CN102599199B - Microcapsule suspending agent as well as preparation method and application thereof - Google Patents
Microcapsule suspending agent as well as preparation method and application thereof Download PDFInfo
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- CN102599199B CN102599199B CN201210034629.9A CN201210034629A CN102599199B CN 102599199 B CN102599199 B CN 102599199B CN 201210034629 A CN201210034629 A CN 201210034629A CN 102599199 B CN102599199 B CN 102599199B
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Abstract
The invention relates to a microcapsule suspending agent and a preparation method of the microcapsule suspending agent. The microcapsule suspending agent comprises the following components by weight:1.0 part of 50% by mass of pyrethrin crude oil, 1.25 parts of 40% of a rotenone drug substance, 6.75 parts of a mixed solution of cyclohexanone and dimethylbenzene, 2.25 parts of an emulsifying agent,0.75 parts of toluene-2,4-diisocyanate, 0.375 parts of glycerol, 78 parts of a polyvinyl alcohol aqueous solution with the concentration of 0.5 % by mass and 10 parts of an organic acid. The microcapsules are of a spherical shape, and the mean grain size of the microcapsules is 20.78 plus or minus 0.39mum. The preparation method of the microcapsule suspending agent is simple and comprises the following steps: after dissolving core materials, dispersing the dissolved core materials with the emulsifying agent and toluene-2,4-diisocyanate in the polyvinyl alcohol solution, then adding glycerol, forming capsules, and regulating a pH value to prepare the microcapsule suspending agent. The microcapsule suspending agent has a better and more durable preventing and curing effect on aleurodicus dispersus russell and phyllotreta striolata than that of the existing rotenone missible oil and pyrethrin missible oil.
Description
Technical field
The invention belongs to pesticide producing processing and operation technique field, be specifically related to a kind of micro-capsule suspension and its preparation method and application.
Background technology
Spiral aleyrodid
aleurodicus dispersusrussell belongs to Homoptera Homoptera, Aleyrodidae Aleyrodidae, and little Aleyrodes, is a kind of polyphagy insect of new invasion.This worm host range is very extensive, and the farm-forestry crop such as fruit tree to Hainan Province, ornamental plants, street tree causes seriously causes harm.The generation of spiral aleyrodid the agriculture and forestry of Hainan and even China mainland are produced all form greatly and threaten [Liu Kui etc., the field control effectiveness test of common insecticide to new invasion insect spiral aleyrodid. Chinese agronomy circular, 2007,23(12): 333-337].At present, the control of spiral aleyrodid mainly adopt chemical pesticide [Wen HC, Hsu TC, and Chen CN. Yield loss and control of spiralling whitefly (
aleurodicus dispersusrussell). Journal of Agricultural Research of China. 1995,44 (2): 147-156; Mariam MA., and Chandram ohan N. Evaluation of chemical insecticides and botan icals against various stages of spiraling whitefly,
aleurodicus dispersusrussel1 on mulberry. Madras Agricultural. 2001,87:379-381; Yao Gang etc., lethality rate and the hatching lethality impact of several agricultural chemicals on spiral vermicelli nit. Agriculture of Anhui science, 2008,36(17): 7316-7317], a large amount of uses of chemical pesticide, not only cause environmental pollution, and can cause agricultural chemicals " 3R " (pesticide resistance resistance, rampant resurgence again, residual residue) generation.Botanical pesticide is efficient, safety, Environmental compatibility are good and meet agriculture and forestry sustainable development requirement.Therefore, the control action by further investigation plant resource active substance to spiral aleyrodid, can provide new approaches and methods for the comprehensive regulation of spiral vermicelli lice, and this is also the study hotspot of preventing and treating at present spiral aleyrodid both at home and abroad.Dubey and Sundararay [Dubey A K., and Sundararaj R. Evaluation of neem products against
aleurodicus dispersusrussell (Aleyrodidae:Homoptera) on Bauhinia variegata and Michelia champaca. Indian Journal of Plant Protection. 2004,32 (2): 126-128] result of study shows that neem extract has good control efficiency to spiral aleyrodid.We have carried out toxicity test with 9 Plants insects active components to spiral aleyrodid, and result shows that pyrethrin, rotenone, nimbin etc. all have very high insecticidal activity to spiral aleyrodid.Further field test results shows, pyrethrin and rotenone emulsion have good quick-acting equally to spiral aleyrodid, but the lasting period only has 1～2 day.How to extend these two kinds of medicaments in the lasting period in field, reducing spraying times is to produce upper problem demanding prompt solution.
Phyllotreta striolata [
phyllotrata triolata(Fabricius)] be one of the important pests of brassicaceous vegetable.Adult food leaf causes a lot of holes on vegetable leaf, and the larva dish root of causing harm has a strong impact on the Quality and yields of vegetables, especially to seedling stage vegetables usually cause destructive harm [Smith E H. Revision of the genus
phyllotretachevrtolat of America north of Mexico. Part 1. The maculate species (Coleoptera:Chrysomelidae, Alticimae). Fieldiana (Zool), 1985,28:1-38; Tian Kunfa. brassicaceous vegetable striped flea-beetle occurs and control. vegetables, 1999, (11): 20-21; Zhang Mao is new, Ling Bing, Liang Guangwen. the investigation of phyllotreta striolata population dynamic and analysis on brassicaceous vegetable. and plant protection, 2000,26 (4): 1-3].In recent years; along with the continuous expansion of brassicaceous vegetable cultivated area; the raising of cropping index; for phyllotreta striolata provides abundant foodstuff source; the Infection and damage of phyllotreta striolata be also on the rise [Nie Hexing. phyllotreta striolata endangers serious reason and Preventing Countermeasures. Agriculture in Hunan science; 2007, (5): 122-124; Shen Jinfa. the generation of phyllotreta striolata and integrated control technique. Fujian agriculture science and technology, 2007, (2): 58-59].Mainly prevent and treat with chemical agent for phyllotreta striolata for a long time; cause phyllotreta striolata population to decline to the susceptibility of insecticide; concentration and the number of times of vegetable grower's applying pesticide constantly increase; Pesticide Residues in Vegetables increases the weight of that [Zhang Mao is new; Ling Bing. the new development of phyllotreta striolata Study of Prevention Technology. plant protection; 2000,26 (6): 31-33; Wang Zeqing. the 10% acetamiprid EC control phyllotreta striolata test of pesticide effectiveness. guangdong agricultural science, 2008, (10): 72-73; Wang Liyan, Sun Qiang, Lin Zhiwei, etc. spring rape flea beetle pests occurrence rule and study on prevention. Heilongjiang Bayi Agricultural Reclamation University's journal, 1997,9 (3): 16-19].Therefore, in the urgent need to developing the new formulation of safety, efficient, low toxicity.It is reported; many plant extractss have food refusal, avoid the effect such as keep away phyllotreta striolata; this control that is phyllotreta striolata provides a new way [Shen Changpeng; Luo Wanchun; Mu Wei; Deng. the field control action of sophora alopecuroides extract mixture to Cruciferous Vegetable Pests. Laiyang Agricultural College journal, 1998,15 (3): 195-200; Hou Youming, the outstanding people's livelihood, Pang Xiongfei, etc. plant protection product defendance moral is simulated phyllotreta striolata control action. life science, 2001,5 (4): 362-369; Zhao Hui, Zhang Mao is new, Ling Bing, etc. non-host plant volatile oil on the sense of smell of phyllotreta striolata adult, take food and the impact of the behavior of laying eggs. Agricultural University Of South China's journal (natural science edition), 2003,24 (2): 38-40].Prevent and treat phyllotreta striolata by pyrethrin (pyrethrins) and rotenone (rotenone) mixture and have not yet to see report.
Pyrethrin (pyrethrins) is two kinds of plant insecticides different to insect mechanism of action with rotenone (rotenone).Pyrethrin be from pyrethrum flowers (
pyreyhrum cineriifoliuntrebr) in, the mixture of active principles with insecticidal effect of separating and extracting, is mainly made up of pyrethrin I (pyrethrins I), pyrethrin II (pyrethrins II).Act on the nervous system of insect, insect is knocked down active strong, to people and animals' low toxicity, low-residual, can be used for preventing and treating the insect [Chen Fengying etc. such as prodenia litura, cabbage caterpillar, Americal rice leaf miner and vegetable aphid, 5% pyrethrin missible oil control prodenia litura field control effectiveness test. Jiangxi plant protection, 2005,28 (2): 84-85; Lu Jijun etc., the 5% natural pyrethrin cream control cucumber Americal rice leaf miner test of pesticide effectiveness. rural science and technology, 2009, (8): 46; Wang Zhongwei etc., 1.5% pyrethrin EW control brassicaceous vegetable aphid test. Chinese gardening digest, 2010, (1): 172-173].Rotenone (rotenone) is the material that has insecticidal activity extracting from the plants such as Derris, belong to flavonoids, the mode of action to insect is comprehensive, mainly action of contace poison and stomach poison function, also have certain Antifeedant Effects, suppress [the Xu Hanhong such as the effect of growing and ovicidal action, pesticide plant and vegetable insecticide. Chinese agriculture publishing house, 2001:289-309].Can be used for preventing and treating multiple aphid, lepidoptera pest and stored grain insects [Nawrot etc., Antifeeding activity of rotenone and some derivatives towards selected insect storage pests. Biochem. System. Ecol., 1989,17 (1): 55-57; Zhao Shanhuan and yellow clear glad, rotenone insecticide safely and efficiently. plant protection, 1988,14(1): 44-45; Mo Meihua, yellow Zhang Xin, the toxic effect research to vegetable-crop pest-insect of rotenone and mixture thereof. Agricultural University Of South China's journal, 1994,15(4): 58-62; Xu Hanhong, Zhang Yeguang, Huang Jiguang etc., the impact on cabbage caterpillar and pupal cell wall of Africa mountain soya bean extract and rotenone. Agricultural University Of South China's journal, 2001,22(2): 27-30; Xu Hanhong, pesticide plant and vegetable insecticide. Chinese agriculture publishing house, 2001:289-309].Rotenone is a kind of respiration inhibitor that acts on electron transport chain, the electron transport chain of insect cell is suppressed, thereby makes insect can not get energy supply, growth retardation, drumble and slowly dead.Pyrethrins different mechanism of action is mixed with rotenone use and may delay the drug-fast generation of spiral aleyrodid.But, this two Plants insecticide is owing to containing the unstable groups such as two keys, ester bond in its molecule, in environment, running into air, illumination, acid, alkali and water etc. easily decomposes, be applied in residence time on crop short, make the defect that existing rotenone emulsifiable solution, particularly pyrethrin missible oil are poor at field application existence and stability, the lasting period is short.
Microcapsule method is an important application technology in formulations of pesticide preparation, compared with conventional pesticide formulation, microcapsules have protective core materials/substances to be avoided the impact of environmental condition, the decomposition rate of pesticide activity component is slowed down, reduces pesticide activity component volatilization loss, thereby improve the availability of active component, extend its lasting period, reduce the advantage such as number of times and frequency [the bear China etc. of dispenser, determining of rotenone microcapsule parameter. Pesticide Science journal, 2005,7 (2): 165-170; Fu Guohui etc., the application of microcapsules technology in the formulations of pesticide. Jiangxi chemical industry, 2004, (1): 10-13].But after agricultural chemicals has carried out being coated, declining often appears in its quick-acting.Document Investigation result shows, the published preparation method who has pyrethrin microcapsule formulations and rotenone microcapsule agent at present.Inventor discloses pyrethrin and nimbin mixed microcapsule formulations preparation method accepting in patent (application number is 201110222275.6).But the report of the synergy microcapsules that pyrethrin mixes with other drug is still little.There is not a kind of vegetable insecticide micro-capsule suspension that is applicable to prevent and treat phyllotreta striolata of report yet.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of micro-capsule suspension being made up of the former medicine of rotenone and pyrethrin crude oil is provided, described micro-capsule suspension is greater than 100 to the co-toxicity coefficient of spiral aleyrodid, demonstrates obvious synergy; The control efficiency of phyllotreta striolata is also obviously better than to it and uses separately, meanwhile, it can maintain high control efficiency in a long time.
Another object of the present invention is to provide the preparation method of described micro-capsule suspension.
Another object of the present invention is to provide the application of described micro-capsule suspension.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of micro-capsule suspension, described micro-capsule suspension is made up of the following component of calculating by weight:
1.25 parts of the former medicines of 40 quality % rotenone;
50 1.0 parts of quality % pyrethrin crude oil;
6.75 parts of the mixed solutions of cyclohexanone and dimethylbenzene;
2.25 parts of emulsifier;
Toluene-2,4-diisocyanate, 0.75 part of 4-vulcabond;
0.375 part of glycerine;
Polyvinyl alcohol concentration is 78 parts of the aqueous solution of 0.5 quality %;
10 parts of organic acids;
50 quality % pyrethrin crude oil and the former medicine of 40 quality % rotenone form the core of described microcapsules;
Toluene-2,4-diisocyanate, 4-vulcabond and glycerine form the cyst wall of described microcapsules.
Cyclohexanone-dimethylbenzene mixed solution is a kind of solvent in system, dissolves core; Polyvinyl alcohol water solution is dispersion.There is following relation in the mass ratio between described each component: the mixed solution of cyclohexanone and dimethylbenzene: core is 3:1; Emulsifier: the mixed solution of cyclohexanone and dimethylbenzene is 1:3; Toluene-2,4-diisocyanate, 4-vulcabond: glycerine is 2:1, cyst wall: core is 1:2.In the microcapsules that prepare under such ratio, rotenone embedding rate is 99.40%, and the embedding rate of pyrethrin is 97.44%.
As most preferably scheme of one, described emulsifier most preferably is agriculture breast 0206.
The applicant has selected natural plant extract rotenone and pyrethrin mixture (1:1) to carry out determination of activity to spiral adult whitefly, after result shows rotenone and pyrethrin mixture, use has obvious synergistic effect to spiral aleyrodid, its co-toxicity coefficient (CTC) is 115.8, is greater than 100.Due to this two Plants insecticide mechanism of action different to insect, mix use and can delay the drug-fast generation of spiral aleyrodid.And pyrethrin is very strong to the knockdown effect of insect in this two Plants insecticide, after using with, can improve the quick-acting performances of preparation.
Being shaped as of described microcapsules is spherical, and the average grain diameter of described microcapsules is 20.78 ± 0.39 μ m.
The preparation method of described micro-capsule suspension, comprise the steps: to take in proportion rotenone and pyrethrin, add the mixed solution of cyclohexanone and dimethylbenzene that rotenone and pyrethrin are fully dissolved, add Toluene-2,4-diisocyanate, after 4-vulcabond, emulsifier mix, join in polyvinyl alcohol water solution, after stirring and emulsifying, add glycerine, under room temperature, stir and carry out polymerisation, encystation, with organic acid for adjusting pH value to 6 ~ 6.5, obtain described micro-capsule suspension.
As a kind of preferred version, the rotating speed of described stirring and emulsifying is preferably 800～1000r/min, and the speed of agitator of polymerisation is preferably 200r/min, and polymerization reaction time is preferably 30min.
As a kind of preferred version, described organic acid is preferably 20 volume % acetic acid solutions.
The 40 former medicines of quality % rotenone described in the application and 50 quality % pyrethrin crude oil, be all to purchase on the market the available rotenone or the pyrethrin that obtain of extracting from natural plants, do not contain other auxiliary agent.
Commercially available another product in addition, 5% rotenone emulsifiable solution or 2% pyrethrin microemulsion, be to have added the appropriate auxiliary agent that can improve rotenone or pyrethrin activity.
As most preferably scheme of one, prepare micro-capsule suspension of the present invention with following process conditions:
Take in proportion the former medicine 1.25g of 40 quality % rotenone and 50 quality % pyrethrin crude oil 1.0g(make the effective mass of final rotenone and pyrethrin account for final products gross mass 1%), fully dissolve with 6.75g cyclohexanone-dimethylbenzene, add 0.75g Toluene-2,4-diisocyanate, after mixing, 4-vulcabond and 2.25g agriculture breast 0206 join in the poly-vinyl alcohol solution of 0.5 quality % of 78g, with 800～1000r/min rotating speed stirring and emulsifying.Then add 0.375g glycerine, under room temperature, stir 30min, encystation with 200r/min rotating speed; With 20 volume % acetic acid solutions adjusting pH to 6.0～6.5 of 10g.Make 100g 1% pyrethrin-rotenone mixed type micro-capsule suspension.
Although pyrethrin has the high effect of eliminating to spiral aleyrodid at present, but because it easily decomposes, therefore drug effect is difficult to continue, and expensive (50% approximately 3500 yuan/kilogram of the pyrethrin crude oil of pyrethrin, approximately 1000 yuan/kilogram of the former medicines of 40% rotenone), therefore, rotenone provided by the present invention and pyrethrin mixture microcapsules, the drug effect that has extended on the one hand pyrethrin still keeps the high effect of eliminating simultaneously, has also significantly reduced on the other hand production cost.
Pyrethrin of the present invention and rotenone mixed type microcapsules are to the obvious inhibitory action of having taken food of phyllotreta striolata, and the lasting period, effect was remarkable obviously than the prolongation of independent use 5% rotenone emulsifiable solution or 2% pyrethrin missible oil 2 ~ 3 days.
Compared with prior art, the present invention has following beneficial effect:
The applicant has selected natural plant extract rotenone and pyrethrin mixture to carry out determination of activity to spiral aleyrodid, after result shows rotenone and pyrethrin mixture, use has obvious synergistic effect to spiral aleyrodid, its co-toxicity coefficient (CTC) is 115.8, is greater than 100; The active ingredient embedding rate of micro-capsule suspension of the present invention is high, and heat storage and cold storage good stability have good controlled release properties simultaneously; Rotenone of the present invention and pyrethrin mixture micro-capsule suspension are being sprayed onto while preventing and treating spiral aleyrodid and phyllotreta striolata on crop, average preventive effect is than more than spraying separately pyrethrin missible oil or having extended 2～3d respectively in the lasting period of rotenone emulsifiable solution formulation, and cost accounting reduces greatly; The preparation technology of micro-capsule suspension of the present invention is simple, is easy to industrialization.
Accompanying drawing explanation
Fig. 1 is microcapsule preparation process flow chart of the present invention;
Fig. 2 is the stereo micrograph of microcapsules of the present invention;
Fig. 3 is the laboratory tests of microcapsules of the present invention to spiral adult whitefly lasting effect.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but embodiments of the present invention is not limited in any way.
The test method using in embodiment if no special instructions, is conventional method; The material, the reagent etc. that use if no special instructions, are reagent and the material that can obtain from commercial channels.
5% rotenone emulsifiable solution (Yunnan Nan Bao plant Co., Ltd), refers to and contains the missible oil that rotenone effective content is 5 quality %, has wherein added the auxiliary agent that strengthens drug effect.
2% pyrethrin missible oil (Yunnan Nan Bao plant Co., Ltd), refers to and contains the missible oil that pyrethrin effective content is 2 quality %, has wherein added the auxiliary agent that strengthens drug effect.
The former medicine of 40% rotenone (purchased from Yunnan Nan Bao plant Co., Ltd), refers to directly from natural plants, to extract to obtain, and containing other additive, rotenone effective content is the former medicine of the rotenone of 40 quality %.
50% natural pyrethrosin primary oil (purchased from Yunnan Nan Bao plant Co., Ltd), refers to directly from natural plants, to extract to obtain, and containing other additive, pyrethrin effective content is the pyrethrin crude oil of 50 quality %.
embodiment 1rotenone and the mensuration of pyrethrin mixture to the synergistic effect of spiral aleyrodid
The conventional abundant grade of Sun Yun of the synergistic effect (chief editor of Agricultural University Of South China of two kinds of mixed pesticides; chemical protection of plant (second edition). Beijing: agriculture publishing house; 1990) co-toxicity coefficient (Co-toxicity coefficient) proposing judges; it is synergistic effect that the co-toxicity coefficient of obtaining by poison exponent (Toxicity indexes) is significantly greater than at 100 o'clock, and equaling 100 o'clock is summation action.So we have measured the co-toxicity coefficient to spiral adult whitefly after rotenone mixes in the ratio of effective content 1:1 with pyrethrin.Concrete assay method is as follows:
Test liquid preparation: with the former medicine of 5% rotenone (Yunnan Nan Bao plant Co., Ltd), 2% pyrethrin crude oil (Yunnan Nan Bao plant Co., Ltd) and rotenone-pyrethrin in the ratio mixture of effective content 1:1, according to indication result of the test, first prepare respectively the mother liquor of every kind of reagent agent with acetone, then be diluted to 5 concentration with clear water, add clear water as contrast take acetone.
Mist measuring method: the leaf dish of getting olive kernel leaf sheet and be cut into diameter d=7cm, put into the culture dish (diameter d=7cm) that is lined with moistening filter paper, 30～35 of access spiral adult whiteflies, the culture dish that connects worm is put in Potter spray tower, spray tower debugging pressure is 65kPa, every processing 1ml liquid of quantitatively spraying, the sedimentation time is 10s.3 repetitions are established in every processing.The dead borer population of 24h investigation spiral adult whitefly after processing, calculation correction lethality.Then, obtain respectively the mixed toxicity regression linear equation of rotenone, pyrethrin and rotenone and pyrethrin 1:1, calculate respectively their LC with this
50the co-toxicity coefficient (CTC) of value and confection.Result of the test is in table 1.
Synergistic effect to spiral adult whitefly after table 1 rotenone and pyrethrin mixture
Note: A+B(1:1) refer to that the former medicine of rotenone and pyrethrin crude oil compare mixture by the quality of effective content 1:1.
As known from Table 1, rotenone, pyrethrin and pyrethrin and the LC of rotenone 1:1 mixture to spiral adult whitefly
50value is respectively 12.71mg/L, 0.82 mg/L and 1.33mg/L.Be 115.8 by the co-toxicity coefficient (CTC) that calculates confection, be greater than 100, show that the use of rotenone and pyrethrin (1:1) mixture has obvious synergistic effect to spiral adult whitefly.
embodiment 2determining of pyrethrin and nimbin mixed type micro-capsule suspension preparation parameter
(1) selection of solvent
Consider the factors such as toxicity, safety, volatility, chemical property and the solubility property to Dalmatian chrysanthemum, rotenone of solvent, selected the solvent of cyclohexanone-dimethylbenzene mixed solvent as pyrethrin-rotenone mixture.Solubility property measurement result shows (table 2), cyclohexanone and dimethylbenzene are best to the solubility property of Dalmatian chrysanthemum-rotenone mixture, the minimum amount that can all dissolve Dalmatian chrysanthemum-rotenone mixture is respectively 2 times of mixture quality ratio and 2.5 times (in literary composition, not indicated is mass ratio), for preventing the impact of the factors such as temperature on dissolution with solvents degree, determine that solvent load is 3 times of mixture quality.
The dissolving situation of table 2 different solvents to Dalmatian chrysanthemum-rotenone mixture
Note: "-" number represents insoluble or be partly dissolved, and "+" number represents all to dissolve
(2) selection of emulsifier
At a certain amount of Dalmatian chrysanthemum-rotenone mixture, cyclohexanone-dimethylbenzene mixed solvent and Toluene-2,4-diisocyanate, in the oil-phase solution of 4-vulcabond (TDI) composition, add the emulsifier that accounts for oil phase quality 20%, mix rear with this mixed liquor of syringe absorption 0.5mL, slowly inject about 2cm place above the 100ml test tube liquid level of 100ml standard hard water is housed, by the grade scale observed and recorded of table 3 emulsion dispersion and the stable emulsifying proterties (in table 4) of 11 kinds of emulsifier.
The classification of table 3 emulsifier emulsion dispersion and stable emulsifying proterties in hard water
The emulsifiability of table 4 emulsifier to oil phase
Result of the test shows (table 4), in each emulsifier or emulsifier hybrid combining, emulsion dispersion and the stable emulsifying performance of emulsifier 0206 to oil phase is best, can be at 100 mg/L, 342 mg/L, in the standard hard water of a 500 mg/L concentration, be cloud rapid dispersion, and leaving standstill after 1h without missible oil and Precipitation, can meet the emulsifiability requirement to oil phase.Therefore preparing with interfacial polymerization in the technique of microcapsules, select the emulsifier of agriculture breast 0206 as oil phase.
(3) Orthogonal Optimization Test of pyrethrin and rotenone mixed type microcapsule wall material and dispersant dosage
The mensuration of pyrethrin-rotenone mixed type microcapsule formulations embedding rate is with reference to [Zheng Mingdong etc. such as Zheng Mingdong, chemical engineering data modeling and assay optimization design. Hefei: publishing house of China Science & Technology University, 2001:93-116] method, have the cyst wall of material impact and core proportioning, TDI and glycerine proportioning and 3 factors of polyethylene of dispersing agent alcohol consumption to carry out Orthogonal Optimum Design on affecting the performance parameter of pyrethrin and rotenone mixed type micro-capsule suspension, the Orthogonal Experiment and Design of 3 factor 3 levels is in table 5.
Table 5 orthogonal experiment factor level table
The mensuration of pyrethrin and rotenone mixed type microcapsule formulations embedding rate is with reference to [Tang Jingen etc. such as Tang Jingen, the HPLC analytical method of cyanogen-horse microcapsule formulations. forestry science and technology exploitation, 1997, (1): 30-31], [the Ye Min etc. such as Ye Min, the capillary gas chromatography quantitative analysis of natural pyrethrum. research and development of natural products, 2009, 21:27-29, 35] and Zhang Shanxue [Zhang Shanxue, extraction separation and the bioactivity research thereof of derride. Agricultural University Of South China, 2002] etc. method is measured respectively the embedding rate of pyrethrin and rotenone in pyrethrin and rotenone mixture microcapsule formulations.Orthogonal Optimization Test design result is in table 6 and table 7.
From table 6 and table 7 result, when cyst wall and the ratio of capsule-core are that 1:2, cyst material TDI are 2:1 with the ratio of glycerine, when dispersant dosage is 0.5%, in the pyrethrin-rotenone microcapsule of gained, the embedding rate of nimbin and pyrethrin is best, now rotenone embedding rate is 99.40%, and the embedding rate 97.44 of pyrethrin is %.
By above-mentioned test, the best technology of preparing parameter of pyrethrin and rotenone mixed type micro-capsule suspension is: solvent cyclohexanone-dimethylbenzene: capsule-core is 3:1, cyst wall: capsule-core is 1:2, emulsifier: solvent is 1:3, encystation monomer TDI: glycerine is 2:1, the content of polyethylene of dispersing agent alcohol in water is 0.5mg/g, with 800～1000r/min rotating speed stirring and emulsifying, stir polymerisation 30min, encystation with 200r/min rotating speed.
Table 6 optimization of orthogonal test design and rotenone embedding rate measurement result
In table 6, the level 1,2,3 in numeral 1,2, the 3 corresponding tables 5 in T-1 ~ T-9.
Table 7 optimization of orthogonal test design and pyrethrin embedding rate measurement result
In table 7, the level 1,2,3 in numeral 1,2, the 3 corresponding tables 5 in T-1 ~ T-9.
embodiment 3optimization Technology is prepared pyrethrin and rotenone mixed type micro-capsule suspension
(1) Fig. 1 is shown in the technological process of micro-capsule suspension of the present invention.
(2) prepare the step of 100g 1% pyrethrin-rotenone (1:1) mixed type micro-capsule suspension with above-mentioned optimum preparating condition as follows:
Taking 50% pyrethrin crude oil 1.0g and 40% nimbin raw medicine 1.25g(is that active ingredient is than being 1:1), fully dissolve with 6.75g cyclohexanone-dimethylbenzene mixed solvent, add 0.75g Toluene-2,4-diisocyanate, after mixing, 4-vulcabond (TDI) and 2.25g emulsifier 0206 join in 0.5% dispersant (polyvinyl alcohol) solution of 78g, with 800～1000r/min rotating speed stirring and emulsifying 10min.Then add 0.375g the second cyst material glycerine, under room temperature, stir 30min, encystation with 200r/min rotating speed.With 20% acetic acid solution adjusting PH to 6.0～6.5 of 10g.
(3) pyrethrin and rotenone mixed type microcapsules shape are observed
Pyrethrin-rotenone mixed type microcapsules prepared by said method are subsphaeroidal, see Fig. 2.
Get pyrethrin-rotenone mixed type micro-capsule suspension dilution drop on slide, under stereoscope, choose at random 10 visuals field, the particle diameter of 10 microcapsules of each perimetry, observes 100 microcapsules altogether, and obtaining its average grain diameter is 20.78 ± 0.39 μ m.
embodiment 4the hot and cold storage test of pyrethrin and rotenone mixed type micro-capsule suspension
Get 2 parts of 1% pyrethrin that embodiment 3 obtains and rotenone mixed type micro-capsule suspensions in wide-mouth bottle, be placed in respectively 50 ± 2 ℃ and 0 ℃ of environmental condition and store 7d.Then detect the changes of contents of rotenone with HPLC, calculate as follows the degradation rate of rotenone in microcapsules:
Degradation rate (%)=(the rear rotenone content of rotenone content-processing before processing)/rotenone content × 100 before processing
The hot and cold storage Stability Determination of rotenone in table 8 1% Dalmatian chrysanthemum-rotenone microcapsule
As can be seen from Table 8,1% pyrethrin-rotenone mixed type microcapsules have good hot and cold storage stability.Through cold storage (0 ℃) and heat storage (50 ± 2 ℃) test of 7d, the degradation rate of rotenone is respectively 5.51% and 6.32%, and between microcapsules, without hardening phenomenon, microcapsules shape is unchanged, and without broken capsule, requirement conforms with the regulations.
embodiment 5pyrethrin and the toxicity test of rotenone mixed type micro-capsule suspension to spiral aleyrodid
Adopt spraying method and medicine embrane method to measure respectively 1% pyrethrin-rotenone mixed type micro-capsule suspension that embodiment 3 obtains, 50% pyrethrosin primary medicine and the virulence of the former medicine of 40% rotenone to spiral aleyrodid.Spray-on process is with embodiment 1.
Medicine embrane method is that the TERMINALIA CATAPPA blade shearing is laid in the culture dish (diameter is 7cm) that is lined with filter paper.Then will prepare medicine liquid spray to TERMINALIA CATAPPA leaf before with spray tower, every 1ml that repeats to spray, each processing is established repetition 3 times, take clear water as contrast.After liquid natural air drying etc. TERMINALIA CATAPPA leaf surface, access spiral adult whitefly, the lethality of 24h statistics spiral aleyrodid.
As can be seen from Table 9, no matter be spray-on process or medicine embrane method, pyrethrin-rotenone (1:1) mixed type micro-capsule suspension is processed 24h has obvious action of contace poison to spiral aleyrodid, obviously improves than the toxic action of independent use rotenone.
Table 9 pyrethrin and the virulence of rotenone mixed type micro-capsule suspension to spiral aleyrodid
embodiment 6the lasting effect test of pyrethrin-rotenone mixed type micro-capsule suspension to spiral aleyrodid and phyllotreta striolata
(1) mensuration of 1% pyrethrin-rotenone (1:1) mixed type micro-capsule suspension that embodiment 3 makes to spiral aleyrodid lasting effect
The 1000 times of liquid of 1% pyrethrin-rotenone (1:1) mixed type micro-capsule suspension that make with embodiment 3 and commercially available 1000 times of liquid of 5% rotenone emulsifiable solution (Yunnan Nan Bao plant Co., Ltd) and 3000 times of liquid of 2% pyrethrin missible oil (Yunnan Nan Bao plant Co., Ltd) have been measured their holding effect performances to spiral adult whitefly under laboratory condition.Assay method is that the TERMINALIA CATAPPA blade shearing is laid in the culture dish (diameter is 7cm) that is lined with filter paper.Then use manual sprayer (50ml) by the medicine liquid spray preparing to TERMINALIA CATAPPA leaf, till squirting.Take clear water as contrast.12 blades of every kind of chemicals treatment, wait after the liquid natural air drying of processing TERMINALIA CATAPPA leaf surface with preservative film sealing and on preservative film, prick aperture.Respectively at the same day, 1d, 2 d and 3 d that process, in every chemicals treatment, get 3 blades as 3 repetitions, often repeat to access 35～45 of spiral adult whiteflies, record respectively the dead borer population of 24h and calculate lethality, the results are shown in Figure in 3, Fig. 3 on the same day alphabetical identical person in data represents through DMRT check difference in 1% level not remarkable.
As can be seen from Figure 3, spray medicine accessed spiral adult whitefly after 24h the same day, and the examination worm lethality of the 3 kinds of chemicals treatment all utmost point, significantly higher than contrast, shows good control efficiency.Wherein, the examination worm average mortality of pyrethrin and rotenone mixed type microcapsules and pyrethrin missible oil processing is the highest, reaches 100%; Next is rotenone emulsifiable solution processing, and examination worm average mortality reaches 91.84%.Spray medicine 2d connects worm, the spiral aleyrodid lethality of pyrethrin missible oil and rotenone emulsifiable solution processing is all starkly lower than the processing of pyrethrin-rotenone microcapsule, only have 71.0～74.5%, the spiral aleyrodid lethality of pyrethrin-rotenone mixing microcapsule suspending agent processing is still more than 94.96%; Spray medicine 3d, the spiral aleyrodid lethality of pyrethrin missible oil processing only has 24.1%; And pyrethrin-rotenone mixed type micro-capsule suspension and rotenone emulsifiable solution spray medicine to spiral aleyrodid lethality rate still 74.1%～75.8%.These results show, prevent and treat spiral adult whitefly and not only just imitate, and the drug effect phase also obviously extends with 1% pyrethrin-rotenone (1:1) mixed type micro-capsule suspension.
(2) the control test to phyllotreta striolata adult of 1% pyrethrin that embodiment 3 makes and rotenone (1:1) mixed type micro-capsule suspension
1% pyrethrin that 5% rotenone emulsifiable solution, 2% pyrethrin missible oil and embodiment 3 are made and rotenone (1:1) mixed type micro-capsule suspension are diluted with water to for examination concentration (in table 10).Be sprayed onto equably and be planted in flowerpot (flowerpot diameter is 10cm for reagent liquid different with manual sprayer, high 9.5 cm) in cabbage heart seedling on (cabbage heart kind is the dark green rape heart, cotyledon period, every basin has seedling 25 strains), until Brassica campestris leaves positive and negative all squirts, to spray clear water as contrast.Disposable processing 12 basins of every processing.After liquid natural air drying on dish seedling, in the random 3 ready-to-cook dish of meat, vegetables, etc. hearts that take out of spray medicine every processing on the same day, in each flowerpot upper cover, be 9cm with the diameter that transparent film paper is made, the cylinder of high 15cm, then access 10 of the phyllotreta striolata adults of hungry 3h, will after cylinder end sealing, live by culture dish cover buckle again with preservative film.The dish seedling of other processing covers with a large dependent insect cage, avoids phyllotreta striolata to cause harm.After spray medicine, within the 2nd day, the 3rd day, the every processing seedling in large dependent insect cage, take out at random again the 3 ready-to-cook dish of meat, vegetables, etc. hearts respectively, then connect worm, cylindrical cap on cover.All after meeting worm 24h and 48h, add up phyllotreta striolata on cabbage heart seedling cause harm the worm channel number and the examination worm lethality that take food.
Investigation result statistical analysis shows, in each processing, lethality and the contrast difference of phyllotreta striolata adult are not remarkable, but between worm channel number on different disposal cabbage heart seedling and compared with the control difference reaches utmost point significance level.Therefore, calculated the control efficiency of each processing to phyllotreta striolata with following formula:
Worm channel number × 100 of control efficiency (%)=(the worm channel number of the worm channel number-processed group of control group)/control group
Table 10 1% pyrethrin and the control efficiency of rotenone (1:1) mixed type micro-capsule suspension to phyllotreta striolata
As can be seen from Table 10,1% pyrethrin and rotenone mixed type microcapsules are to the obvious inhibitory action of having taken food of phyllotreta striolata, and the lasting period is obviously than the length that uses separately 5% rotenone emulsifiable solution and 2% pyrethrin missible oil.In the time of 62.5 mg/L concentration, the control efficiency of 1～2d is suitable with the independent effect of 5% rotenone emulsifiable solution (62.5 mg/L) that uses, but when 3～4d, using the control efficiency of 5% rotenone emulsifiable solution processing is separately zero, and the control efficiency of 1% pyrethrin and the processing of rotenone mixed type microcapsules is still 30.91～47.24%.Even more than the lasting period of 1% pyrethrin of low concentration and rotenone mixed type microcapsules processing (25 mg/L and 43.75mg/L) also can reach 4d.The inhibitory action that uses 2% pyrethrin missible oil spraying (concentration is 25 mg/L) to take food phyllotreta striolata is lower, and control efficiency is 27.36%, and the lasting period only has 1d.
Show from above result, control efficiency and the lasting period of pyrethrin-rotenone mixed type microcapsule formulations to spiral aleyrodid and phyllotreta striolata is all better than 5% rotenone emulsifiable solution and 2% pyrethrin missible oil.
Claims (4)
1. the application of micro-capsule suspension in control phyllotreta striolata, is characterized in that, described micro-capsule suspension is made up of the following component of calculating by weight:
1.25 parts of the former medicines of 40 quality % rotenone;
50 1.0 parts of quality % pyrethrin crude oil;
6.75 parts of the mixed solutions of cyclohexanone and dimethylbenzene;
2.25 parts of emulsifier;
Toluene-2,4-diisocyanate, 0.75 part of 4-vulcabond;
0.375 part of glycerine;
Polyvinyl alcohol concentration is 78 parts of the aqueous solution of 0.5 quality %;
10 parts of organic acids;
50 quality % pyrethrin crude oil and the former medicine of 40 quality % rotenone form the core of described microcapsules;
Toluene-2,4-diisocyanate, 4-vulcabond and glycerine form the cyst wall of described microcapsules;
Described emulsifier is agriculture breast 0206;
Being shaped as of described microcapsules is spherical, and the average grain diameter of described microcapsules is 20.78 ± 0.39 μ m.
2. application as claimed in claim 1, it is characterized in that, the preparation method of described micro-capsule suspension, comprise the steps: to take in proportion rotenone and pyrethrin, add the mixed solution of cyclohexanone and dimethylbenzene that rotenone and pyrethrin are fully dissolved, add Toluene-2,4-diisocyanate, after mixing, 4-vulcabond, emulsifier join in polyvinyl alcohol water solution, after stirring and emulsifying, add glycerine, under room temperature, stir and carry out polymerisation, encystation, with organic acid for adjusting pH value to 6 ~ 6.5, obtain described micro-capsule suspension.
3. application as claimed in claim 2, is characterized in that, the rotating speed of stirring and emulsifying is 800～1000r/min, and the speed of agitator of polymerisation is 200r/min, and polymerization reaction time is 30min.
4. application as claimed in claim 2, is characterized in that, described organic acid is 20 volume % acetic acid solutions.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102057955A (en) * | 2010-12-17 | 2011-05-18 | 华南农业大学 | Application of pyrethrin in preventing and controlling Aleurodicus disperses Russell and pyrethrin synergistic composition |
| CN102239890A (en) * | 2011-08-04 | 2011-11-16 | 华南农业大学 | Microcapsule suspension used for preventing and controlling spiraling whitefly and preparation method thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102057955A (en) * | 2010-12-17 | 2011-05-18 | 华南农业大学 | Application of pyrethrin in preventing and controlling Aleurodicus disperses Russell and pyrethrin synergistic composition |
| CN102239890A (en) * | 2011-08-04 | 2011-11-16 | 华南农业大学 | Microcapsule suspension used for preventing and controlling spiraling whitefly and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| 5%鱼藤酮微乳剂对黄曲条跳甲的室内毒力测定;张庭英等;《湖北植保》;20110630(第6期);第9-11页 * |
| Bloszyk E et al..Effectiveness of antifeedant of plant origin in protection of packaging materials against storage insects.《Journal of Applied Entomology》.1990,第110卷(第1期),第96-100页. |
| Effectiveness of antifeedant of plant origin in protection of packaging materials against storage insects;Bloszyk E et al.;《Journal of Applied Entomology》;19901231;第110卷(第1期);第96-100页 * |
| 张庭英等.5%鱼藤酮微乳剂对黄曲条跳甲的室内毒力测定.《湖北植保》.2011,(第6期),第9-11页. |
| 王运儒等.鱼藤酮与除虫菊素对小菜蛾幼虫的协同增效作用.《植保科技创新与病虫防控专业化-中国植物保护学会2011年学术年会论文集》.2011,第241-244页. |
| 鱼藤酮与除虫菊素对小菜蛾幼虫的协同增效作用;王运儒等;《植保科技创新与病虫防控专业化-中国植物保护学会2011年学术年会论文集》;20111231;第241-244页 * |
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Effective date of registration: 20160330 Address after: Moon Road, Science City high tech Industrial Development Zone of Guangzhou City, Guangdong province 510530 No. 80 science and technology innovation base D 607-612 unit Patentee after: GUANGZHOU RUIFENG BIOTECHNOLOGY CO., LTD. Address before: 510642 Tianhe District, Guangdong, No. five road, No. 483, Patentee before: South China Agricultural University |
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Inventor after: Lu Yongyue Inventor after: Lin Xiaojun Inventor after: Jin Xin Inventor after: Ling Bing Inventor after: Wang Jianming Inventor after: Zhang Maoxin Inventor after: Miao Xiaoxing Inventor after: Bao Shulin Inventor after: Cao Xi Inventor after: Li Shenlei Inventor after: Chen Fang Inventor before: Ling Bing Inventor before: Wang Jianming Inventor before: Zhang Maoxin Inventor before: Miao Xiaoxing Inventor before: Bao Shulin Inventor before: Cao Xi |
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