CN103387456A - Polymer-coated controlled release pesticide granule and preparation method thereof - Google Patents
Polymer-coated controlled release pesticide granule and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polymer-coated controlled release pesticide granule and a preparation method thereof. The polymer-coated controlled release pesticide granule comprises a pesticide granule and a polymer layer, wherein the pesticide granule is coated by the polymer layer; the pesticide granule contains one or more effective pesticide components; the polymer layer is a hydrophobic membrane layer and comprises a water-based polyacrylate membrane material or a polyurethane membrane material; the mass of the polymer layer accounts for 3%-15% of the weight of the polymer-coated controlled release pesticide granule. The effective pesticide components are acted on the peripheries of crop roots after the polymer-coated controlled release pesticide granule disclosed by the invention is applied along with a base fertilizer. The polymer-coated controlled release pesticide granule has good prevention and control effects on farmland weeds, soil insects and soil-borne diseases, and the coating material synthesis and preparation process is advanced and the polymer-coated controlled release pesticide granule has good controlled release property. The polymer-coated controlled release pesticide granule provided by the invention has the advantages of pesticide utilization ratio improvement, environment pollution reduction, sustainable development and wide application prospect.
Description
Technical field
The present invention relates to a kind of polymer coated controlled release granular pesticide and preparation method thereof.
Background technology
Agricultural chemicals can prevent, eliminates or control disease, worm, grass and other harmful organisms of harm agricultural, forestry, is that agricultural produce is protected the important guarantee of receiving.According to Food and Argriculture OrganizationFAO (FAO) statistics, the whole world uses the agricultural-food loss that the pesticide control disease and pest is retrieved to account for 30% of total output of grain.China is a large agricultural country, is also a populous nation.Because explosive population growth, the minimizing of ploughing, Agricultural Bio-disasters take place frequently, the grain imbalance between supply and demand increasingly sharpens, and grain security is subject to serious threat.For guaranteeing grain yield, annual have a large amount of agricultural chemicals to put in agriculture production to go, and consumption increases rapidly year by year, and according to statistics, the annual chemical prevention area of China is up to 400,000,000 hectares, and the former medicine year production of chemical pesticide speedup surpasses 20%.This shows, agricultural chemicals has become the requisite means of agricultural production of modern agriculture and has dropped into.
Yet the widespread use of agricultural chemicals has brought serious environmental pollution, when serving the mankind, is also threatening the mankind's health, and the defect of this and Traditional Agricultural pharmaceutically dosage form nature has much relations.After conventional formulation is administered to farmland, always be subject to the effect of infiltration, evaporation, degraded (comprising photodissociation, hydrolysis, microbiological deterioration etc.), easily run off, drug effect is poor, and the lasting period is short.The effective rate of utilization of tradition agricultural chemicals only has 20%～30%, and traditional agricultural chemicals of 90% all can not meet the crop demand aspect lasting period, release characteristics.Pesticide slow-releasing agent can extend the agricultural chemicals lasting period, reduces spraying times, effectively increases operation rate, and reduces effective constituent and runs off, and then reduce and pollute.Therefore, pesticide slow-releasing agent becomes the main direction of pesticide preparation development.
Slow release formulation mainly is divided into physical and chemotype both at home and abroad at present.Physical comprises microcapsule, sorbent material, equal potion and inclusion compounds; Chemotype is for to synthesize by chemical action the inertia derivative (US20060188572, US20030031694, EP1142477, El-Refaie Kenawy, 2001) that contains the pesticide active ingredient group.Chemotype requires harshness to the chemical structure of pesticide active ingredient, need to possess the particular functional group, and development is very limited; Sustained release dosage research is focusing more in the research and development of physical sustained release dosage.
The physical pesticide slow-releasing agent is divided into microcapsule, equal potion, sorbent material and inclusion compounds.Microcapsule be occur the earliest, most study, the most ripe slow release formulation (US20030013612, US7070795, WO2001068234, WO2001068234, US6730635, WO07033931, WO2006092409, CN200810132625), the microcapsule slow release effect is better, applied widely, the effective constituent of having made microcapsule has more than 20 kinds such as fenitrothion 95, parathion-methyl, pyrethrin.But its technique is loaded down with trivial details, and preparation cost is high, and coated fertilizer uses many, and the difficult degradation of film material, easily cause environmental pollution.All potion and sorbent material (Doane, 1990, US5516520, US4439488, CN200810132625, CN1951186A, CN201010534717.6, Cardoso, 2006 etc.) preparation technology is relatively simple, and cost is lower.E.I.Du Pont Company applies for a patent US4435383 and US4557929, has invented a kind of solid particulate agent, with hydrophobic unsaturated monomer vinylbenzene and α-methylstyrenecopolymer,, as matrix, loads agricultural chemicals.Schreiber in 1987 etc. have reported a kind of method with starch xanthate parcel weedicide trifluralin on Weed Science magazine, said preparation is respond well in field experiment; Calendar year 2001 Zhu and Zhuo have reported with starch-vinyl alcohol copolymer and have done matrix on European Polymer Journal magazine, prepare weedicide 2, the equal potion of 4,6-trichlorophenoxyacetic acid, this type of method of making matrix of treated starch also has report in US5516520, CN1951186A; Zhao in 2003 and Wilkins have reported and have a kind ofly made matrix with degradable natural macromolecular material xylogen and load the weedicide fluometuron, prepared the method for particle slow release agent on J.Agric.Food Chem. magazine; Voinova gave to the world the result of one's studies on Applied Biochemistry and Microbiology magazine in 2009, and report is made matrix with the microbial polymer poly-hydroxy fatty acid and loaded the method for sterilant, and the material therefor degradation property is good; Celis equals to report on J.Agric.Food Chem. magazine with inorganic, organic clay in 2002, and absorption weedicide hexazinone, effectively extend the lasting period simultaneously, reduces the leaching loss of agricultural chemicals; EP1142477A2 has described a kind of method for preparing the slow-release solid granular preparation with the charcoal absorption agricultural chemicals; Cardoso equals to report on J.Agric.Food Chem. magazine in 2006 and a kind ofly loads acid herbicide with anion exchange absorbing material water talcum and realize the method for slowly-releasing, adopt same principle, domestic patent CN200710116303 has invented a kind of preparation method of Provado/hydrotalcite-like compounds nano hybrid.Slow release effect is poor, the lasting period is short (slow-release period is generally within a week), the problem of poor stability but equal potion and absorption preparation exist.
On the Research foundation of equal potion and sorbent material,, by outer coating, can effectively extend the lasting period of equal potion and sorbent material, increase its environmental compatibility and resistance, improve safety in utilization.The U.S. is green can wooden company apply for a patent EP1063215 (A2), has described the gac core core that adopts polyacrylate(s) coated fertilizer parcel to adsorb pulvis/pesticide emulsion and has been prepared into pesticide slow-releasing agent.Hargrove has described a kind of multilayer pesticide granules in US Patent No. 6682751, center is nitrogenous fertilizer core core, adopts urethane-acephate homogeneous material to carry out the original position coating, and then with polyurethanes film material, carries out outer coating.Fern á ndez-P é rez etc. report in Carbohydrate Polymers83 (2011) 1672 – 1679: xylogen is evenly mixed under molten state with pyrazon, make equal potion, outer with the material coated pesticide slow-releasing agent that makes of ethyl cellulose after pulverizing,, by adjusting function monomer and content of plasticizing agent in the ethyl cellulose material, realize in release period 10～20 days controlled; Next year, with Flores-C é spedes of seminar etc.,, at J.Agric.Food Chem.2012, reported in 60,1042-1051 that similar approach prepares the method for Provado sustained release dosage.Domestic correlative study focuses mostly in the fertile research and development of controlled release medicine (CN1046887, CN101302130, CN102276356): Nanjing soil institute of the Chinese Academy of Sciences has proposed with granulating method fertilizer and agricultural chemicals granulation in CN1046887, skin adds the mentality of designing of polymeric membrane, but specific embodiment is not quite clear; It is the core core that Zhengzhou University and the fertile patent of invention CN101302130 of Guangxi Tianyuan Biochemical Co., Ltd.'s serial medicine of application, CN102276356, CN201210239491.6 take conventional particles fertilizer; perhaps by the compound fertilizer granulation process, prepare the fertile core core of medicine; skin is granule in pan-type pelletizer; different activities composition used additives layer (clay) is isolated; then directly with the clay coating or transfer to coating equipment in sugar production line and carry out high polymer film-coated; the Product transport for preparing is safe to use, and the composition performance that is mixed is good.CN1951186A has described and a kind ofly with treated starch, has made matrix, loads auxiliary agent and pesticide active ingredient under the gelatinization state, outer method with the vegetables oil coating after granulating and drying.CN102823619A has described the preparation method of a kind of Provado particle slow release agent: after Provado being fixed on the sorbent materials such as clay, gac, molecular sieve, at granulator granulation, skin makes with polymer capsule.
Foreign patent focuses mostly in all potion research, and the high molecular polymer usage quantity is large, and cost is higher.Domestic patent is the rough polymer capsule material of having enumerated several large class commodity only, shortage is studied molecular designing, coating process and the farm chemical release characteristic aspect of material, as: polymerization process and condition (polymerization temperature, stirring velocity, order of addition(of ingredients) etc.), initiator type and consumption, monomeric species, monomer ratio and consumption, form membrane property etc.In addition, have sorbent material and the equal ubiquitous problem of potion: drug loading is little, the lasting period is short, releasing rule is difficult for grasping etc.Therefore, the pesticide action-controlling granule of aforesaid method preparation also is significantly improved and room for promotion.
Summary of the invention
The purpose of this invention is to provide a kind of polymer coated controlled release granular pesticide and preparation method thereof.
Polymer coated controlled release granular pesticide provided by the present invention, be comprised of pesticide granules and the polymer layer of the described pesticide granules of parcel; Wherein, the quality of described polymer layer is the 2%～7%(preferred 3%～5% of described polymer coated controlled release granular pesticide quality);
Described polymer layer is the hydrophobicity rete, and it is comprised of water base polyacrylate(s) film material or polyurethanes film material;
Described pesticide granules is made by the following raw material of 100 mass parts: the auxiliary agent of commercially available various powdered pesticide preparations commonly used or 0～45 part, the former powder of pesticide soluble, 0～75 part of commercially available various powdered fertilizer commonly used and commercially available various liquid pesticide commonly used or 0～20 part of agricultural chemicals stoste and surplus; The content of described powdered pesticide preparation or the former powder of pesticide soluble and described liquid pesticide or agricultural chemicals stoste is not 0 simultaneously, and the content of described auxiliary agent is not 0.
Wherein, described auxiliary agent can be selected from following at least a: activated carbon, zeolite powder, diatomite, kaolin, wilkinite, attapulgite, treated starch, calcium dodecylbenzene sulphonate, sodium laurylsulfonate, OP-10, Tween-60 all needed 80 mesh sieves before use.Described commercially available various powdered pesticide preparations commonly used or the former powder of pesticide soluble can be selected from following at least a: Provado, Chlorpyrifos 94, benbbensulfuronmethyl, Piao's grass are clean, benbbensulfuronmethyl, terbufos, thiram, jingganmycin and hymexazol.Described commercially available various powdered fertilizers commonly used can be selected from following at least a: nitrogen-phosphorus-potassium compound fertilizer, ammonium chloride, urea, volatile salt, ammonium nitrate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, Repone K, vitriolate of tartar and Zinc Sulphate Heptahydrate.Described commercially available various liquid pesticides commonly used or agricultural chemicals stoste can be selected from following at least a: alachlor, acetochlor, metolachlor, Butachlor technical 92 and Stam F-34.
The median size of described pesticide granules is 2～6mm.
Pesticide granules described in the present invention is to prepare according to the method that comprises the steps:
1) auxiliary agent, commercially available various powdered pesticide preparations commonly used or the former powder of pesticide soluble and commercially available various powdered fertilizer commonly used are added in tablets press, mix;
2) add atomized water in the surface spray of mixed material, then on described material surface, at the uniform velocity drip described commercially available various liquid pesticides commonly used or agricultural chemicals stoste, complete granulation;
The pesticide granules that 3) will obtain carries out drying, screening, obtains required 2～6mm grade pesticide granules core core.
Wherein, tablets press described in step 1) is specially adjustable rotating speed
Granulating disc.
In the described mixing process of step 1), the rotating speed of granulating disc is 5～10r/min, preferred 7r/min mixing 5min.
Step 2) in, described granulating disc rotating speed is 25～35r/min, preferred 32r/min.Described atomized water is realized by atomizer; It adds with 10～500g/min flow with peristaltic pump.
When the polymer layer of described polymer coated controlled release granular pesticide is comprised of water base polyacrylate(s) film material, one deck organic matter layer is also wrapped up on the surface of described pesticide granules, and the thickness of described organic matter layer is 2～10 μ m.Described organism can be Viscotrol C or palm fibre oil.
Described in the present invention, the second-order transition temperature of water base polyacrylate(s) film material is 0～60 ℃, and polymericular weight is 10
3～10
8.
Described water base polyacrylate(s) film material carries out polyreaction by the material of following mass parts and prepares: 0.5～2 part of 100 parts of monomers, 0.5～1 part of initiator, 100～150 parts, water and emulsifying agent; Described monomer be following a) or b): a) vinylformic acid and/or acrylate monomer, b) mix monomer of vinylformic acid and/or acrylate monomer and response type function monomer.
1), in reactor concrete preparation method is as follows:, add in mass ratio 100～150 parts, water, 0.5～2 part of emulsifying agent, heating, stir, logical nitrogen, treat that temperature is increased to 70～90 ℃, with 100 parts of described monomers, 0.5～1 part of initiator is added drop-wise in reactor under fully stirring, initiated polymerization, after reaction 2～7h, obtain the emulsion of described water base polyacrylate(s) film material.
described vinylformic acid and/or acrylate monomer are comprised of at least a material of following mass parts: vinylformic acid 0～30, 0～30 part of methyl acrylate, 0～60 part of ethyl propenoate, 0～60 part of butyl acrylate, Hydroxyethyl acrylate 0～40, 0～70 part of methyl methacrylate, 0～50 part of butyl methacrylate, methacrylic acid 0～20, 0～50 part of the different monooctyl ester of vinylformic acid-2-, 0～30 part of n-methylolacrylamide, 0～20 part of glycidyl acrylate, 0～20 part of Viscoat 295, 0～20 part of 0～30 part of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
Described function monomer is comprised of at least a material of following mass parts: 0～60 part of vinylbenzene, 0～30 part of vinyl acetate, 0～25 part of 4-vinylpridine, 0～25 part of 2-vinyl pyridine, 0～10 part of Vinylstyrene.
The OP-10(alkylphenol polyoxyethylene), sodium laurylsulfonate and Sodium dodecylbenzene sulfonate described emulsifying agent is selected from following at least a:.
Described initiator is Potassium Persulphate and/or ammonium persulphate.
The film of polyurethanes described in the present invention material, the raw material of making it comprises: isocyanic ester, polyvalent alcohol, furtherance film and chainextender, wherein in isocyanic ester in isocyano and polyvalent alcohol the mol ratio of institute's hydroxyl group be 1:2～2:1, the furtherance film accounts for 0.1%～30% of described polyurethanes film material total mass, and chainextender accounts for 0%～15% of described polyurethanes film material total mass.
described isocyanic ester is selected from following at least a: tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), naphthalene diisocyanate (NDI), to the phenylmethane vulcabond, Isosorbide-5-Nitrae-bicyclohexane vulcabond, xylylene diisocyanate, the cyclohexanedimethyleterephthalate vulcabond, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, the many phenyl isocyanate of many subunits (PAPI), the liquefaction diphenylmethanediisocyanate, toluene diisocyanate dimer (liquefied mdi, the TDI dimer), tolylene diisocyanate (TDI) tripolymer, tolylene diisocyanate-TriMethylolPropane(TMP) (TDI-TMP) affixture, tolylene diisocyanate-hexamethylene diisocyanate (HDI) biuret, isophorone diisocyanate (IPDI) tripolymer, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4-phenyl isocyanate) and dimethyl triphenyl methane tetraisocyanate.
Described polyvalent alcohol is for containing at least the polyvalent alcohol of 2 hydroxyls, its be selected from following a) and/or b) and/or c) at least a:
Described a) at least a in following polyether glycol: polyoxyethylene polyvalent alcohol, polyoxypropyleneglycol, polyoxytrimethylene triol, polyether triol, polyether tetrols, quadrol polyether glycol, functionality are 3 polyether glycol, polytetrahydrofuran diol, contain the side chain polytetrahydrofuran diol;
Described b) at least a in following vegetable oil polyol: Viscotrol C, soybean oil polyvalent alcohol (containing at least 2 hydroxyls) and plam oil polyvalent alcohol (containing at least 2 hydroxyls);
Described c) be at least a in following polyester polyol: polyethylene glycol succinate, poly butylene succinate and polyethylene glycol adipate.
Described chainextender is selected from following at least a: BDO, 2,3-butanediol, glycol ether, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP) and sorbyl alcohol.
Described furtherance film is selected from following at least a: paraffin, clorafin, sulfonation paraffin and rosin ester.
The raw material of making described polyurethanes film material also comprises catalyzer, and consumption is 0.1%～1% of monomer mass.
Described catalyzer is following at least a for being selected from: dibutyl tin laurate, stannous octoate, triethylamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, diethylenetriamine, triethylenediamine, tetramethyl butane diamine and N-Ethylmorphine quinoline.
A further object of the present invention is to provide the preparation method of above-mentioned polymer coated controlled release granular pesticide.
When the polymer layer of described polymer coated controlled release granular pesticide is comprised of water base polyacrylate(s) film material, the preparation method of described polymer coated controlled release granular pesticide comprises the steps:
1) in reactor, add in mass ratio 100～150 parts, water, 0.5～2 part of emulsifying agent, heating, stir, logical nitrogen, treat that temperature is increased to 70～90 ℃, with 100 parts of monomers, 0.5～1 part of initiator is added drop-wise in reactor under fully stirring, initiated polymerization, obtain the emulsion polymer coating liquid, and cooling discharging is standby;
2) described pesticide granules is placed in coating equipment in sugar production line and carries out preheating, then organism is sprayed at the described pesticide granules surface after preheating, until the thickness of organic matter layer is 2～10 μ m, then, again with the described pesticide granules surface that is sprayed at after the atomization of described emulsion polymer coating liquid after the preheating that is in fluidized state, carry out coating; The quality of effective constituent in the emulsion polymer coating liquid that wherein, uses (referring to outer other component that dewaters) is 3%～15% of described pesticide granules quality;
3) after coating is completed, the pesticide granules after coating is carried out abundant drying remove moisture in rete, namely obtain the polymer coated controlled release granular pesticide after cooling.
Wherein, the reaction times of polyreaction described in step 1) is 2～7h.
The condition of preheating step 2) is: at 75～90 ℃ of lower preheating 10～15min.
Step 2) organism described in can be Viscotrol C or brown wet goods.Be coated with the machine thing at pesticide granules, can improve the particle surface performance, increase the adhesivity of mould material, make film forming more even.
The atomization of the coating liquid of emulsion polymer step 2) realizes by atomizing nozzle, and described atomizing nozzle is the pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015～0.0080MPa, and transfer rate is 5～200ml/min.
Step 2) coating equipment in sugar production line described in is rotary drum and the fluidized-bed of various routines.
Described pesticide granules after the preheating of fluidized state step 2) is by regulating rotary drum rotating speed 5～10r/min, or fluidized-bed centrifugal blower frequency 35～45Hz realizes.
When the polymer layer of described polymer coated controlled release granular pesticide is comprised of polyurethanes film material, the preparation method of described polymer coated controlled release granular pesticide comprises the steps:
1) with following a) and b) be preheating to respectively molten state,, then with its mixing, make polymer capsule liquid; Describedly a) by described isocyanic ester and furtherance film, formed; Described b) comprise described polyvalent alcohol and chainextender;
2) described pesticide granules is placed in coating equipment in sugar production line and carries out preheating, then, with the described pesticide granules surface that is sprayed at after the atomization of described polymer capsule liquid after the preheating that is in fluidized state, carry out coating; Coating is cooling after finishing, and obtains the polymer coated controlled release granular pesticide.
The time of wherein, mixing described in step 1) is 0.1～20s.B described in step 1)) also comprise described catalyzer in.
The condition of preheating step 2) is: at 50～90 ℃ of lower preheating 10～15min.
The atomization of the liquid of polymer capsule step 2) realizes by atomizing nozzle, and described atomizing nozzle is the pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015～0.8MPa, and transfer rate is 0.01～1kg/min.
Step 2) coating equipment in sugar production line described in is rotary drum and the fluidized-bed of various routines.
Described pesticide granules after the preheating of fluidized state step 2) is by regulating rotary drum rotating speed 5～10r/min, or fluidized-bed centrifugal blower frequency 35～45Hz realizes.
The prepared polymer coated controlled release granular pesticide of the present invention can be by controlling macromolecular material molecular size range and distribution and then reach the effect that effective constituent discharges of controlling, two class film materials are to the equal effective iris action of the release of pesticide active ingredient.Concrete advantage is as follows:
1, this serial coated fertilizer water repelling property is good, and the specific aim of material application is high, and can degrade voluntarily in physical environment, belongs to environment-friendly materials.
2,, by changing the mould material formula, can regulate and control molecular size range and the distribution of film material, water tolerance, the performances such as hardness.Can be by regulating aspect mould material formula and mould material consumption two, thus realize the good controlled-release effect of product.
3, effectively solve the losing issue of water soluble pesticide, preparation is with strong points, can lasting prevention effect be arranged to weeds, subterranean pest-insect, soil-borne disease, and the lasting period is long, uses conveniently.
4, coating all adopts the traditional methods such as common fluidized-bed or rotary drum coating, simple possible, and processing condition are advanced, and the mould material consumption is few, and film forming is even, thin film thickness.
The present invention realizes the agricultural chemicals granulation by the compound fertilizer granulating technology, and by polymer capsule, realizes pesticide action-controlling, extends drug effect, realizes that one season of dispenser is effective, and reduces residual in edatope of agricultural chemicals, environmental friendliness.
Description of drawings
Fig. 1 is the cumulative release curve of Butachlor technical 92 in the polyurethane coated granular pesticide of embodiment 1 preparation.
Fig. 2 is the cumulative release curve of benbbensulfuronmethyl in the polyurethane coated granular pesticide of embodiment 1 preparation.
Embodiment
The present invention will be described below by specific embodiment, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, be ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
At present, the evaluation of effective constituent release performance in the pesticide slow-release formulation be there is no unified standard method both at home and abroad, the controlled release properties of the polymer capsule granular pesticide of flooding method evaluation the present invention preparation that reference has been reported.Following example is all taked this method:
The mensuration of control-released agent Pesticides content: the 20mg sample particle is dissolved in 50ml methyl alcohol, and ultra sonic bath 15min, make the complete disintegration of particle.Be settled to 100mL with ultrapure water, this solution is placed in tool plug Erlenmeyer flask and 25 ± 0.1 ℃ of thermostatic baths in the 24h that vibrates, then, with the syringe nylon filter filtration of gained extracting solution with 0.20 μ m.The concentration of agricultural chemicals is measured by high performance liquid chromatography (HPLC), and various agricultural chemicals HPLC detection methods are specifically with reference to standard GB/T/T5009.218-2008.
Detecting for slowly-releasing property: coated release-controlled dose of the agricultural chemicals that takes preparation approximately 1g(claims to be accurate to 0.1mg) put into the pouch that 100 order nylon gauzes are made, after sealing, pouch is put into 250mL vial or Plastic Bottle, add 200mL water, seal, be placed in respectively the biochemical constant incubator of 25 ℃ or 40 ℃, be 24h, 2d, 3d, 5d, 7d, 10d, 14d, 28d sample time, the timed interval of sampling is 28d later, until accumulation effective constituent release rate reaches more than 80%, is considered as discharging fully.During sampling, bottle is turned upside down three times, make the strength of fluid in bottle consistent, move in the 250mL volumetric flask, be settled to scale after being cooled to room temperature, in order to HPLC, detect.
Coated release-controlled agricultural chemicals film material degradation property is estimated:
Accurately take the polymer capsule material of preparation, imbed in the natural soil environment, length of embedment is 10cm.Got sample every 1 month one time, clean up material surface earth, drying is weighed, the Calculating material rate of weight loss.Material rate of weight loss W
l=W
0-W
t/ W
0* 100%, W
0For material initial mass, W
tThe quality of materials of constantly removing from soil for t.
The pesticide granules that uses in following embodiment, all standby according to the below legal system:
1) at adjustable speed
In the small-sized disc tablets press, auxiliary agent, commercially available various powdered pesticide preparations commonly used or the former powder of pesticide soluble and commercially available various powdered fertilizer commonly used are added by consumption, with 7r/min mixing 5min.
2), regulate the granulating disc rotating speed to 32r/min, add atomized water in the spray of material surface, slowly at the uniform velocity drip liquid pesticide on the material surface, complete granulation.
3), with above-mentioned pesticide granules drying treatment in drying plant, screening namely obtains required 2～6mm grade pesticide granules core core.
Embodiment 1
Take particle diameter 3mm self-control pesticide granules 10kg, be placed in rotary drum, open the heater switch of rotary drum, carry out the preheating of fertilizer, until homo(io)thermism is at 85 ℃.Take tolylene diisocyanate (TDI) 100g, add sulfonation paraffin (furtherance film) 60g, be placed in 70 ℃ of heating kettle melting constant temperature.Take polyether glycol series (Long Hua oil company, Jing Zhou 635 types) 220g, 1,6-hexylene glycol (chainextender) 20g, and add 0.1g stannous octoate (catalyzer), be placed in 80 ℃ of heating kettle melting constant temperature.Then open the venting valve of proportioning pump, then open and pump into valve, two ingredient liquids is mixed through Hi-mixer, the pressure of adjusting pump is 0.1Mpa, and total speed of spraying is 0.075L/min, starts spraying.Continuous spray 6 minutes, sprayed fully to coating liquid, and 90 ℃ of insulation reaction after 10 minutes, cool, and obtain the coated release-controlled granular pesticide of polyurethanes.Wherein, the quality of polyurethanes coating layer is the coated release-controlled granular pesticide total mass 3.8% of described polyurethanes.
In described self-control pesticide granules, the mass ratio of each batching is: and fertilizer (ammonium chloride: diammonium phosphate: vitriolate of tartar=200:150:200): liquid pesticidal (Butachlor technical 92): the former powder of pesticide soluble (benbbensulfuronmethyl): auxiliary agent (wilkinite)=550:50:10:390.Adopt water-extraction method to measure the controlled release properties of this coated release-controlled granular pesticide, Butachlor technical 92 initial stage solubility rate is 4.2%, and the controlled release phase (accumulation effective constituent release rate reaches more than 80%) is 18 days; Benbbensulfuronmethyl initial stage solubility rate is 5.3%, and the controlled release phase is 15 days, the degraded 11% in 12 months of polymeric membrane material.
Above-mentioned sample, carry out prevention and control weeds field test according to herbicides for use in paddy field test GBT17980-40-2000.Test-results shows, during sample mu consumption 7.5kg, after using 70 days, still several main weeds in rice field all there is favorable effect, survey producing result during results shows: the sample preparation district such as compares at the check plot volume increase 25.75% that nitrogen content composite fertilizer processes, and has remarkable effect of increasing production.
Table 1 rice field main weeds preventive effect table
Annotate: in table 1, data are the control of weeds effect, for: (the remaining careless number of blank district careless number-treatment zone alive) * 100/ blank district careless number alive)
Contrast as can be known with the fresh weight preventive effect, weedicide of the present invention can effectively suppress weeds emerges, and makes its plant short and small, and the fresh weight preventive effect is obvious.
Embodiment 2
Add 100 parts of deionized waters in reactor, 0.5 part of sodium laurylsulfonate, 0.5 part of OP-10, heating, stirring, logical nitrogen protection.Treat that temperature is elevated to 82 ℃, with the mix monomers of 100 parts (methyl methacrylate: ethyl propenoate: Hydroxyethyl acrylate: butyl methacrylate is by weight 45:45:7:3), 0.5 part of ammonium persulphate, drop in reactor initiated polymerization.React and obtained emulsion polymer in 4 hours, cooling stand-by.Be that 4mm self-control pesticide granules is packed in fluidized-bed with the 1000g diameter, be heated to 90 ℃.Viscotrol C is sprayed at self-control pesticide granules surface, and spraying Viscotrol C thicknesses of layers is about 5 μ m.Then, be 4kpa with two-fluid spray nozzle at atomizing pressure, with the speed of per minute 2g, polymer emulsion is sprayed at particulate state castor-oil plant oil reservoir surface, fully remove in rete institute after drying moisture, namely be prepared into the coated release-controlled granular pesticide of polyacrylate(s).Wherein, the polyacrylate(s) coating accounts for 4.1% of the coated release-controlled granular pesticide total mass of described polyacrylate(s).
It is as follows that mould material accounts for the measuring method of per-cent of total particle agent: get 10g coated fertilizer sample, with high-speed grinder, grind, with the powder 200 purpose nylon string bags of packing into, the deionized water soaking and water washing, oven dry, the quality of weighing mould material, calculate mould material and account for the per-cent of total fertilizer.
Calculation formula: R=(W
1/ W
0) * 100%
W0 is the quality of coated fertilizer;
W1 is the quality of coated fertilizer putamina.
In described self-control pesticide granules, ratio of components is fertilizer (diammonium phosphate): and auxiliary agent (treated starch: calcium dodecylbenzene sulphonate: zeolite powder=20:80:200): the former powder of pesticide soluble (Chlorpyrifos 94): liquid pesticidal (acetochlor)=100:800:50:50.
Adopt water-extraction method to measure the controlled release properties of this coated release-controlled granular pesticide, Chlorpyrifos 94 initial stage solubility rate is 7.7%, and the controlled release phase (accumulation effective constituent release rate reaches more than 80%) is 25 days, and acetochlor initial stage solubility rate is 7.1%, the controlled release phase is 23 days, the degraded 9% in 12 months of polymeric membrane material.
Embodiment 3
Take particle diameter 3mm self-control pesticide granules 10kg, be placed in rotary drum, open the rotary drum heater switch, make the pesticide granules preheating by oneself, until homo(io)thermism is at 85 ℃.Take diphenylmethanediisocyanate (MDI) 150g, add paraffin (furtherance film) 60g, be placed in heating kettle melting constant temperature to 75 ℃.Take poly adipate succinic acid ester 210g, 2,3-butanediol (chainextender) 20g, be placed in 90 ℃ of heating kettle melting constant temperature.Then open the venting valve of proportioning pump, then open and pump into valve, two component liquid are mixed through Hi-mixer, adjust the pressure position 0.1Mpa of pump, total speed of spraying is 0.15 liter/min of clock, opens spraying.After continuous spray 3 minutes, stop spraying, 90 ℃ of insulations, react and cool after 8 minutes, obtains the coated release-controlled granular pesticide of polyurethanes.Wherein, the quality of described polyurethanes coating layer is 4.2% of the coated release-controlled granular pesticide total mass of polyurethanes.
In described self-control pesticide granules, ratio of components is: fertilizer (Zinc Sulphate Heptahydrate): and the former powder of pesticide soluble (thiram: hymexazol=200:160): auxiliary agent (activated carbon: wilkinite: SDS=300:319:1)=20:360:620.
Adopt water-extraction method to measure its controlled release properties, thiram initial stage solubility rate is 4.2%, and the controlled release phase is 38 days, and hymexazol initial stage solubility rate is 3.8%, and the controlled release phase is 40 days, the degraded 12% in 12 months of polymeric membrane material.
Embodiment 4
Take particle diameter 2mm self-control pesticide granules 10kg, be placed in rotary drum, open the heater switch of rotary drum, the preheating of making pesticide granules by oneself, until homo(io)thermism is at 80 ℃.Take polymethylene multi-phenenyl isocyanate (PAPI) 140g, add clorafin (furtherance film) 80g, be placed in 85 ℃ of heating kettle melting constant temperature.Take polytetrahydrofuran diol 300g, glycerine (chainextender) 15g, and add 0.1g N-Ethylmorphine quinoline, be placed in 80 ℃ of heating kettle melting constant temperature.Then open the venting valve of proportioning pump, then open and pump into valve, two ingredient liquids is mixed through Hi-mixer, the pressure of adjusting pump is 0.1Mpa, and total speed of spraying is 0.065L/min, starts spraying.Continuous spray 4 minutes, sprayed fully to coating liquid, and 80 ℃ of insulation reaction after 8 minutes, cool, and obtain the coated release-controlled granular pesticide of polyurethanes.Wherein, the quality of described polyurethanes coating layer is 5.1% of the coated release-controlled granular pesticide total mass of polyurethanes.
In described self-control pesticide granules, ratio of components is: and fertilizer (ammonium chloride: monoammonium phosphate: Repone K=300:280:300): the former powder of pesticide soluble (benbbensulfuronmethyl): liquid pesticide (Stam F-34): auxiliary agent (activated carbon: OP-10=100:80)=880:20:100:180.
Adopt water-extraction method to measure its controlled release properties, Stam F-34 initial stage solubility rate is 6.3%, and the controlled release phase is 51 days, and benbbensulfuronmethyl initial stage solubility rate is 6.1%, and the controlled release phase is 53 days, the degraded 12% in 12 months of polymeric membrane material.
Take particle diameter 3mm self-control pesticide granules 10kg, be placed in rotary drum, open the heater switch of rotary drum, carry out the preheating of fertilizer, until homo(io)thermism is at 85 ℃.Take dicyclohexyl methane diisocyanate (HMDI) 165g, add petroleum resin (furtherance film) 90g, be placed in 80 ℃ of heating kettle melting constant temperature.Take polyethylene glycol succinate 240g, sorbyl alcohol (chainextender) 25g, and add 0.1g triethylamine (catalyzer), be placed in 90 ℃ of heating kettle melting constant temperature.Then open the venting valve of proportioning pump, then open and pump into valve, two ingredient liquids is mixed through Hi-mixer, the pressure of adjusting pump is 0.1Mpa, and total speed of spraying is 0.075L/min, starts spraying.Continuous spray 5 minutes, sprayed fully to coating liquid, and 90 ℃ of insulation reaction are after 9 minutes, cool, obtain the coated release-controlled granular pesticide of polyurethanes, wherein, the quality of described polyurethanes coating layer is 4.9% of the coated release-controlled granular pesticide total mass of polyurethanes.
In described self-control pesticide granules, ratio of components is: and fertilizer (diammonium phosphate: Zinc Sulphate Heptahydrate=100:20): the former powder of pesticide soluble (jingganmycin: hymexazol: thiram=10:100:100): auxiliary agent (zeolite powder: attapulgite=150:5)=120:210:155.
Adopt water-extraction method to measure its controlled release properties, hymexazol initial stage solubility rate is 5.1%, and the controlled release phase is 34 days, thiram initial stage solubility rate is 4.7%, and the controlled release phase is 31 days, and jingganmycin initial stage solubility rate is 3.9%, the controlled release phase is 37 days, the degraded 15% in 12 months of polymeric membrane material.
Embodiment 6
Add 100 parts of deionized waters in reactor, 0.5 part of sodium laurylsulfonate, 0.5 part of OP-10, heating, stirring, logical nitrogen protection.Treat that temperature is elevated to 78 ℃, with the mix monomers of 100 parts (methyl methacrylate: vinyl acetate: vinylformic acid: butyl methacrylate is by weight 45:47:7:1), 0.5 part of ammonium persulphate, drop in reactor initiated polymerization.React and obtained emulsion polymer in 2 hours, cooling stand-by.Be that 2mm self-control pesticide granules is packed in fluidized-bed with the 1500g diameter, be heated to 90 ℃.Viscotrol C is sprayed at self-control pesticide granules surface, and spraying Viscotrol C thicknesses of layers is about 5 μ m.Then, be 4kpa with two-fluid spray nozzle at atomizing pressure, with the speed of per minute 2g, polymer emulsion is sprayed at particulate state castor-oil plant oil reservoir surface, fully remove in rete institute after drying moisture, namely be prepared into coated release-controlled dose of polyacrylate(s) agricultural chemicals.Wherein, the polyacrylate(s) coating accounts for 4.6% of the coated release-controlled granular pesticide total mass of described polyacrylate(s).
In described self-control pesticide granules, ratio of components is auxiliary agent (treated starch: wilkinite: gac=100:500:100): the former powder of pesticide soluble (Chlorpyrifos 94): liquid pesticide (Butachlor technical 92)=700:100:200.
Adopt water-extraction method to measure the controlled release properties of this coated release-controlled granular pesticide, Butachlor technical 92 initial stage solubility rate is 6.7%, and the controlled release phase is 25 days, and Chlorpyrifos 94 initial stage solubility rate is 8.9%, and the controlled release phase is 20 days.
Claims (10)
1. a polymer coated controlled release granular pesticide, be comprised of pesticide granules and the polymer layer of the described pesticide granules of parcel; Wherein, the quality of described polymer layer is 2%～15% of described polymer coated controlled release granular pesticide quality;
Described polymer layer is the hydrophobicity rete, and it is comprised of water base polyacrylate(s) film material or polyurethanes film material;
Described pesticide granules is made by the following raw material of 100 mass parts: the auxiliary agent of commercially available various powdered pesticide preparations commonly used or 0～45 part, the former powder of pesticide soluble, 0～75 part of commercially available various powdered fertilizer commonly used and commercially available various liquid pesticide commonly used or 0～20 part of agricultural chemicals stoste and surplus; The mass parts of described powdered pesticide preparation or the former powder of pesticide soluble and described liquid pesticide or agricultural chemicals stoste is not 0 simultaneously, and the mass parts of described auxiliary agent is not 0.
2. polymer coated controlled release granular pesticide according to claim 1, it is characterized in that: described powdered pesticide preparation or the former powder of pesticide soluble are selected from following at least a: Provado, Chlorpyrifos 94, benbbensulfuronmethyl, Piao's grass are clean, benbbensulfuronmethyl, terbufos, thiram, jingganmycin and hymexazol;
Described liquid pesticide or agricultural chemicals stoste are selected from following at least a: alachlor, acetochlor, metolachlor, Butachlor technical 92 and Stam F-34;
Described fertilizer is selected from following at least a: nitrogen-phosphorus-potassium compound fertilizer, ammonium chloride, urea, volatile salt, ammonium nitrate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, Repone K, vitriolate of tartar and Zinc Sulphate Heptahydrate;
Described auxiliary agent is selected from following at least a: activated carbon, zeolite powder, diatomite, kaolin, wilkinite, attapulgite, treated starch, calcium dodecylbenzene sulphonate, sodium laurylsulfonate, OP-10, Tween-60, and described auxiliary agent all needed 80 mesh sieves before using;
The median size of described pesticide granules is 2～6mm.
3. polymer coated controlled release granular pesticide according to claim 1 and 2, it is characterized in that: described pesticide granules is to prepare according to the method that comprises the steps:
1) auxiliary agent, powdered pesticide preparation or the former powder of pesticide soluble and fertilizer are added in tablets press, mix;
2) add atomized water in the surface spray of mixed material, then on described material surface, at the uniform velocity drip described liquid pesticide or agricultural chemicals stoste, complete granulation;
The pesticide granules that 3) will obtain carries out drying, screening, obtains pesticide granules core core;
Wherein, tablets press described in step 1) is specially adjustable rotating speed
Granulating disc;
In the described mixing process of step 1), the rotating speed of granulating disc is 5～10r/min, preferred 7r/min mixing 5min;
Step 2) in, described granulating disc rotating speed is 25～35r/min, preferred 32r/min; Described atomized water is realized by atomizer; It adds with 10～500g/min flow with peristaltic pump.
4. the described polymer coated controlled release granular pesticide of any one according to claim 1-3, it is characterized in that: the polymer layer of described polymer coated controlled release granular pesticide is comprised of water base polyacrylate(s) film material, and described pesticide granules is the pesticide granules that surface coats organic matter layer; The thickness of described organic matter layer is 2～10 μ m; Described organism is Viscotrol C or palm fibre oil.
5. according to claim 1-4 described polymer coated controlled release granular pesticides of any one, it is characterized in that: the second-order transition temperature of described water base polyacrylate(s) film material is 0～60 ℃, polymericular weight is 10
3～10
8
Described water base polyacrylate(s) film material carries out polyreaction by the material of following mass parts and prepares: 0.5～2 part of 100 parts of monomers, 0.5～1 part of initiator, 100～150 parts, water and emulsifying agent; Described monomer be following a) or b): a) vinylformic acid and/or acrylate monomer, b) mix monomer of vinylformic acid and/or acrylate monomer and response type function monomer.
6. the described polymer coated controlled release granular pesticide of any one according to claim 1-5, it is characterized in that: described water base polyacrylate(s) film material is to prepare according to the method that comprises the steps: in reactor, add in mass ratio 100～150 parts, water, 0.5～2 part of emulsifying agent, heating, stir, logical nitrogen, treat that temperature is increased to 70～90 ℃, with 100 parts of described monomers, 0.5～1 part of initiator is added drop-wise in reactor under fully stirring, initiated polymerization, after reaction 2～7h, obtain the emulsion of described water base polyacrylate(s) film material;
wherein, described vinylformic acid and/or acrylate monomer are comprised of at least a material of following mass parts: vinylformic acid 0～30, 0～30 part of methyl acrylate, 0～60 part of ethyl propenoate, 0～60 part of butyl acrylate, Hydroxyethyl acrylate 0～40, 0～70 part of methyl methacrylate, 0～50 part of butyl methacrylate, methacrylic acid 0～20, 0～50 part of the different monooctyl ester of vinylformic acid-2-, 0～30 part of n-methylolacrylamide, 0～20 part of glycidyl acrylate, 0～20 part of Viscoat 295, 0～20 part of 0～30 part of dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate,
Described function monomer is comprised of at least a material of following mass parts: 0～60 part of vinylbenzene, 0～30 part of vinyl acetate, 0～25 part of 4-vinylpridine, 0～25 part of 2-vinyl pyridine, 0～10 part of Vinylstyrene;
Described emulsifying agent is selected from following at least a: OP-10, sodium laurylsulfonate and Sodium dodecylbenzene sulfonate;
Described initiator is Potassium Persulphate and/or ammonium persulphate.
7. the described polymer coated controlled release granular pesticide of any one according to claim 1-3, it is characterized in that: described polyurethanes film material, the raw material of making it comprises: isocyanic ester, polyvalent alcohol, furtherance film and chainextender, wherein in isocyanic ester in isocyano and polyvalent alcohol the mol ratio of institute's hydroxyl group be 1:2～2:1, the furtherance film accounts for 0.1%～30% of described polyurethanes film material total mass, and chainextender accounts for 0%～15% of described polyurethanes film material total mass;
described isocyanic ester is selected from following at least a: tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, to the phenylmethane vulcabond, 1, 4-bicyclohexane vulcabond, xylylene diisocyanate, the cyclohexanedimethyleterephthalate vulcabond, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, the many phenyl isocyanate of many subunits, the liquefaction diphenylmethanediisocyanate, toluene diisocyanate dimer, toluene diisocyanate trimer, tolylene diisocyanate-TriMethylolPropane(TMP) affixture, tolylene diisocyanate-hexamethylene diisocyanate biuret, isophorone diisocyanate trimer, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4-phenyl isocyanate) and dimethyl triphenyl methane tetraisocyanate,
Described polyvalent alcohol is for containing at least the polyvalent alcohol of 2 hydroxyls, its be selected from following a) and/or b) and/or c) at least a:
Described a) at least a in following polyether glycol: polyoxyethylene polyvalent alcohol, polyoxypropyleneglycol, polyoxytrimethylene triol, polyether triol, polyether tetrols, quadrol polyether glycol, functionality are 3 polyether glycol, polytetrahydrofuran diol, contain the side chain polytetrahydrofuran diol;
Described b) be at least a in following vegetable oil polyol: Viscotrol C, soybean oil polyvalent alcohol and plam oil polyvalent alcohol;
Described c) be at least a in following polyester polyol: polyethylene glycol succinate, poly butylene succinate and polyethylene glycol adipate;
Described chainextender is selected from following at least a: BDO, 2,3-butanediol, glycol ether, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP) and sorbyl alcohol;
Described furtherance film is selected from following at least a: paraffin, clorafin, sulfonation paraffin and rosin ester.
8. polymer coated controlled release granular pesticide according to claim 7, it is characterized in that: the raw material of making described polyurethanes film material also comprises catalyzer;
Described catalyzer is following at least a for being selected from: dibutyl tin laurate, stannous octoate, triethylamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, diethylenetriamine, triethylenediamine, tetramethyl butane diamine and N-Ethylmorphine quinoline; Its consumption is 0.1%～1% of described isocyanic ester total mass.
9. the method for the polymer coated controlled release granular pesticide that is comprised of water base polyacrylate(s) film material of preparation claim 5 or 6 described polymer layer, comprise the steps:
1) in reactor, add in mass ratio 100～150 parts, water, 0.5～2 part of described emulsifying agent, heating, stir, logical nitrogen, treat that temperature is increased to 70～90 ℃, with 100 parts of described monomers, 0.5～1 part of described initiator is added drop-wise in reactor under fully stirring, initiated polymerization, obtain the emulsion polymer coating liquid, and cooling discharging is standby;
2) described pesticide granules is placed in coating equipment in sugar production line and carries out preheating, then organism is sprayed at the described pesticide granules surface after preheating, until the thickness of organic matter layer is 2～10 μ m, then, again with the described pesticide granules surface that is sprayed at after the atomization of described emulsion polymer coating liquid after the preheating that is in fluidized state, carry out coating; The quality of the outer component that dewaters in the emulsion polymer coating liquid that wherein, uses is 3%～15% of described pesticide granules quality;
3) after coating is completed, the pesticide granules after coating is carried out drying, namely obtain described polymer coated controlled release granular pesticide after cooling;
Wherein, the reaction times of polyreaction described in step 1) is 2～7h;
The condition of preheating step 2) is: at 75～90 ℃ of lower preheating 10～15min;
Step 2) organism described in is Viscotrol C or palm fibre oil;
The atomization of the coating liquid of emulsion polymer step 2) realizes by atomizing nozzle, and described atomizing nozzle is the pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015～0.0080MPa, and transfer rate is 5～200ml/min.
Step 2) coating equipment in sugar production line described in is rotary drum or fluidized-bed;
Described pesticide granules after the preheating of fluidized state step 2) is by regulating rotary drum rotating speed 5～10r/min, or fluidized-bed centrifugal blower frequency 35～45Hz realizes.
10. the method for the polymer coated controlled release granular pesticide that is comprised of polyurethanes film material of preparation claim 7 or 8 described polymer layer, comprise the steps:
1) with following a) and b) be preheating to respectively molten state,, then with its mixing, make polymer capsule liquid; Describedly a) by described isocyanic ester and furtherance film, formed; Described b) described polyvalent alcohol and chainextender;
2) described pesticide granules is placed in coating equipment in sugar production line and carries out preheating, then, with the described pesticide granules surface that is sprayed at after the atomization of described polymer capsule liquid after the preheating that is in fluidized state, carry out coating; Coating is cooling after finishing, and obtains described polymer coated controlled release granular pesticide; The quality of described polymer layer is 3%～15% of described coated release-controlled pesticide granules quality;
The time of wherein, mixing described in step 1) is 0.1～20s;
The condition of preheating step 2) is: at 50～90 ℃ of lower preheating 10～15min;
The atomization of the liquid of polymer capsule step 2) realizes by atomizing nozzle, and described atomizing nozzle is the pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015～0.8MPa, and transfer rate is 0.01～1kg/min.
Step 2) coating equipment in sugar production line described in is rotary drum or fluidized-bed.
Described pesticide granules after the preheating of fluidized state step 2) is by regulating rotary drum rotating speed 5～10r/min, or fluidized-bed centrifugal blower frequency 35～45Hz realizes.
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