mixing in high-speed shearing machine with diphenyl phenol polyethenoxy polyethenoxy ether 5.0kg, sodium dodecyl aminopropionitrile 4.5kg, sulfosuccinate di-sec-octyl sodium salt 4.0kg, acetone 3.0kg, cyclohexanone 2.5kg, sodium sorbate 3.0kg and potassium dihydrogen phosphate 1.5kg, add at last deionized water 46.5kg, mix, left standstill 6 hours, be heated to 47 ℃, after fully stirring, namely can be made into 30% Rynaxypyr microemulsion.Use 2000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 94.8%, 95.7% and 93.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 96.1%, 97.9% and 94.3%.
Embodiment 13: take by weighing Rynaxypyr 35.0kg, then after mixing in high-speed shearing machine with sodium dodecyl aminopropionitrile 6.5kg, azone 5.5kg, pyrrolidones 4.0kg and sodium sorbate 3.5kg, add at last deionized water 45.5kg, mix, left standstill 8 hours, be heated to 48 ℃, after fully stirring, namely can be made into 35% Rynaxypyr microemulsion.Use 2500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 93.5%, 94.6% and 90.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 94.8%, 95.6% and 93.5%.
Embodiment 14: take by weighing Rynaxypyr 40.5kg, then after mixing in high-speed shearing machine with castor oil ethylene oxide adduct 2.5kg, polyoxyethylene groups styrene phenolic group ether 6.0kg, octyl phosphate sodium salt 2.5kg, glycerine 3.0kg and benzinum 2.5kg, add at last deionized water 43.0kg, mix, left standstill 9 hours, be heated to 55 ℃, after fully stirring, namely can be made into 40.5% Rynaxypyr microemulsion.Use 3000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 92.9%, 94.5% and 91.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 94.8%, 95.6% and 93.5%.
Embodiment 15: take by weighing Rynaxypyr 42.0kg, then after mixing in high-speed shearing machine with styrenated phenol APEO 7.0kg, sulfosuccinate di-sec-octyl sodium salt 3.0kg, ethyl acetate 2.0kg, propane diols 1.5kg, urea 2.5kg and potassium dihydrogen phosphate 1.5kg, add at last deionized water 40.5kg, mix, left standstill 11 hours, be heated to 57 ℃, after fully stirring, namely can be made into 42% Rynaxypyr microemulsion.Use 2500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 93.5%, 95.4% and 92.5%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 95.0%, 95.9% and 94.5%.
Embodiment 16: take by weighing Rynaxypyr 29.0kg, then after mixing in high-speed shearing machine with sodium dodecyl aminopropionitrile 10.0kg, sulfosuccinate di-sec-octyl sodium salt 3.0kg, ethanol 12.5kg and benzinum 2.5kg, add at last deionized water 43.0kg, mix, left standstill 7 hours, be heated to 55 ℃, after fully stirring, namely can be made into 29% Rynaxypyr microemulsion.Use 2000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 94.7%, 95.9% and 91.3%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 95.5%, 96.4% and 94.6%.
Embodiment 17: take by weighing Rynaxypyr 11.5kg, then after mixing in high-speed shearing machine with sodium dodecyl aminopropionitrile 2.5kg, ethyl acetate 3.0kg, azone 3.0kg, benzinum 2.5kg and cresyl glycidyl ether 2.5kg, add at last deionized water 75.0kg, mix, left standstill 5 hours, be heated to 50 ℃, after fully stirring, namely can be made into 11.5% Rynaxypyr microemulsion.Use 1500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 90.1%, 91.7% and 89.6%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 93.9%, 94.8% and 92.6%.
Embodiment 18: take by weighing Rynaxypyr 18.5kg, then after mixing in high-speed shearing machine with polyoxyethylene groups styrene phenolic group ether 4.5kg, sodium dodecyl aminopropionitrile 3.0kg, sulfosuccinate di-sec-octyl sodium salt 3.5kg, ethyl acetate 3.0kg and sodium sorbate 2.5kg, add at last deionized water 65.0kg, mix, left standstill 13 hours, be heated to 55 ℃, after fully stirring, namely can be made into 18.5% Rynaxypyr microemulsion.Use 1500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 93.9%, 94.8% and 90.5%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 95.6%, 96.4% and 94.0%.
Embodiment 19: take by weighing Rynaxypyr 12.0kg, then with alkylbenzene naphthalene sulfonate 7.5kg, sodium dodecyl aminopropionitrile 10.0kg, styrenated phenol APEO 9.5kg, sulfosuccinate di-sec-octyl sodium salt 3.5kg, octyl phosphate sodium salt 8.0kg, azone 3.5kg, ethanol 5.0kg, n-butanol 3.0kg, ethylene glycol 3.0kg, urea 3.5kg, after potassium dihydrogen phosphate 4.0kg and sodium sorbate 2.5kg mix in high-speed shearing machine, add at last deionized water 25.0kg, mix, left standstill 8 hours, be heated to 45 ℃, after fully stirring, namely can be made into 12% Rynaxypyr microemulsion.Use 1000 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 92.9%, 93.8% and 91.5%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 93.6%, 94.4% and 92.8%.
Embodiment 20: take by weighing Rynaxypyr 5.0kg, then with sodium alginate 11.0kg, diphenyl phenol polyethenoxy polyethenoxy ether 9.0kg, natural carboxylates 7.0kg, sulfosuccinate di-sec-octyl sodium salt 2.0kg, propane diols 15.0kg, glycerine 13.0kg, acetone 12.0kg, 3-chloro-1,2-expoxy propane 2.5kg, after benzinum 3.5kg and cresyl glycidyl ether 4.0kg mix in high-speed shearing machine, add at last deionized water 16.0kg, mix, left standstill 6 hours, be heated to 50 ℃, after fully stirring, namely can be made into 5% Rynaxypyr microemulsion.Use 700 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 93.1%, 94.2% and 90.1%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 93.5%, 95.6% and 94.1%.
Embodiment 21: take by weighing Rynaxypyr 2.0kg, then after mixing in high-speed shearing machine with Tea Saponin 10.0kg, polyoxyethylene groups styrene phenolic group ether 5.0kg, alkylphenol polyoxyethylene phosphate 6.0kg, azone 2.0kg, cyclohexanone 15.0kg, pyrrolidones 9.0kg, ethyl acetate 10.0kg and benzinum 3.5kg, add at last deionized water 37.5kg, mix, left standstill 5 hours, be heated to 40 ℃, after fully stirring, namely can be made into 2% Rynaxypyr microemulsion.Use 500 times of liquid of said preparation to carry out field control effectiveness test, control efficiency to the 4th day, 8 days and 12 days after the medication of vegetable-crop pest-insect diamond-back moth is respectively 92.6%, 93.5% and 90.8%, and the control efficiency of the 5th day, 10 days and 15 days after the cabbage aphid medication is respectively 93.5%, 95.3% and 94.2%.
Above-described embodiment shows, Rynaxypyr microemulsion of the present invention is remarkable to pest controling effects such as vegetable-crop pest-insect diamond-back moth and cabbage aphids, and this microemulsion has overcome the shortcomings such as environmental pollution that the Traditional Agricultural pharmaceutically dosage forms such as missible oil are brought take water as matrix, to environment, people and animals and other beneficial organism safety, be difficult for producing poisoning.Chlorantraniliprole microemulsion flash-point of the present invention is high, produces, stores, uses safety, has good stability, and with low cost, preparation technology is simpler, is appropriate to the scale of chemical production and large scale application.
Claims (2)
1. Rynaxypyr microemulsion, it is characterized in that: by weight percentage, its composition of raw materials consists of: Rynaxypyr 0.1-60%, emulsifier 3-27%, bleeding agent 2-15%, stabilizing agent 1-10%, cosolvent 2-40% and deionized water 15-79%;
Described emulsifier is one or more in alkylphenol polyoxyethylene phosphate, styrenated phenol APEO, sodium dodecyl aminopropionitrile, sodium alginate, natural carboxylates, polyoxyethylene groups styrene phenolic group ether and the Tea Saponin;
Described bleeding agent is one or more in sulfosuccinate di-sec-octyl sodium salt, octyl phosphate sodium salt and the azone;
Described cosolvent is one or more in ethanol, n-butanol, ethylene glycol, propane diols, glycerine, acetone, cyclohexanone, pyrrolidones and the ethyl acetate;
Described stabilizing agent is urea, potassium dihydrogen phosphate, sodium sorbate, 3-chloro-1, one or more in 2-expoxy propane, benzinum and the cresyl glycidyl ether.
2. the compound method of the described Rynaxypyr microemulsion of claim 1, it is characterized in that: after first Rynaxypyr, emulsifier, bleeding agent, cosolvent and stabilizing agent being mixed in high-speed shearing machine, add again deionized water, mix, then left standstill 5-13 hour, be heated to 45-65 ℃, after fully stirring, namely can be made into the Rynaxypyr microemulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010513752 CN101971802B (en) | 2010-10-20 | 2010-10-20 | Chlorantraniliprole pesticidal microemulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010513752 CN101971802B (en) | 2010-10-20 | 2010-10-20 | Chlorantraniliprole pesticidal microemulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101971802A CN101971802A (en) | 2011-02-16 |
| CN101971802B true CN101971802B (en) | 2013-04-17 |
Family
ID=43571738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010513752 Expired - Fee Related CN101971802B (en) | 2010-10-20 | 2010-10-20 | Chlorantraniliprole pesticidal microemulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101971802B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105360139A (en) * | 2015-12-14 | 2016-03-02 | 济南舜昊生物科技有限公司 | Insecticidal composition containing benclothiaz and chlorantraniliprole |
| CN109463382B (en) * | 2018-10-10 | 2021-06-22 | 安徽久易农业股份有限公司 | Insecticidal nano-emulsion taking tea saponin as surfactant and preparation method thereof |
| CN113367144A (en) * | 2021-06-09 | 2021-09-10 | 浙江省亚热带作物研究所 | Compound preparation of N6- (2-hydroxyethyl) adenosine and chlorantraniliprole |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951189A (en) * | 2006-11-14 | 2007-04-25 | 华南理工大学 | Kresoxim-methyl microemulsion and preparation method thereof |
| CN101779640A (en) * | 2009-01-20 | 2010-07-21 | 江苏扬农化工股份有限公司 | Pesticidal composite |
-
2010
- 2010-10-20 CN CN 201010513752 patent/CN101971802B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951189A (en) * | 2006-11-14 | 2007-04-25 | 华南理工大学 | Kresoxim-methyl microemulsion and preparation method thereof |
| CN101779640A (en) * | 2009-01-20 | 2010-07-21 | 江苏扬农化工股份有限公司 | Pesticidal composite |
Non-Patent Citations (4)
| Title |
|---|
| 徐尚成等.新杀虫剂氯虫苯甲酰胺及其研究开发进展.《现代农药》.2008,第7卷(第5期),8-11. |
| 新杀虫剂氯虫苯甲酰胺及其研究开发进展;徐尚成等;《现代农药》;20081031;第7卷(第5期);8-11 * |
| 无.氯虫苯甲酰胺.《农药科学与管理》.2009,第30卷(第6期),57-58. |
| 氯虫苯甲酰胺;无;《农药科学与管理》;20091231;第30卷(第6期);57-58 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101971802A (en) | 2011-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101743969B (en) | Mixed insecticide of tea saponin and neonicotine insecticide | |
| CN101743967B (en) | Mixed insecticide of tea saponin and carbamate insecticide | |
| CN103300019B (en) | Pesticidal composition | |
| CN104012527B (en) | Chlorpyrifos micro emulsion and application thereof | |
| CN101755752B (en) | Pesticide by mixing tea saponin with pyrrole and pyrazole pesticide | |
| CN101971802B (en) | Chlorantraniliprole pesticidal microemulsion and preparation method thereof | |
| CN102365958A (en) | Synergistic insecticidal composition containing rotenone and emamectin benzoate | |
| CN101755821B (en) | Pesticide by mixing tea saponin with thepyrethroid pesticide | |
| CN101743968B (en) | Mixed insecticide of tea saponin and organophosphate insecticide | |
| CN102599167A (en) | Chlorantraniliprole and Spinetoram compound suspending agent and preparation method thereof | |
| CN101507438A (en) | Emamectin-benzoate aqueous emulsion | |
| CN101933509A (en) | Methylamino abamectin benzoate micro-emulsion serving as agricultural insecticide and preparation method | |
| CN102047884A (en) | Aconitine plant source insecticidal micro emulsion and preparation method thereof | |
| CN102228056B (en) | Pesticide composition containing sulfur-fluorine oxime ether and part of organophosphorus pesticides | |
| CN101961009B (en) | Flubendiamide insecticidal microemulsion and preparation method thereof | |
| CN101288409A (en) | Fipronil, chlopyrifos and production method thereof | |
| CN100426964C (en) | Micellar emulsion prepared by mixing Kresoxim and jinggangmycin and preparation method | |
| CN101449680A (en) | Emamectin benzoate microemulsion and its preparation method | |
| CN102210320A (en) | Sulfoxaflor-containing insecticidal composition | |
| CN102524276A (en) | Chlorantraniliprole and emamectin benzoate compounded suspending agent and preparation method thereof | |
| CN101971866B (en) | Chlorantraniliprole and natural pyrethrin compound insecticidal microemulsion and preparation method thereof | |
| CN101971832A (en) | Compounded pesticidal microemulsion of chlorantraniliprole and rotenone and preparation method thereof | |
| CN100450357C (en) | Kresoxim-methyl and nimbin mixed microemulsion and preparation method thereof | |
| CN103125501A (en) | Abamectin-spinosad emulsion in water and preparing method thereof | |
| CN102550573B (en) | Chlorantraniliprole and rotenone compound suspending agent and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130417 Termination date: 20151020 |
|
| EXPY | Termination of patent right or utility model |