CN101611708A - A kind of rotenone micro-emulsion - Google Patents

A kind of rotenone micro-emulsion Download PDF

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Publication number
CN101611708A
CN101611708A CN200910041257A CN200910041257A CN101611708A CN 101611708 A CN101611708 A CN 101611708A CN 200910041257 A CN200910041257 A CN 200910041257A CN 200910041257 A CN200910041257 A CN 200910041257A CN 101611708 A CN101611708 A CN 101611708A
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rotenone
emulsion
micro
mass percentage
content
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王龙江
毛润乾
简美玲
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Guangdong Entomological Institute
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Guangdong Entomological Institute
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Abstract

The invention discloses a kind of rotenone micro-emulsion, aim to provide a kind of rotenone content height, good stability, rotenone micro-emulsion that control efficiency is good.It is to supply 100% by rotenone 3~6%, solvent 20-40%, composite anion-nonionic emulsifier 9-20%, assistant for emulsifying agent 0.1-5%, all the other waters.Described composite anion-nonionic emulsifier is by mass fraction, and tween is 40-80%, and anion surfactant is 1-10%; Surplus is the hydrophily polar solvent.Described tween is made up of two or more non-ionic surface active agents, and by mass percentage, wherein the content of any one non-ionic surface active agent is not higher than 80%.The present invention is used for the control of insect of the nuisanceless production of agriculture field.

Description

A kind of rotenone micro-emulsion
Technical field:
The present invention relates to a kind of agricultural chemicals, be specifically related to a kind of rotenone micro-emulsion.
Background technology:
Rotenone is the efficient insecticide active substance of generally acknowledging in the world, and it is to environment, people and animals, pest natural enemy and other beneficial organism safety, and insect is not easy to develop immunity to drugs, and therefore belongs to environment amenable insecticide active substance.Development along with agricultural science, especially country strengthened the attention to agricultural development in nearly 2 years, make that its importance at control agricultural disease, worm, grass is particularly outstanding, develop multiple rotenone insecticide variety in succession, but formulation mostly is cream preparation, and the use of this cream preparation agricultural chemicals has also brought negative effect to environment, the aromatic hydrocarbons organic solvent that missible oil consumption is a large amount of when improving crop yield, these toxic solvents cause environmental pollution, are detrimental to health.
The modern formulations of pesticide promptly are the formulations of pesticide of matrix with water, promptly with big old formulations of missible oil of water baseization pesticidal preparations replace organic solvent consumption such as suspending agent, microemulsion, aqueous emulsions towards water baseization, ultramicronising, no efflorescence and the development of sustained release aspect.Wherein microemulsion be a kind of organic solvent can be less with in addition the novel pesticide formulation of no, good drug efficacy, environmentally-friendly water-basedization, also be a kind of good liquid dosage form that replaces emulsifiable concentrates for agricultural chemicals.Publication number is that CN101379996 discloses a kind of rotenone micro-emulsion, and this microemulsion comprises that rotenone 1.5-2.5%, solvent 6-17%, emulsifier 9-18%, stable transparent agent 0.01-0.3%, antifreezing agent 0.1-0.6%, surplus are water.But in the above-mentioned rotenone micro-emulsion, rotenone content is low, poor stability and control efficiency are relatively poor.
Summary of the invention:
A kind of rotenone content height, good stability, rotenone micro-emulsion that control efficiency is good have been the purpose of this invention is to provide.
The present invention utilizes the mixing theory of modules and micelle increase-volume theory to be the basis, and the HLB value method and the micellar theory of reference surface activating agent are selected, with environmental friendliness insecticide active substance rotenone and composite blended emulsifier, thereby the microemulsion that is mixed with water baseization has been realized purpose of the present invention.
The present invention is achieved by the following technical programs:
Rotenone micro-emulsion of the present invention comprises by mass fraction:
Rotenone 3~6%
Solvent 20-40%
Composite anion-nonionic emulsifier 9-20%
Assistant for emulsifying agent 0.1-5%
All the other waters complement to 100%.
Described composite anion-nonionic emulsifier is by mass fraction, and tween is 40-80%, and anion surfactant is 1-10%, and surplus is the hydrophily polar solvent.
Described tween is made up of two or more non-ionic surface active agents, and by mass percentage, wherein the content of any one non-ionic surface active agent is not higher than 80%.
Described composite anion-nonionic emulsifier is nonionic and anion surfactant and hydrophilic polar solvent composite obtaining under stirring fast, and this emulsifier has good emulsifying effectiveness.Described tween is the two or more combinations in benzylphenol APEO, alkaryl phenol polyethenoxy ether phosphate, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, castor oil polyoxyethylene ether, styryl phenyl APEO, the polyol fatty acid ester, and wherein the content of any one non-ionic surface active agent is not higher than 80% in tween.Described anion surfactant is one or more the combination in alkylbenzenesulfonate, ether alcohol sulfate, triphen ethyl-phenol polyoxyethylene phosphate and the sulphate.Described polar solvent is one or more the combination in methyl alcohol, ethanol, n-butanol, the ethyl acetate.
Described solvent is one or more the combination in ether, acetone, cyclohexanone, ethyl acetate, dimethyl formamide, the N-Methyl pyrrolidone.
Described assistant for emulsifying agent is one or more the combination in propyl alcohol, hexanol, octanol, isobutanol, ethylene glycol, glycerine, cyclohexanol, methyl diethylene glycol (DEG), ethyl diethylene glycol (DEG), castor oil, the lauryl sodium sulfate.
Described water can be with deionized water or running water or drinking water or natural water.
Of the present invention preferably by mass percentage: rotenone content is 3%, and solvent is a cyclohexanone, and content is 26.7%, and composite anion-nonionic emulsifier is 16%, and assistant for emulsifying agent is a castor oil, and content is 1.3%, and the surplus water supplies 100%; Described composite anion-nonionic emulsifier is: tween is 54.1%, and anion surfactant is a calcium dodecyl benzene sulfonate, and content is 4.1%, and surplus supplies 100% with polar solvent methyl alcohol; Described tween is: fatty alcohol-polyoxyethylene ether 38.5%, OPEO 61.5%.
Rotenone micro-emulsion of the present invention is preparation like this, at first rotenone all is dissolved in the solvent, then emulsifier is slowly added in the entry, and the limit edged stirs, and forms emulsifier aqueous solution, adds assistant for emulsifying agent again, stirs; At last the rotenone of dissolving is directly joined in the emulsifier aqueous solution to mix and stir to become in 0.5-1.0 hour transparence solution and get final product.
Beneficial effect of the present invention is as follows:
1. the present invention substitutes most organic solvent with water; reduce environmental pollution; help ecological environmental protection; also can greatly reduce production costs, save a large amount of petrochemical industry resources, and the present invention adopts and not contain the phenyl ring class and to the solvent of environment or human body low toxicity; significantly reduce organic solvent to the pollution of human body and environment and residual; produce pollution, explosive and poisoning problem in avoiding producing, pesticide processing is hanged down poison, ensure human and mammiferous safety and health.
2. the present invention adopts rotenone and composite anion-nonionic emulsifier and the rotenone micro-emulsion that disposes, this microemulsion stable transparent dispersion on thermodynamics is, spray droplet is little in use, have better wetting to crop and polypide, sprawl, adhere to and permeability, the absorption soup is many, improve drug effect, this microemulsion is active high to crop pests, compare with the rotenone micro-emulsion of prior art, the content height, stability is strong, safety is good, rotenone is being diluted under the identical situation of application concentration, the control efficiency of rotenone micro-emulsion of the present invention is apparently higher than rotenone micro-emulsion of the prior art.Rotenone micro-emulsion provided by the invention has efficiently, low toxicity, pollution-free, environmentally friendly, person poultry safety, the characteristics that insect is difficult for developing immunity to drugs.
Embodiment:
The present invention is further elaborated below in conjunction with embodiment, but be not limitation of the present invention.
Example one
Take by weighing rotenone 0.68g, be dissolved in the 6.0g cyclohexanone; Take by weighing fatty alcohol-polyoxyethylene ether 0.75g, OPEO 1.2g, calcium dodecyl benzene sulfonate 0.15g, be dissolved among the hydrophilic polar solvent methyl alcohol 1.5g under stirring fast, add entry 12.2g then, in the emulsification still, stir, add castor oil 0.3g again and stir, make transparent emulsifier aqueous solution; Solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, is stirred to transparently, promptly makes rotenone micro-emulsion.
The test of pesticide effectiveness of rotenone micro-emulsion designs with reference to " pesticide field efficacy medicine test criterion " related standards.Test totally 4 processing, as shown in table 1, reagent agent is rotenone micro-emulsion and 2.0% rotenone micro-emulsion (the referenced patent CN200810073722.4: chloroform 12% according to the present embodiment configuration, cyclohexanone 5%, alkyl benzene calcium sulfonate 8%, diphenyl phenolic group polyoxyethylene 10%, nitrogen ammonia 0.02%, ethanol 0.3%), three replicated plots of each chemicals treatment, blank sprays clear water.
In each processing of herbary and check plot, the vegetables of 50 health of picked at random respectively at the number of being injured of 1d, 3d, 5d record vegetables after the dispenser, are calculated the rate of being injured of vegetables.
The field control effectiveness test of table 1 rotenone micro-emulsion
The dispenser date Test area For studying thing Controlling object Weather conditions
??2007 100 mu Heart of a cabbage Phyllotreta striolata ??20-25℃
??2007 200 mu Rape Phyllotreta striolata ??23-30℃
??2008 100 mu Wild cabbage Phyllotreta striolata ??18-23℃
??2008 150 mu Cauliflower Phyllotreta striolata ??25-35℃
Annotate: this test divides to be carried out in two years, totally 4 tests
Dispenser and investigation method:
Medicament is converted dispenser after the water dilution process by different dosages, rotenone micro-emulsion according to the present embodiment configuration, dilution is 1500 times when using, referenced patent CN200810073722.4 prepares 2% rotenone micro-emulsion, dilution is 800 times when using, so that the concentration of the rotenone during both dispensers is basic identical.Use knapsack hand sprayer, carry out even spraying in the experimental field, spraying is wanted comprehensively, does not drip with the blade face and is advisable.Investigate the strain number of being injured of each test region mark respectively at 1d, 3d, 5d before the dispenser and behind the medicine, and check that medicament has or not poisoning and to the influence of other biological, calculates the rate of being injured of vegetables crop.The drug effect of rotenone is calculated with the henderson-tilton method, and result of the test is as shown in table 2.
Table 2 rotenone micro-emulsion is to the control efficiency of phyllotreta striolata
Figure G2009100412570D00041
Annotate: data are the mean value that repeats for 3 times in the table, have same letter and represent that difference is not remarkable on p 〉=0.05 level, otherwise then significantly (DMRT).
By above-mentioned experiment as can be known, the control efficiency of the rotenone micro-emulsion of present embodiment is significantly higher than 2% rotenone micro-emulsion of the prior art.
Example two
Take by weighing rotenone 4g, be dissolved in 30.0g ethyl acetate and N-Methyl pyrrolidone (pressing mass ratio 1: the 2) solvent; Take by weighing fatty alcohol-polyoxyethylene ether 5.0g, castor oil polyoxyethylene ether 7.0g, calcium dodecyl benzene sulfonate 1.0g, be dissolved among the hydrophilic polar solvent methyl alcohol 4.0g under stirring fast, add entry 48.5g then, stir, add cyclohexanol 0.5g again, in the emulsification still, stir, make transparent emulsifier aqueous solution; Solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, is stirred to transparently, promptly makes rotenone micro-emulsion.
Test of pesticide effectiveness method with reference to embodiment 1, carry out the test of pesticide effectiveness, reagent agent is according to 2000 times of the 4% rotenone micro-emulsion dilutions of present embodiment configuration and 1000 times of (referenced patent CN200810073722.4: chloroform 12% of 2.0% rotenone micro-emulsion dilution, cyclohexanone 5%, alkyl benzene calcium sulfonate 8%, diphenyl phenolic group polyoxyethylene 10%, nitrogen ammonia 0.02%, ethanol 0.3%), three replicated plots of each chemicals treatment, blank sprays clear water.Result of the test is as shown in table 3.
Table 3 rotenone micro-emulsion is to the control efficiency of phyllotreta striolata
Figure G2009100412570D00042
Annotate: data are the mean value that repeats for 3 times in the table, have same letter and represent that difference is not remarkable on p 〉=0.05 level, otherwise then significantly (DMRT).
Experimental results show that under the identical situation of the spraying medicine concentration of rotenone, the present embodiment rotenone micro-emulsion have a good control efficiency, its control efficiency is significantly higher than 2% rotenone micro-emulsion of the prior art.
Example three
Take by weighing rotenone 6g, be dissolved in 40.0g cyclohexanone and the N-Methyl pyrrolidone (pressing mass ratio 1: 1); Take by weighing alkyl phenol formaldehyde resin polyoxyethylene ether 4.0g, styryl phenyl APEO 6.0g, calcium dodecyl benzene sulfonate 1.7g, ether alcohol sulfate (AES) 2.0g, be dissolved among the hydrophilic polar solvent methyl alcohol 4.0g under stirring fast, then, add entry 31.3g, stir to transparent, add ethyl diethylene glycol (DEG) and glycerine (pressing mass ratio 1: 4) 5.0g again, fully dissolving stirs the transparent emulsifier aqueous solution of system in the emulsification still; Solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, stirs 30min to transparent, promptly makes rotenone micro-emulsion.
Test of pesticide effectiveness method with reference to embodiment 1, carry out the test of pesticide effectiveness, experimental results show that under the identical situation of the spraying medicine concentration of rotenone, the present embodiment rotenone micro-emulsion have a good control efficiency, its control efficiency is apparently higher than 2% rotenone micro-emulsion of the prior art.
Test of pesticide effectiveness method with reference to embodiment 1, carry out the test of pesticide effectiveness, reagent agent is according to 3000 times of the 6% rotenone micro-emulsion dilutions of present embodiment configuration and 1000 times of (referenced patent CN200810073722.4: chloroform 12% of 2.0% rotenone micro-emulsion dilution, cyclohexanone 5%, alkyl benzene calcium sulfonate 8%, diphenyl phenolic group polyoxyethylene 10%, nitrogen ammonia 0.02%, ethanol 0.3%), three replicated plots of each chemicals treatment, blank sprays clear water.Result of the test is as shown in table 4.
Table 4 rotenone micro-emulsion is to the control efficiency of phyllotreta striolata
Figure G2009100412570D00051
Annotate: data are the mean value that repeats for 3 times in the table, have same letter and represent that difference is not remarkable on p 〉=0.05 level, otherwise then significantly (DMRT).
Experimental results show that under the identical situation of the spraying medicine concentration of rotenone, the present embodiment rotenone micro-emulsion have a good control efficiency, its control efficiency is significantly higher than 2% rotenone micro-emulsion of the prior art.
Example four
Take by weighing rotenone 5g, be dissolved in the 26.9gN-methyl pyrrolidone; Take by weighing fatty alcohol-polyoxyethylene ether 8.0g, alkylphenol polyoxyethylene 6.0g, triphen ethyl-phenol polyoxyethylene phosphate 1.0g is dissolved among the hydrophilic polar solvent ethanol 5.0g under stirring fast, adds entry 43.1g then, fully stirring and dissolving is extremely transparent in the emulsification still, add ethylene glycol 5.0g again, stir, the transparent emulsifier aqueous solution of system, solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, stirs 30min to transparent getting final product.
Test of pesticide effectiveness method with reference to embodiment 1, carry out the test of pesticide effectiveness, experimental results show that under the identical situation of the spraying medicine concentration of rotenone, the present embodiment rotenone micro-emulsion have a good control efficiency, its control efficiency is significantly higher than 2% rotenone micro-emulsion of the prior art.
Example five
Take by weighing rotenone 3.5g, be dissolved in the 26.5g cyclohexanone; Take by weighing castor oil polyoxyethylene ether 5.5g, polyol fatty acid ester 5.0g, calcium dodecyl benzene sulfonate 1.5g), be dissolved among hydrophilic polar solvent ethyl acetate and methyl alcohol (pressing mass ratio 1: the 1) 5.0g under stirring fast, add entry 52.0g then, in the emulsification still, add glycerine 1.0g again, stir, make transparent emulsifier aqueous solution; Solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, is stirred to transparently, promptly makes rotenone micro-emulsion.
In the emulsification still, stir; Solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, is stirred to transparently, promptly makes rotenone micro-emulsion.
Test of pesticide effectiveness method with reference to embodiment 1, carry out the test of pesticide effectiveness, experimental results show that under the identical situation of the spraying medicine concentration of rotenone, the present embodiment rotenone micro-emulsion have a good control efficiency, its control efficiency is significantly higher than 2% rotenone micro-emulsion of the prior art.
Embodiment six
Take by weighing rotenone 3.5g, be dissolved in 20.0g acetone and the N-Methyl pyrrolidone (pressing mass ratio 1: 3); Take by weighing alkylphenol polyoxyethylene 2g, castor oil polyoxyethylene ether 1g, styryl phenyl APEO 2g, triphen ethyl-phenol polyoxyethylene phosphate 0.5g, be dissolved among hydrophilic polar solvent ethyl acetate and the methyl alcohol 5g (pressing mass ratio 1: 1) under stirring fast, add entry 62g then and be stirred to clear solution, add hexanol 4g again, fully dissolving stirs in the emulsification still, makes transparent emulsifier aqueous solution; Solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, stirs 30min to transparent, promptly makes rotenone micro-emulsion.
Test of pesticide effectiveness method with reference to embodiment 1, carry out the test of pesticide effectiveness, experimental results show that under the identical situation of the spraying medicine concentration of rotenone, the present embodiment rotenone micro-emulsion have a good control efficiency, its control efficiency is apparently higher than 2% rotenone micro-emulsion of the prior art.
Embodiment seven
Take by weighing rotenone 3.8g, be dissolved in the ethyl acetate, dimethyl formamide, N-Methyl pyrrolidone mixture of 38g in (pressing mass ratio 1: 1: 1); Take by weighing alkylphenol polyoxyethylene 4.0g, castor oil polyoxyethylene ether 3.0g, triphen ethyl-phenol polyoxyethylene phosphate 0.3g, be dissolved among hydrophilic polar solvent methyl alcohol, ethanol, n-butanol (pressing mass ratio 1: 1: the 1) 6.7g under stirring fast, add entry 41.2g stirring and dissolving then to transparent, add hexanol 3g again, fully dissolving in the emulsification still, stir, make transparent emulsifier aqueous solution; Solution with rotenone under high-speed stirred joins in the aqueous solution of emulsifier, stirs 30min to transparent, promptly makes rotenone micro-emulsion.
Test of pesticide effectiveness method with reference to embodiment 1, carry out the test of pesticide effectiveness, experimental results show that under the identical situation of the spraying medicine concentration of rotenone, the present embodiment rotenone micro-emulsion have a good control efficiency, its control efficiency is apparently higher than 2% rotenone micro-emulsion of the prior art.
The present invention can also be according to the multiple rotenone micro-emulsion of being combined to form of above-mentioned component and content, and these microemulsions all have good control efficiency, and its control efficiency is all apparently higher than 2% rotenone micro-emulsion of prior art.

Claims (7)

1. rotenone micro-emulsion is characterized in that containing by mass percentage:
Rotenone 3~6%
Solvent 20-40%
Composite anion-nonionic emulsifier 9-20%
Assistant for emulsifying agent 0.1-5%
All the other waters complement to 100%
Described composite anion-nonionic emulsifier by mass percentage, tween is 40-80%, anion surfactant is 1-10%, surplus is hydrophilic polar solvent;
Described tween is made up of two or more non-ionic surface active agents, and by mass percentage, wherein the content of any one non-ionic surface active agent is not higher than 80%.
2. rotenone micro-emulsion according to claim 1 is characterized in that described solvent is one or more the combination in ether, acetone, cyclohexanone, ethyl acetate, dimethyl formamide, the N-Methyl pyrrolidone.
3. rotenone micro-emulsion according to claim 1 is characterized in that described assistant for emulsifying agent is one or more the combination in propyl alcohol, hexanol, octanol, isobutanol, ethylene glycol, glycerine, cyclohexanol, methyl diethylene glycol (DEG), ethyl diethylene glycol (DEG), castor oil, the lauryl sodium sulfate.
4. rotenone micro-emulsion according to claim 1 is characterized in that described non-ionic surface active agent is benzylphenol APEO, alkaryl phenol polyethenoxy ether phosphate, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, castor oil polyoxyethylene ether, styryl phenyl APEO or polyol fatty acid ester.
5. rotenone micro-emulsion according to claim 1 is characterized in that described anion surfactant is one or more the combination in alkylbenzenesulfonate, ether alcohol sulfate, triphen ethyl-phenol polyoxyethylene phosphate and the sulphate.
6. rotenone micro-emulsion according to claim 1 is characterized in that described polar solvent is one or more the combination in methyl alcohol, ethanol, n-butanol, the ethyl acetate.
7. rotenone micro-emulsion according to claim 1, it is characterized in that by mass percentage: described rotenone content is 3%, solvent is a cyclohexanone, content is 26.7%, composite anion-nonionic emulsifier is 16%, assistant for emulsifying agent is a castor oil, and content is 1.3%, and the surplus water supplies 100%; Described composite anion-nonionic emulsifier is: by mass percentage, tween is 54.1%, and anion surfactant is a calcium dodecyl benzene sulfonate, and content is 4.1%, and surplus supplies 100% with polar solvent methyl alcohol; Described tween is: by mass percentage, and fatty alcohol-polyoxyethylene ether 38.5%, OPEO 61.5%.
CN200910041257A 2009-07-20 2009-07-20 A kind of rotenone micro-emulsion Pending CN101611708A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102423297A (en) * 2011-12-23 2012-04-25 厦门金达威集团股份有限公司 Self-microemulsion and preparation method thereof
CN104814021A (en) * 2015-03-31 2015-08-05 广西大学 Insecticidal composition containing rotenone and carbosulfan and preparation thereof
CN104970053A (en) * 2015-04-14 2015-10-14 安徽农业大学 Moso bamboo extract emulsion in water and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102423297A (en) * 2011-12-23 2012-04-25 厦门金达威集团股份有限公司 Self-microemulsion and preparation method thereof
CN102423297B (en) * 2011-12-23 2013-11-20 厦门金达威集团股份有限公司 Self-microemulsion and preparation method thereof
CN104814021A (en) * 2015-03-31 2015-08-05 广西大学 Insecticidal composition containing rotenone and carbosulfan and preparation thereof
CN104970053A (en) * 2015-04-14 2015-10-14 安徽农业大学 Moso bamboo extract emulsion in water and preparation method thereof
CN104970053B (en) * 2015-04-14 2018-05-01 安徽农业大学 A kind of mao bamboon extract aqueous emulsion and preparation method thereof

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Application publication date: 20091230