CN103651497A - Synergistic insecticidal composition containing clothianidin and flubendiamide and application of synergistic insecticidal composition - Google Patents
Synergistic insecticidal composition containing clothianidin and flubendiamide and application of synergistic insecticidal composition Download PDFInfo
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- CN103651497A CN103651497A CN201210314272.XA CN201210314272A CN103651497A CN 103651497 A CN103651497 A CN 103651497A CN 201210314272 A CN201210314272 A CN 201210314272A CN 103651497 A CN103651497 A CN 103651497A
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- clothianidin
- fipronil bisamide
- synergistic insecticidal
- insecticidal compositions
- synergistic
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Abstract
The invention discloses a synergistic insecticidal composition containing clothianidin and flubendiamide and an application of the synergistic insecticidal composition. The clothianidin and the flubendiamide are used as main effective ingredients of the insecticidal composition, wherein the weight ratio of the clothianidin to the flubendiamide is (0.1-80): (0.5-80). The insecticidal composition has the effects of expanding a prevention and control spectrum and synergizing, can be used for reducing the pesticide cost, and can be prepared into emulsion oil, wettable powder, a microemulsion, a water emulsion, a suspending agent and water dispersible granules to prevent and control various pests such as lepidoptera, hemiptera, hymenoptera, coleoptera and the like.
Description
Technical field
The invention belongs to the pesticide field that contains heterocyclic compound, be specifically related to a kind of Pesticidal combination and application thereof that clothianidin and fipronil bisamide be main active ingredient of take.
Background technology
Clothianidin (Clothianidin), chemical name: E)-1-(the chloro-1,3-thiazoles-5-of 2-ylmethyl)-3-methyl-2-nitroguanidine; Chemical molecular formula: C
6h
8clN
5o
2s; Sterling outward appearance is white crystals, 176.8 ℃ of fusing points, vapour pressure (20 ℃) 3.8 * 10-11Pa, solvability (g/L, 25 ℃): 0.327 (20 ℃) in water, in ethyl acetate 2.03, <0.00104 in normal heptane, in dimethylbenzene 0.0128, in carrene 1.32, in octanol 0.938, in acetone 15.2, in methyl alcohol 6.26.Structural formula:
Clothianidin acute oral toxicity, rat male and female: LD50 > 5000mg/kg, acute dermal toxicity: rat male and female: LD50 > 2000mg/kg, inhales people's toxicity: rat male and female, 6.1mg/L.
Clothianidin belongs to anabasine insecticide, be a kind of activity high, there is interior absorption, tag and the broad spectrum pesticide of stomach poison function.Shi Wu field company is after Nitenpyram (Nitenpyram), and another nicotinic insecticide of discovery, belongs to the second generation.The mechanism of action is in conjunction with the nAChR that is positioned at neural post-synapse.Be applicable to foliar spray, soil treatment effect, show good quick-acting, the lasting period is about 7 days.Be mainly used in paddy rice, vegetables, fruit tree and other crop, control Semiptera, coleoptera, diptera and some lepidoptera pest.
Fipronil bisamide (Flubendiamide), the iodo-N ＇ of chemical name: 3--(2-mesyl-1,1-dimethyl ethyl group-N-{4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]-0-tolyl } phthalamide, structural formula is:
Fipronil bisamide belongs to Novel ortho benzenedicarboxamide insecticides, activates calcium release channel in blue Buddhist nun's alkali recipient cell, causes the property out of control of storing calcium ion to discharge.It is at present few in number compounds that acts on blue Buddhist nun's alkali (Ryanodine) acceptor of insect cell.Lepidoptera pest is had to spectrum preventive effect, produce without cross resistance with existing insecticide, be suitable for very much the control that existing insecticide produces the insect of resistance.Larva is had to very outstanding preventive effect, limited to adult preventive effect, there is no ovicidal action.After in infiltration plant body, by xylem, slightly conduct.Resistance of rainwater washing against.
Often there is defect in the insecticide variety containing single component: use is easily developed immunity to drugs continuously, and insecticidal spectrum is narrow, can not provide comprehensive protection for crop, and peasant's drug cost is high in agricultural chemicals control of insect.By two kinds or being combined in to a certain extent of two or more active components, can overcome to a certain extent above-mentioned shortcoming.There is two kinds of synergistic effect or the combination of two or more active components and be mixed, can improve preventive effect, reduce active ingredient ground dosage, cost-saving, slow down pest resistance occur, and can expanding prevention spectrum, play that many worms are double to be controlled, reduce peasant's use cost.
Summary of the invention
The Synergistic insecticidal compositions that the object of this invention is to provide a kind of clothianidin-containing and fipronil bisamide, said composition can be used for preventing and treating various agricultural insect, such as preventing and treating rice hoppers or cotton cotton bollworm and vegetables diamond-back moth etc., can reach the effect that a drug is prevented and treated dissimilar insect.
The Synergistic insecticidal compositions that another object of the present invention is to provide clothianidin-containing and fipronil bisamide is prevented and treated the application in the insecticidal materials of one or more insects in resistance Lepidoptera, Semiptera, Hymenoptera or coleoptera in preparation.
The present invention adopts following technical scheme:
A Synergistic insecticidal compositions for clothianidin-containing and fipronil bisamide, it take clothianidin and fipronil bisamide is main active ingredient, wherein, the weight ratio of clothianidin and fipronil bisamide is 0.1 ~ 80:0.5 ~ 80.Be preferably 1 ~ 60:1 ~ 70,1 ~ 10:1 ~ 10, more preferably 1 ~ 30:1 ~ 30, further preferred weight ratio, when the ratio of fipronil bisamide and clothianidin is 1 ~ 10:1, mixed synergies is the most remarkable.This Synergistic insecticidal compositions can only contain active ingredient clothianidin and fipronil bisamide, also can when using or prepare, in active component, add other components, and the effective ingredient of above-mentioned Insecticidal combinations is present in composition with synergy effective dose.
At the Synergistic insecticidal compositions of clothianidin-containing of the present invention and fipronil bisamide, the two weight percentage in this Synergistic insecticidal compositions of clothianidin and fipronil bisamide is 2% ~ 80%, is preferably 8% ~ 60%, and optimum is 20% ~ 40%.
The Synergistic insecticidal compositions of above-mentioned clothianidin-containing and fipronil bisamide be take clothianidin and fipronil bisamide and is mixed with any one formulation allowing on agricultural chemicals as main active ingredient (active component) and insecticides adjuvant, excipients.The preferred pulvis of formulation, wetting powder, suspending agent, missible oil and water dispersion granule.
Aforementionedly can be applicable to the not special restriction of insecticides adjuvant of the present invention, include, but are not limited to calcium dodecyl benzene sulfonate, alkylphenol polyoxyethylene, the rare block compound of polyoxyethylene polyoxy third (as agriculture breast 33
#), polyoxyethylene nonylphenol ether etc., aforementionedly can be applicable to excipient of the present invention and be also not particularly limited, include, but are not limited to cyclohexanone, dimethylbenzene, solvent naphtha, water, antifreezing agent (as propane diols), deionized water etc.Above auxiliary agent, excipient and the upper known auxiliary material of other agricultural can alone or and use.
Application in the insecticidal materials of above-mentioned clothianidin-containing and the Synergistic insecticidal compositions of fipronil bisamide one or more insects in preparation control Lepidoptera, Semiptera, Hymenoptera or coleoptera.Especially the effect of preventing and treating in the insecticidal materials of rice hoppers or cotton cotton bollworm and vegetables diamond-back moth in preparation is remarkable.
Synergistic insecticidal compositions antagonism lepidoptera pest of the present invention has significant preventive effect, especially for rice hoppers or the easy various pests that produces resistance such as cotton cotton bollworm and vegetables diamond-back moth, has good preventive effect; And suppress insect to the pesticide resistance generation of unitary agent (clothianidin or fipronil bisamide) and can prevent and treat Semiptera insect as thrips, aleyrodid, leafhopper etc. simultaneously.
The insecticidal materials of being prepared by the Synergistic insecticidal compositions of described clothianidin-containing and fipronil bisamide, when preventing and treating resistance Lepidoptera, Hymenoptera or coleopteran pest, can be prevented and treated Semiptera insect again, has expanded control spectrum, reaches the effect that a medicine is controlled more." % " of the present invention is mass percent.
Pesticidal combination of the present invention compared with prior art, produces following beneficial effect: (1) is compared with single dose, and said composition insect has notable synergistic, has obviously improved control efficiency; (2) one medicines are controlled more, and a dispenser can prevent and treat various pests simultaneously, reduce control recruitment cost; (3) alternative high-toxic pesticide, and significantly reduce field dosage, effectively reduce environmental pollution and residue of pesticide; (4) have concurrently quick-acting and long-acting; (5) compare with clothianidin single dose, produce and use cost reduction; (6) suppressing insect strengthens the resistance of agricultural chemicals;
Embodiment
Below in conjunction with embodiment, the invention will be further described, but do not limit the present invention in any way.
Embodiments of the invention are the methods that adopt indoor bioassay and field trial to combine.First by indoor bioassay, the co-toxicity coefficient after clear and definite two kinds of medicaments are composite by a certain percentage; On this basis, then carry out field trial.
Embodiment 1:
Take 30g clothianidin and fipronil bisamide, calcium dodecyl benzene sulfonate 4g, phenethyl phenol polyethenoxy ether 3g, vegetable oil to 100g.The method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and makes the clothianidin fipronil bisamide missible oil that main active ingredient weight percentage is 30%.The concrete ratio of clothianidin and fipronil bisamide is in Table 1,2.
Adopt feed to add malicious method and measure clothianidin and fipronil bisamide and the virulence of composite sample to rice hoppers thereof, every processing repeats 3 times, and every concentration is processed 30, uses LC
50value is pressed the abundant method of Sun Yun and is calculated co-toxicity coefficient:
Table 1 clothianidin, fipronil bisamide and composite sample thereof are to the toxicity test of rice hoppers and co-toxicity coefficient
In table, data show, after clothianidin and fipronil bisamide are mixed, rice hoppers are had to synergistic effect, and four proportioning co-toxicity coefficients listed in table are all much larger than 120, so clothianidin and fipronil bisamide are mixed and have significant synergies.Wherein when the ratio of fipronil bisamide and clothianidin is 1:1, be mixed and kill the synergistic effect maximum of rice hoppers, co-toxicity coefficient is 206.28.
Embodiment 2:
Taking clothianidin, fipronil bisamide adopts conventional formulation method to be mixed with by different proportion the clothianidin fipronil bisamide missible oil that main active ingredient weight percentage is 30%.Concrete ratio is in Table 2.
Adopt infusion process to measure clothianidin and fipronil bisamide and the virulence of composite sample to cotton cotton bollworm thereof, every processing repeats 3 times, uses LC
50value is pressed the abundant method of Sun Yun and is calculated co-toxicity coefficient:
Table 2 clothianidin, fipronil bisamide and composite sample thereof are to the toxicity test of cotton cotton bollworm and co-toxicity coefficient
In table, data show, after clothianidin and fipronil bisamide are mixed, cotton cotton bollworm are had to synergistic effect, and four proportioning co-toxicity coefficients listed in table are all much larger than 120, so clothianidin and fipronil bisamide are mixed and have significant synergies.Wherein when the ratio of clothianidin and fipronil bisamide is 1:5, be mixed and kill the synergistic effect maximum of cotton cotton bollworm, co-toxicity coefficient is 219.32.
Embodiment 3:
Take 5g clothianidin, 20g fipronil bisamide, calcium dodecyl benzene sulfonate 4g, phenethyl phenol polyethenoxy ether 3g, dimethylbenzene to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and makes the clothianidin fipronil bisamide missible oil that main active ingredient weight percentage is 25%.
Adopt 3 sample product of embodiment to carry out the field trial of control in field rice hoppers, contrast medicament is 15% clothianidin EC and 20% fipronil bisamide WDG, and concrete consumption is in Table 3, every mu of water consumption is 30kg, looks into 7 days after medicine 3 days, 14 days, 28 days results, result of the test is in Table 3:
The field test results of table 3 example 3 samples to rice hoppers
3 pairs of rice hoppers of example have fabulous quick-acting as can be seen from Table 3, and the lasting period is more intense, in field performance well, are the outstanding medicaments of preventing and treating rice hoppers.
Embodiment 4:
Adopt 3 sample product of embodiment to carry out the field trial of control in field cotton cotton bollworm, contrast medicament is 15% clothianidin EC and 20% fipronil bisamide WDG, and concrete consumption is in Table 3, every mu of water consumption is 30kg, looks into 7 days after medicine 3 days, 14 days, 28 days results, result of the test is in Table 4:
The field test results of table 4 example 3 samples to cotton cotton bollworm
Example 3 samples have fabulous effect to cotton cotton bollworm as can be seen from Table 4, and the lasting period is long, in field performance well, are the outstanding medicaments of control cotton cotton bollworm.
Through indoor synergism test, measure and show: by clothianidin and fipronil bisamide built agent, rice hoppers and cotton cotton bollworm are all had to significant synergistic insecticidal action; Field control effectiveness test equally also shows that all built agents of the present invention are all significantly higher than the effect of corresponding single dose agricultural chemicals to the insecticidal effect of rice hoppers and cotton cotton bollworm.
Embodiment 5:
Take 0.2g clothianidin, 20g fipronil bisamide, lignin 10g, Negel 2g, with kaolin, add to 100g, above raw material is mixed in micronizer, make the clothianidin fipronil bisamide wetting powder that main active ingredient weight percentage is 20.2%.
Embodiment 6:
Take 78g clothianidin, 0.5g fipronil bisamide, calcium dodecyl benzene sulfonate 8g, phenethyl phenol polyethenoxy ether 6g, dimethylbenzene and add to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and makes the clothianidin fipronil bisamide missible oil that main active ingredient weight percentage is 78.5%.
Embodiment 7:
Take 2g clothianidin, 10g fipronil bisamide, nonyl phenol phosphate 5g, alkylphenol polyoxyethylene 4g, n-butanol 3g, the dimethylbenzene of 30g and the pyrrolidones of 20g, the xanthans of 0.1g, all the other waters are supplied 100g, n-butanol and water-soluble solution form water, and all the other component mix and blends form oil phases, go in slowly water being added to oil phase under clipper effect, and continue to shear 10 ~ 30 minutes, make the clothianidin fipronil bisamide aqueous emulsion that main active ingredient weight percentage is 12%.
Embodiment 8:
Take 10g clothianidin, 30g fipronil bisamide, calcium dodecyl benzene sulfonate 5g, alkylphenol polyoxyethylene 4g, the solvent xylene of 30g and the pyrrolidones of 15g, all the other waters complement to 100g, former medicine, solvent, emulsifier, cosolvent mix and blend form homogeneous phase transparent solution, then slowly add water and stir to form clear solution, be the clothianidin fipronil bisamide microemulsion that main active ingredient weight percentage is 40%.
Embodiment 9:
Take 4g clothianidin, 4g fipronil bisamide, calcium dodecyl benzene sulfonate 5g, phenethyl phenol polyethenoxy ether 3g, dimethylbenzene to 100g.The method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and makes the clothianidin fipronil bisamide missible oil that main active ingredient weight percentage is 8%.
Embodiment 10:
Take 3g clothianidin, 30g fipronil bisamide, sodium lignin sulfonate 3g, polyoxyethylene poly-oxygen propylene aether and sulphate 4g thereof, xanthans 0.2g, ethylene glycol 10g, silica ethane 0.1g, aluminium-magnesium silicate 0.5g, water is supplied 100g, makes the clothianidin fipronil bisamide suspension agent that main active ingredient weight percentage is 33% under the effect of sand mill.
Embodiment 11:
Take 5g clothianidin, 60g fipronil bisamide, alkylphenol polyoxyethylene 14g, phenethyl phenol polyethenoxy ether 15g, dimethylbenzene to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and makes the clothianidin fipronil bisamide missible oil that main active ingredient weight percentage is 65%.
Embodiment 12:
Take 45g clothianidin, 5g fipronil bisamide, sodium lignin sulfonate 8g, lauryl sodium sulfate 2g, ammonium sulfate 5g, polyvinyl alcohol 5g, borax 2g, kaolin 28g, makes by the method for water dispersion granule the clothianidin fipronil bisamide water dispersible granules that main active ingredient weight percentage is 50% by above raw material.
Embodiment 13:
Take 25g clothianidin, 25g fipronil bisamide, alkylphenol polyoxyethylene 14g, phenethyl phenol polyethenoxy ether 15g, dimethylbenzene to 100g, the method that above raw material is prepared to missible oil routinely drops in mixing kettle mixes, and makes the clothianidin fipronil bisamide missible oil that main active ingredient weight percentage is 50%.
Claims (10)
1. a Synergistic insecticidal compositions for clothianidin-containing and fipronil bisamide, is characterized in that it is main active ingredient that this Synergistic insecticidal compositions be take clothianidin and fipronil bisamide, and wherein, the weight ratio of clothianidin and fipronil bisamide is 0.1 ~ 80:0.5 ~ 80.
2. the Synergistic insecticidal compositions of clothianidin-containing according to claim 1 and fipronil bisamide, is characterized in that the effective ingredient clothianidin of this Pesticidal combination and the weight ratio of fipronil bisamide are 1 ~ 60:1 ~ 70.
3. the Synergistic insecticidal compositions of clothianidin-containing according to claim 2 and fipronil bisamide, is characterized in that the effective ingredient clothianidin of this Pesticidal combination and the weight ratio of fipronil bisamide are 1 ~ 30:1 ~ 30.
4. the Synergistic insecticidal compositions of clothianidin-containing according to claim 3 and fipronil bisamide, is characterized in that the effective ingredient clothianidin of this Pesticidal combination and the weight ratio of fipronil bisamide are 1 ~ 10:1 ~ 10.
5. the Synergistic insecticidal compositions of clothianidin-containing according to claim 1 and fipronil bisamide, is characterized in that the two weight percentage in this Synergistic insecticidal compositions of clothianidin and fipronil bisamide is 2% ~ 80%.
6. the Synergistic insecticidal compositions of clothianidin-containing according to claim 5 and fipronil bisamide, is characterized in that the two weight percentage in this Synergistic insecticidal compositions of clothianidin and fipronil bisamide is 8% ~ 60%.
7. the Synergistic insecticidal compositions of clothianidin-containing according to claim 1 and fipronil bisamide, is characterized in that this Synergistic insecticidal compositions take clothianidin and fipronil bisamide and be mixed with any one formulation allowing on agricultural chemicals as main active ingredient and insecticides adjuvant, excipients.
8. the Synergistic insecticidal compositions of clothianidin-containing according to claim 7 and fipronil bisamide, is characterized in that described formulation is missible oil, wetting powder, microemulsion, aqueous emulsion, suspending agent or water dispersion granule.
9. the application in the insecticidal materials of the Synergistic insecticidal compositions of clothianidin-containing claimed in claim 1 and fipronil bisamide one or more insects in preparation control Lepidoptera, Semiptera, Hymenoptera or coleoptera.
10. application according to claim 9, the Synergistic insecticidal compositions that it is characterized in that clothianidin-containing and fipronil bisamide is prevented and treated the application in the insecticidal materials of rice hoppers or cotton cotton bollworm and vegetables diamond-back moth in preparation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104106590A (en) * | 2013-04-19 | 2014-10-22 | 陕西美邦农药有限公司 | Insecticidal composition containing flubendiamide and neonicotinoids |
| CN104430475A (en) * | 2014-11-04 | 2015-03-25 | 浙江省化工研究院有限公司 | Insecticidal composition containing clothianidin and chlorofluorocarbon cyantraniliprole |
| CN104472528A (en) * | 2014-11-25 | 2015-04-01 | 广东中迅农科股份有限公司 | Pesticide composition for preventing and treating diseases and pest insects of rice |
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| WO2007123853A2 (en) * | 2006-04-20 | 2007-11-01 | E. I. Du Pont De Nemours And Company | Five-membered heterocyclic invertebrate pest control agents |
| CN102273440A (en) * | 2011-09-13 | 2011-12-14 | 广西田园生化股份有限公司 | Ultralow volume liquid containing clothianidin |
| CN102405928A (en) * | 2011-12-19 | 2012-04-11 | 河南金田地农化有限责任公司 | Pesticide composition of flubendiamide and neonicotinoid insecticide |
-
2012
- 2012-08-29 CN CN201210314272.XA patent/CN103651497A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007123853A2 (en) * | 2006-04-20 | 2007-11-01 | E. I. Du Pont De Nemours And Company | Five-membered heterocyclic invertebrate pest control agents |
| CN102273440A (en) * | 2011-09-13 | 2011-12-14 | 广西田园生化股份有限公司 | Ultralow volume liquid containing clothianidin |
| CN102405928A (en) * | 2011-12-19 | 2012-04-11 | 河南金田地农化有限责任公司 | Pesticide composition of flubendiamide and neonicotinoid insecticide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104106590A (en) * | 2013-04-19 | 2014-10-22 | 陕西美邦农药有限公司 | Insecticidal composition containing flubendiamide and neonicotinoids |
| CN104430475A (en) * | 2014-11-04 | 2015-03-25 | 浙江省化工研究院有限公司 | Insecticidal composition containing clothianidin and chlorofluorocarbon cyantraniliprole |
| CN104472528A (en) * | 2014-11-25 | 2015-04-01 | 广东中迅农科股份有限公司 | Pesticide composition for preventing and treating diseases and pest insects of rice |
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Application publication date: 20140326 |