CN1528143A - Composition containing non-fatty oxime ether pyrethrin insecticide - Google Patents
Composition containing non-fatty oxime ether pyrethrin insecticide Download PDFInfo
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Abstract
The present invention discloses a composite containing non-ester oximoetofenprox pesticide, in particula it is a pesticid composite containing insecticidal activity compound 1-(2-methylthio)-para-chlorophenylacetoxime-chloro-(3- phenoxybenzyl) ether (code name HNPC-A9908). Said invented composite is made up by using HNPC-A9908 or HNPC-A9908 and adding one known pesticide, organic solvent, surfactant, cold-resisting agent, preservative, thickening agent, carrier and water. Said pesticide composite can be used for controlling various injurious insects of rice, vegetable, tea tree and cotton, etc.
Description
Technical field the present invention relates to a kind of non-fatty oxime ether pyrethrin insecticide composition that contains, especially a kind of composition that contains insecticidal active compound 1-(2-methyl mercapto)-rubigan acetoxime-chloro-(3-phenoxy benzyl) ether (code name HNPC-A9908).
Background technology 1-(2-methyl mercapto)-rubigan acetoxime-chloro-(3-phenoxy benzyl) ether (code name HNPC-A9908) is the noval chemical compound with obvious insecticidal activity of Hunan Chemical Research Institute's invention, has applied for patent of invention (application number 99115557.2) on September 10th, 1999 to China Intellectual Property Office.The chemical structural formula of 1-(2-methyl mercapto)-rubigan acetoxime-chloro-(3-phenoxy benzyl) ether (code name HNPC-A9908) is:
The pure product fusing point of this compound is 27.3 ℃～27.7 ℃, dissolves in most of organic solvents.This compound insecticidal spectrum is wide, effect rapidly, toxicity is low, good to natural enemy and crop safety, Environmental compatibility, at present still not single agent of this compound and with the mixture of other agricultural chemicals.
Summary of the invention the purpose of this invention is to provide that a kind of to contain insecticidal active compound 1-(2-methyl mercapto)-rubigan acetoxime-chloro-(3-phenoxy benzyl) ether be insecticides and the preparation method of HNPC-A9908.
The present composition is that HNPC-A9908 or HNPC-A9908 add a kind of known agricultural chemicals, organic solvent, surfactant, antifreeze, preservative, thickener, carrier or water and form jointly by insecticidal active compound 1-(2-methyl mercapto)-rubigan acetoxime-chloro-(3-phenoxy benzyl) ether.The organic solvent that the present composition is selected for use is any or several mixture of cyclohexanone, benzene, methyl alcohol, dimethylbenzene, toluene etc.; The surfactant of selecting for use is one or more in BY series, EL series, 0204C, 0201c, 0203b, T-11,1601,1602,600,601,2000,0206b, No. 500, lignin and derivative sulfonate thereof etc.; The antifreeze of selecting for use is an ethylene glycol; The preservative of selecting for use is formaldehyde, benzoic acid; The thickener of selecting for use is the natural thickener xanthans; The carrier of selecting for use is one or more in white carbon, kaolin, the precipitated calcium carbonate; The water of selecting for use is deionized water; The known agricultural chemicals of selecting for use is any in diazinon, pirimiphos-methyl, malathion, sumithion, chlopyrifos, Bassa, carbaryl, unden, Mobucin etc., cypermethrin, sumicidin, dimehypo, desinsection list, fine, the sharp strength spy of bromine worm, the cartap.The percetage by weight that the present composition is formed is HNPC-A9908 1%-30%, known agricultural chemicals 0%-50%, organic solvent 0%-80%, surfactant 1%-20%, antifreeze 0%-5%, preservative 0%-5%, thickener 0%-3%, carrier 0-90%, water 0%-90%.
The present composition except that water formulation, but all can adopt the conventional preparation method of preparations such as emulsifiable concentrates for agricultural chemicals wet-milling to make.
Water formulation of the present invention is preparation like this: take by weighing all raw materials by prescription earlier, with HNPC-A9908 that weighs up or the mixture that adds another known agricultural chemicals, add a small amount of solvent, surfactant dissolves then again, stir and obtain even oil phase; Also can be with the mixture of HNPC-A9908 or HNPC-A9908 and another known agricultural chemicals, use the surfactant fusion, stirring obtains oil phase, then water, preservative, antifreeze are mixed, form the homogeneous water, under normal temperature and high-speed stirred, oil phase is joined water or water joins oil phase, form finely disseminated aqueous emulsion, measure the product average grain diameter that obtains below 20.00 microns with the particle size distribution test instrument.The mixing speed that the present invention selects is 200 rev/mins-2000 rev/mins; Mixing time is 3-20 minute.
Aqueous emulsion belongs to the pesticides new formulation scope.It is to be dissolved in water-fast organic solvent by water-fast original liquid body or former medicine solid, a kind of pesticidal preparations that the liquid dispersion of gained forms in water, and outward appearance is an opaque and white emulsion.Because poor or do not contain organic solvent in the aqueous emulsion of the present invention, no unpleasant toxic odor, nonflammable explosive, safe in utilization, reduced pollution to soil and environment, improved greatly and stored and transported and user's safety producing.
The present invention has good stability, and the characteristics that toxicity is low can effectively be prevented and kill off cabbage caterpillar, tea geometrid, tea caterpillar, smaller green leaf hopper, mythimna separata, rice leafhopper, rice fulgorid, cotton bollworm, to natural enemy and crop safety.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Take by weighing HNPC-A9908 5.6 grams, chlorfenapyr 5.1 grams, HNPC-A9908 is mixed with chlorfenapyr, add Emulsifier EL-40 8 gram, No. 500 4 grams and solvent cyclohexanone 8 grams then and form oil phases, formaldehyde 0.1 gram, xanthans 0.5 gram, water 68.7 grams are mixed the formation water, under the stirring of normal temperature and 1200 rev/mins, pour water into oil phase, stirred 5 minutes, and obtained finely disseminated aqueous emulsion.
Embodiment 2
Take by weighing HNPC-A9908 10.2 gram, dimethylbenzene 15 grams, EL-20 12 grams, ethylene glycol 3 grams, benzoic acid 0.1 gram, water is mended to 100 grams and is obtained milky aqueous emulsion product.The preparation method is with embodiment 1.
Embodiment 3
Take by weighing HNPC-A9908 5.2 gram, carbosulfan 20 grams, 0204B 10 grams, toluene 64.8 grams and obtain faint yellow missible oil product.
Embodiment 4
Take by weighing HNPC-A9908 10.2 gram, 0206B 12 grams, diazinon 40.1 grams, benzene 37.7 grams and obtain faint yellow missible oil product.
Embodiment 5-18
| The embodiment numbering | Composition is formed |
| ????5 | HNPC-A9908 10.3 grams, chlopyrifos 20.1 grams, 1,601 6.0 grams, No. 500 4.0 grams, dimethylbenzene are mended to 100 grams |
| ????6 | HNPC-A9908 5.1 grams, malathion 20.4 grams, T-11 8.1 grams, No. 500 2.5 grams, toluene are mended to 100 grams |
| ????7 | HNPC-A9908 10.1 grams, sumithion 20.4 grams, No. 2,000 8 grams, dimethylbenzene are mended to 100 grams |
| ????8 | HNPC-A9908 5.0, Bassa 20.3 grams, 0201c 10 grams, toluene are mended to 100 grams |
| ????9 | HNPC-A9908 5.2 grams, unden 20.4 grams, 0203a 10 grams, benzene are mended to 100 grams |
| ????10 | HNPC-A9908 5.4 grams, cypermethrin 5.1 grams, 0204b 10 grams, dimethylbenzene are mended to 100 grams |
| ????11 | HNPC-A9908 5.2 grams, sumicidin 5.1 grams, 0204C 8 grams, toluene are mended to 100 grams |
| ????12 | HNPC-A9908 1.3 grams, special 20.1 grams of sharp strength, No. 602 4.0 grams, xanthans 0.2 gram, water are mended to 100 grams, and the preparation method is with embodiment 1 |
| ????13 | HNPC-A9908 2.0 grams, desinsection list 20.1 grams, EL-15 12 grams, water are mended to 100 grams, and the preparation method is with embodiment 1 |
| ????14 | HNPC-A9908 2.0 grams, dimehypo 20.3 grams, 1,601 5 grams, 1,602 5.1 grams, water are mended to 100 grams, and the preparation method is with embodiment 1 |
| ????15 | HNPC-A9908 30.2 grams, Imidacloprid 30.1 grams, sodium lignin sulfonate 15.6 grams, calcium carbonate 5 grams, white carbon to 100 gram |
| ????16 | HNPC-A9908 2.1 grams, cartap 20.6 grams, BY120 10 grams, water are mended to 100 grams, and the preparation method is with embodiment 1 |
| ????17 | HNPC-A990820.3 gram, No. 2,000 12 grams, No. 500 1 grams, methyl alcohol 5 grams, dimethylbenzene to 100 restrain |
| ????18 | HNPC-A9908 20.5 grams, EL-10 12 grams, ethylene glycol 3 grams, water to 100 gram, the preparation method is with embodiment 1 |
List the hot and cold storage stability test result of embodiment of the invention 1-4 product below with table 1-table 4:
The storage test data of table 1 embodiment 2 products
| The mensuration project | Initially | Storage requirement | |
| 54 ℃ (14 days) | 0 ℃ (7 days) | ||
| HNPC-A9908 content % (w/w) | ????10.20 | ????10..09 | ????10.19 |
| Outward appearance | White emulsion | White emulsion | White emulsion |
| Dilution stability | Qualified | Qualified | Qualified |
| Viscosity | ????1.2mpa.s | ????1.1mpa.s | ????1.2mpa.s |
The storage test data of table 2 embodiment 1 product
| The mensuration project | Initially | Storage requirement | |
| 54 ℃ (14 days) | 0 ℃ (7 days) | ||
| HNPC-A9908 content % (w/w) | ????5.60 | ????5.45 | ????5.60 |
| Chlorfenapyr content % (w/w) | ????5.10 | ????5.12 | ????5.10 |
| Outward appearance | White emulsion | White emulsion | White emulsion |
| Dilution stability | Qualified | Qualified | Qualified |
| Viscosity | ????6mpa.s | ????7mpa.s | ????6mpa.s |
The storage test data of table 3 embodiment 3 products
| The mensuration project | Initially | Storage requirement | |
| 54 ℃ (14 days) | 0 ℃ (7 days) | ||
| HNPC-A9908 content % (w/w) | ????5.2 | ????5.0 | ????5.2 |
| Carbosulfan content % (w/w) | ????20.0 | ????19.9 | ????20.0 |
| Emulsifiability | Qualified | Qualified | Qualified |
The storage test data of table 4 embodiment 4 products
| The mensuration project | Initially | Storage requirement | |
| 54 ℃ (14 days) | 0 ℃ (7 days) | ||
| HNPC-A9908 content % (w/w) | ??10.2 | ????10.05 | ??10.15 |
| Diazinon content % (w/w) | ??40.1 | ????40.0 | ??40.1 |
| Emulsifiability | Qualified | Qualified | Qualified |
With table 5-table 13 effect of the present invention is described below
Biologically active compares, and result of the test is as follows:
The Toxicity Determination result of table 5 pair mythimna separata
Virulence regression equation formula correlation coefficient LC
Reagent agent RT
(Y＝a+bx)??????????(r)????????(mg/l)
HNPC-A9908 95% former medicine Y=2.6338+2.0106x 0.9498 15.03 1.00
Embodiment 2 product Y=1.1041+4.0933x 0.9996 8.95 1.68
Embodiment 17 product Y=1.6140+2.8211x 0.9174 15.86 0.95
Table 6 control cabbage caterpillar field control effectiveness test result
The worm medicine is behind the medicine behind three days medicines seven days one day after before the reagent agent consumption g medicine
Ai/ mu bar/hundred borer population preventive effects alive borer population preventive effects alive (%) borer population preventive effect (%) alive
(％)
Embodiment 2 products 2.0 461 83 82.2 67 85.8 63 86.7
Embodiment 2 products 4.0 464 52 89.1 18 96.2 11 97.7
Embodiment 2 products 8.0 473 23 95.3 7 98.5 4 99.2
10% trebon SC 4.0 454 21 95.5 6 98.7 3 99.3
10% eliminates SC 4.0 459 17 96.3 3 99.5 24 99.6
50% Padan SP 40.0 472 116 76.3 81 83.1 73 85.0
CK???????????/??????457???????462?????/??????466????/???????471????/
Table 7 control cotton bollworm field control effectiveness test result
Behind the medicine behind 1 day medicine behind 3 days medicines behind 5 days medicines behind 7 days medicines 14 days
Test is handled a mu insect population base anti-anti-anti-the living of preventing living alive of living alive and is prevented
Consumption number (head) worm is imitated worm and imitates worm effect worm effect worm effect
Number % count % and count % and count % and count %
Embodiment 2 produces
207?????17???92.4??2????99.2??0????100???0????100???14????95.2
Product 20ml
Embodiment 3 produces
185?????19???90.5??5????97.7??3????98.8??2????99.3??18????93.2
Product 20ml
Embodiment 6 produces
195?????38???82.0??32???86.2??25???90.3??10???88.7??47????83.1
Product 20ml
Embodiment 7 produces
2247????5????97.9??1????99.7??0????100???3????99.1??5?????98.4
Product 30ml
Embodiment 8 produces
284????7???97.7??2????99.4??2????99.5??5????98.9??9????97.8
Product 20ml
Embodiment 9 produces
224????63??74.1??51???80.8??29???90.1??36???89.5??48???84.9
Product 10g
CK?????????241????261??/????286??/?????318??/?????369??/?????343??/
Table 8 control rice fulgorid field control effectiveness test result
Behind the medicine behind 1 day medicine behind 3 days medicines behind 5 days medicines behind 7 days medicines 14 days
Reagent agent and mu consumption
Preventive effect % preventive effect % preventive effect % preventive effect % preventive effect %
Embodiment 12 product 10ml 70.1 78.8 80.8 74.2 64.5
Embodiment 12 product 20ml 73.5 81.0 85.3 76.7 67.2
Embodiment 12 product 40ml 76.8 85.1 90.3 79.4 69.8
CK??????????????????/????????/?????????/?????????/????????/
Table 9 control cabbage caterpillar field control effectiveness test result
The worm medicine is behind the medicine behind three days medicines seven days one day after before the reagent agent consumption medicine
A ml/ mu bar/borer population preventive effect alive (%) borer population preventive effect alive (%) borer population preventive effect (%) alive
Embodiment 18 products 40 67 6 95.07 4 92.15 4 89.57
Embodiment 18 products 20 55 7 86.33 6 87.74 7 79.42
Embodiment 18 products 10 58 13 75.00 10 79.67 13 62.06
10% trebon SC 40 60 12 82.42 4 94.07 2 94.79
10% eliminates SC 40 61 14 74.74 5 90.59 2 95.68
50% Padan SP 80 54 12 76.56 13 71.58 9 71.46
CK????????????/????????62????57??????/?????????53????????????????38????????/
Table 10 control tea geometrid field control effectiveness test result
Average preventive effect %
Reagent agent effective dose g/ mu
Behind the medicine behind 1 day medicine behind 3 days medicines 7 days
Embodiment 17 products 2 87.5 77.8 91.2b
Embodiment 17 products 4 95.8 96.4 97.7a
Embodiment 17 products 8 100 100 100a
10% eliminates SC 4 95.7 88.9 94.1b
CK????????????????/????????0?????????/???????????/
Table 11 control tea caterpillar field control effectiveness test result
Average preventive effect %
Behind the reagent agent effective dose g/ mu medicine behind 1 day medicine behind 3 days medicines 7 days
2?????????????85.7????????91.5??????96.1a
Embodiment 17 products 4 91.3 94.8 98.2a
8?????????????95.2????????100???????100a
10% eliminates SC 4 95.2 91.5 98.0a
CK??????????????/?????????????0???????????/?????????/
Table 12 control smaller green leaf hopper field control effectiveness test result
Average preventive effect %
Behind the reagent agent effective dose g/ mu medicine behind 1 day medicine behind 3 days medicines 7 days
Embodiment 4 products 1 63.0 70.4 80.6a
Embodiment 4 products 2 88.6 92.1 95.8a
Embodiment 4 products 4 94.7 97.4 97.6a
10% eliminates SC 4 85.0 91.2 95.5a
CK?????????????/????????????????0???????????/?????????/
The indoor responsive examination worm joint toxicity measuring comparative test result of table 13
Numbering medicament examination worm and method LC
50(ppm) co-toxicity coefficient
1 HNPC-A9908 mythimna separata, Potter spray-on process 15.03
Chlopyrifos mythimna separata, Potter spray-on process 128.25
HNPC-A9908+ chlopyrifos (1: 2) mythimna separata, Potter spray-on process 31.14 142.0
2 malathion mythimna separatas, Potter spray-on process 205.64
HNPC-A9908+ malathion (1: 4) mythimna separata, Potter spray-on process 40.21 164.3
3 desinsection list mythimna separatas, Potter spray-on process 202.81
HNPC-A9908+ desinsection list (1: 10) mythimna separata, Potter spray-on process 43.53 218.2
4 cartap mythimna separatas, Potter spray-on process 154.22
HNPC-A9908+ cartap (1: 10) mythimna separata, Potter spray-on process 38.96 214.88
5 HNPC-A9908 rice leafhoppers, Potter spray-on process 13.53
Imidacloprid rice leafhopper, Potter spray-on process 12.05
HNPC-A9908+ Imidacloprid (1: 1) rice leafhopper, Potter spray-on process 9.88 143.21
The goth black caudal lobe cicada of 6 sharp strength, Potter spray-on process 11.36
The sharp strength spy of HNPC-A9908+ (1: 20) rice leafhopper, Potter spray-on process 9.14 141.54
7 Bassa rice leafhoppers, Potter spray-on process 65.05
HNPC-A9908+ Bassa (1: 4) rice leafhopper, Potter spray-on process 23.75 213.85
8 unden rice leafhoppers, Potter spray-on process 60.42
HNPC-A9908+ Mobucin (1: 4) rice leafhopper, Potter spray-on process 20.61 223.11
9 cypermethrin mythimna separatas, Potter spray-on process 15.59
HNPC-A9908+ cypermethrin (1: 1) mythimna separata, Potter spray-on process 14.38 106.44
10 sumicidin mythimna separatas, Potter spray-on process 19.96
HNPC-A9908+ sumicidin (1: 1) mythimna separata, Potter spray-on process 15.67 114.82
11 sumithion mythimna separatas, Potter spray-on process 108.68
HNPC-A9908+ sumithion (1: 10) mythimna separata, Potter spray-on process 26.13 265.51
Claims (3)
1. one kind contains the non-fatty oxime ether pyrethrin insecticide composition, it is characterized in that it is that HNPC-A9908, a kind of known agricultural chemicals, organic solvent, surfactant, antifreeze, preservative, thickener, carrier and water are formed jointly by insecticidal active compound 1-(2-methyl mercapto)-rubigan acetoxime-chloro-(3-phenoxy benzyl) ether, the organic solvent that composition is selected for use is any or several mixture of cyclohexanone, benzene, methyl alcohol, dimethylbenzene, toluene; The surfactant of selecting for use is one or more in BY series, EL series, 0204C, 0201c, 0203b, T-11,1601,1602,600,601,2000,0206b, No. 500, lignin and the derivative sulfonate thereof; The antifreeze of selecting for use is an ethylene glycol; The preservative of selecting for use is a formaldehyde, benzoic a kind of; The thickener of selecting for use is the natural thickener xanthans; The carrier of selecting for use is one or more in white carbon, kaolin, the precipitated calcium carbonate; The water of selecting for use is deionized water; The known agricultural chemicals of selecting for use is any in diazinon, pirimiphos-methyl, malathion, sumithion, chlopyrifos, Bassa, carbaryl, unden, Mobucin etc., cypermethrin, sumicidin, dimehypo, desinsection list, fine, the sharp strength spy of bromine worm, the cartap; The percetage by weight that composition is formed is HNPC-A9908 1%-30%, known agricultural chemicals 0%-50%, organic solvent 0%-80%, surfactant 1%-20%, antifreeze 0%-5%, preservative 0%-5%, thickener 0%-3%, carrier 0-90%, water 0%-90%.
2. preparation method who contains the non-fatty oxime ether pyrethrin insecticide composition, it is characterized in that the water formulation preparation in the composition is to take by weighing all raw materials by prescription earlier, again with HNPC-A9908 that weighs up or the mixture that adds a known agricultural chemicals, add a small amount of solvent, surfactant dissolves then, stir and obtain even oil phase; Also can be with the mixture of HNPC-A9908 or a HNPC-A9908 and a known agricultural chemicals, use the surfactant fusion, stirring obtains oil phase, then water, preservative, antifreeze are mixed, form the homogeneous water, under normal temperature and high-speed stirred, oil phase is joined water, or water joins oil phase, form finely disseminated aqueous emulsion, mixing speed is 200 rev/mins-2000 rev/mins; Mixing time is 3-20 minute.
3. according to the described a kind of non-fatty oxime ether pyrethrin insecticide composition that contains of claim 1, it is characterized in that good stability, toxicity is low, can effectively prevent and kill off cabbage caterpillar, tea geometrid, tea caterpillar, smaller green leaf hopper, mythimna separata, rice leafhopper, rice fulgorid, cotton bollworm, to natural enemy and crop safety.
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| CNA031248624A CN1528143A (en) | 2003-09-26 | 2003-09-26 | Composition containing non-fatty oxime ether pyrethrin insecticide |
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| CNA031248624A CN1528143A (en) | 2003-09-26 | 2003-09-26 | Composition containing non-fatty oxime ether pyrethrin insecticide |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379342C (en) * | 2006-10-12 | 2008-04-09 | 江苏省农业科学院 | Composite pesticide of one class preventing and control rice pests |
| CN102228056A (en) * | 2011-06-02 | 2011-11-02 | 青岛海利尔药业有限公司 | Pesticide composition containing sulfur-fluorine oxime ether and part of organophosphorus pesticides |
| CN102228029A (en) * | 2011-06-01 | 2011-11-02 | 青岛海利尔药业有限公司 | Pesticidal and acaricidal composition containing sufluoxime and tebufenpyrad |
| CN102239867A (en) * | 2011-05-12 | 2011-11-16 | 海利尔药业集团股份有限公司 | Pesticide complex composition containing sulfuryl fluoride oxime ether |
| CN102246778A (en) * | 2011-05-18 | 2011-11-23 | 海利尔药业集团股份有限公司 | Efficiency enhanced insecticidal composition, and application thereof |
| CN103053558A (en) * | 2013-01-16 | 2013-04-24 | 海利尔药业集团股份有限公司 | Insecticide composition containing 1-(3-fluoro-4-chlorophenyl)-2-hexamethyl ethyl ketoxime-O-(2-methyl biphenyl) ether and spirotetramat |
| CN108293985A (en) * | 2018-02-13 | 2018-07-20 | 浙江永太科技股份有限公司 | A kind of sulfime ether ultra low volume liquids |
| CN108450476A (en) * | 2018-05-15 | 2018-08-28 | 孙利嫚 | A kind of composition pesticide of ether containing sulfime and butene-fipronil |
| CN109169694A (en) * | 2018-08-21 | 2019-01-11 | 青岛瀚生生物科技股份有限公司 | Agricultural insecticidal composite and its application |
-
2003
- 2003-09-26 CN CNA031248624A patent/CN1528143A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379342C (en) * | 2006-10-12 | 2008-04-09 | 江苏省农业科学院 | Composite pesticide of one class preventing and control rice pests |
| CN102239867B (en) * | 2011-05-12 | 2013-06-12 | 海利尔药业集团股份有限公司 | Pesticide complex composition containing sulfuryl fluoride oxime ether |
| CN102239867A (en) * | 2011-05-12 | 2011-11-16 | 海利尔药业集团股份有限公司 | Pesticide complex composition containing sulfuryl fluoride oxime ether |
| CN102246778A (en) * | 2011-05-18 | 2011-11-23 | 海利尔药业集团股份有限公司 | Efficiency enhanced insecticidal composition, and application thereof |
| CN102228029A (en) * | 2011-06-01 | 2011-11-02 | 青岛海利尔药业有限公司 | Pesticidal and acaricidal composition containing sufluoxime and tebufenpyrad |
| CN102228029B (en) * | 2011-06-01 | 2013-05-15 | 海利尔药业集团股份有限公司 | Pesticidal and acaricidal composition containing sufluoxime and tebufenpyrad |
| CN102228056A (en) * | 2011-06-02 | 2011-11-02 | 青岛海利尔药业有限公司 | Pesticide composition containing sulfur-fluorine oxime ether and part of organophosphorus pesticides |
| CN102228056B (en) * | 2011-06-02 | 2013-03-13 | 海利尔药业集团股份有限公司 | Pesticide composition containing sulfur-fluorine oxime ether and part of organophosphorus pesticides |
| CN103053558A (en) * | 2013-01-16 | 2013-04-24 | 海利尔药业集团股份有限公司 | Insecticide composition containing 1-(3-fluoro-4-chlorophenyl)-2-hexamethyl ethyl ketoxime-O-(2-methyl biphenyl) ether and spirotetramat |
| CN108293985A (en) * | 2018-02-13 | 2018-07-20 | 浙江永太科技股份有限公司 | A kind of sulfime ether ultra low volume liquids |
| CN108293985B (en) * | 2018-02-13 | 2020-09-18 | 浙江永太科技股份有限公司 | Sulfoximine ether ultra-low volume liquid |
| CN108450476A (en) * | 2018-05-15 | 2018-08-28 | 孙利嫚 | A kind of composition pesticide of ether containing sulfime and butene-fipronil |
| CN109169694A (en) * | 2018-08-21 | 2019-01-11 | 青岛瀚生生物科技股份有限公司 | Agricultural insecticidal composite and its application |
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