CN103387456B - 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 to endanger agricultural, the disease of forestry, worm, grass and other harmful organisms, is the important guarantee that agricultural produce protects receipts.According to Food and Argriculture OrganizationFAO (FAO) statistics, the crop loss that the whole world uses pesticide control disease and pest to retrieve accounts for 30% of total output of grain.China is a large agricultural country, Ye Shiyige populous nation.Because explosive population growth, cultivated land area, Agricultural Bio-disasters take place frequently, grain imbalance between supply and demand increasingly sharpens, and grain security is subject to serious threat.For ensureing grain yield, have a large amount of agricultural chemicals to put in agriculture production every year and go, and consumption increases rapidly year by year, according to statistics, the annual chemical prevention area of China is up to 400,000,000 hectares, and chemical pesticide former medicine year production speedup is more than 20%.As can be seen here, agricultural chemicals has become the requisite means of agricultural production input of modern agriculture.
But the widespread use of agricultural chemicals brings serious environmental pollution, while serving the mankind, also threaten the health of the mankind, the defect of this and Traditional Agricultural pharmaceutically dosage form nature has much relations.After conventional formulation is administered to farmland, be always subject to the effect of permeating, evaporating, degrading (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 crop demand in 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 decreasing pollution.Therefore, pesticide slow-releasing agent becomes the Main way of pesticide preparation development.
Slow release formulation is mainly divided into physical and chemotype both at home and abroad at present.Physical comprises microcapsule, sorbent material, all potion and inclusion compounds; Chemotype is by the inertia derivative (US20060188572, US20030031694, EP1142477, El-Refaie Kenawy, 2001) of chemical action synthesis containing pesticide active ingredient group.Chemotype requires harsh to the chemical structure of pesticide active ingredient, need to possess particular functional group, development is very limited; Sustained release dosage research is focusing more in the research and development of physical sustained release dosage.
Physical pesticide slow-releasing agent is divided into microcapsule, all 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), microcapsule slow release effect is better, applied widely, the effective constituent 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, coated fertilizer uses many, and the difficult degradation of film material, easily causes environmental pollution.Equal 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. report the method for a kind of starch xanthate parcel herbicide trifluralin on Weed Science magazine, and said preparation is respond well in field experiment; Calendar year 2001 Zhu and Zhuo reports and does matrix with starch-ethylene alcohol copolymer on European Polymer Journal magazine, prepare weedicide 2, the equal potion of 4,6-trichlorophenoxyacetic acid, this type of also has report by the method that treated starch is cooked matrix in US5516520, CN1951186A; Zhao and Wilkins in 2003 reports one degradable natural macromolecular material xylogen and makes matrix loading weedicide fluometuron on J.Agric.Food Chem. magazine, prepares the method for particle slow release agent; Within 2009, Voinova gives to the world the result of one's studies on AppliedBiochemistry and Microbiology magazine, and report microbial polymer poly-hydroxy fatty acid makes the method that matrix loads sterilant, and material therefor degradation property is good; Celis equals to report on J.Agric.Food Chem. magazine with inorganic, organic clay for 2002, and absorption weedicide hexazinone, effectively extends the lasting period simultaneously, reduce the leaching loss of agricultural chemicals; EP1142477A2 describes a kind of method that slow-release solid granular preparation prepared by charcoal absorption agricultural chemicals; Cardoso equals on J.Agric.Food Chem. magazine, within 2006, report a kind of anion exchange absorbing material water talcum and loads the method that acid herbicide realizes slowly-releasing, adopt same principle, domestic patent CN200710116303 has invented a kind of preparation method of Provado/hydrotalcite-like compounds nano hybrid.But all there is the problem of slow release effect difference, lasting period short (slow-release period is generally within one week), poor stability in potion and sorbent formulation.
On the Research foundation of equal potion and sorbent material, by outer coating, effectively can 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 wooden company can apply for a patent EP1063215 (A2), describes and adopts the gac core core that polyacrylate(s) coated fertilizer parcel has adsorbed pulvis/pesticide emulsion to be prepared into pesticide slow-releasing agent.Hargrove describes a kind of multilayer pesticide granules in US Patent No. 6682751, and center is nitrogenous fertilizer core core, adopts urethane-acephate homogeneous material to carry out original position coating, and then carries out outer coating with polyurethanes film material.Fern á ndez-P é rez etc. report in Carbohydrate Polymers83 (2011) 1672 – 1679: by xylogen and pyrazon Homogeneous phase mixing in the molten state, obtained equal potion, the material coated obtained pesticide slow-releasing agent of skin ethyl cellulose after pulverizing, by function monomer and content of plasticizing agent in adjustment ethyl cellulose material, realize in release period 10 ~ 20 days controlled; Next year, with the Flores-C é spedes etc. of seminar at J.Agric.Food Chem.2012, in 60,1042-1051, report the method that similar approach prepares Provado sustained release dosage.Domestic correlative study focuses mostly at controlled release medicine fertilizer research and development (CN1046887, CN101302130, CN102276356): Nanjing soil institute of the Chinese Academy of Sciences proposes fertilizer and agricultural chemicals granulation with granulating method in CN1046887, skin adds the mentality of designing of polymeric membrane, but specific embodiment is not quite clear; Zhengzhou University and Guangxi Tianyuan Biochemical Co., Ltd. apply for the fertile patent of invention CN101302130 of serial medicine, CN102276356, CN201210239491.6 take conventional particles fertilizer to be core core; or prepare the fertile core core of medicine by compound fertilizer granulation process; skin granule in pan-type pelletizer; different activities composition used additives layer (clay) is isolated; then directly with clay coating or transfer to coating equipment in sugar production line and carry out high polymer film-coated; the Product transport prepared is safe to use, and composition mixture performance is good.CN1951186A describes one treated starch and makes matrix, loads auxiliary agent and pesticide active ingredient under gelatinization state, the outer method with vegetables oil coating after granulating and drying.CN102823619A describes 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, outer obtained with polymer capsule.
Foreign patent focuses mostly on and to study at equal potion, and high molecular polymer usage quantity is large, and cost is higher.The polymer capsule material listing several large class commodity that domestic patent is only rough, the carrying out lacking the molecular designing to material, coating process and farm chemical release characteristic aspect is studied, 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, there is sorbent material and the ubiquitous problem of equal potion: drug loading is little, the lasting period is short, releasing rule is not easily grasped.Therefore, the pesticide action-controlling granule that prepared by aforesaid method is also significantly improved and room for promotion.
Summary of the invention
The object 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, is made up of the polymer layer of pesticide granules and the described pesticide granules of parcel; Wherein, the quality of described polymer layer is the 2% ~ 7%(preferably 3% ~ 5% of described polymer coated controlled release granular pesticide quality);
Described polymer layer is hydrophobic film layer, and it is made up of water base polyacrylate(s) film material or polyurethanes film material;
Described pesticide granules is made up of the following raw material of 100 mass parts: the auxiliary agent of commercially available various conventional powdered pesticide preparation or 0 ~ 45 part, the former powder of pesticide soluble, commercially available various conventional powdered fertilizer 0 ~ 75 part and commercially available various conventional liquid pesticide or agricultural chemicals stoste 0 ~ 20 part 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 0 time different, and the content of described auxiliary agent is not 0.
Wherein, described auxiliary agent can be selected from following at least one: activated carbon, zeolite powder, diatomite, kaolin, wilkinite, attapulgite, treated starch, calcium dodecylbenzene sulphonate, sodium laurylsulfonate, OP-10, Tween-60, all needs 80 mesh sieves before using.Described commercially available various conventional powdered pesticide preparation or the former powder of pesticide soluble can be selected from following at least one: Provado, Chlorpyrifos 94, benbbensulfuronmethyl, Piao careless clean, benbbensulfuronmethyl, terbufos, thiram, jingganmycin and hymexazol.Described commercially available various conventional powdered fertilizer can be selected from following at least one: nitrogen-phosphorus-potassium compound fertilizer, ammonium chloride, urea, volatile salt, ammonium nitrate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, Repone K, potassium sulfate and Zinc Sulphate Heptahydrate.Described commercially available various conventional liquid pesticide or agricultural chemicals stoste can be selected from following at least one: 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 prepares according to the method comprised the steps:
1) auxiliary agent, commercially available various conventional powdered pesticide preparation or the former powder of pesticide soluble and commercially available various conventional powdered fertilizer are added in tablets press, mixing;
2) upon mixing material surface spray add atomized water, then at the uniform velocity drip described commercially available various conventional liquid pesticide or agricultural chemicals stoste on described material surface, complete granulation;
3) pesticide granules obtained is carried out drying, screening, obtain required 2 ~ 6mm grade pesticide granules core core.
Wherein, tablets press described in step 1) is specially adjustable rotating speed
granulating disc.
In mixing process described in 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 made up 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 μm.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 DEG C, 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: monomer 100 parts, initiator 0.5 ~ 1 part, 100 ~ 150 parts, water and emulsifying agent 0.5 ~ 2 part; 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.
Concrete preparation method is as follows: 1), in a kettle., add 100 ~ 150 parts, water in mass ratio, emulsifying agent 0.5 ~ 2 part, heating, stir, logical nitrogen, treats that temperature is increased to 70 ~ 90 DEG C, by described monomer 100 parts, initiator 0.5 ~ 1 part to be added drop-wise in reactor under fully stirring, initiated polymerization, after reaction 2 ~ 7h, obtains the emulsion of described water base polyacrylate(s) film material.
Described vinylformic acid and/or acrylate monomer are made up of at least one material of following mass parts: vinylformic acid 0 ~ 30, methyl acrylate 0 ~ 30 part, ethyl propenoate 0 ~ 60 part, butyl acrylate 0 ~ 60 part, Hydroxyethyl acrylate 0 ~ 40, methyl methacrylate 0 ~ 70 part, butyl methacrylate 0 ~ 50 part, methacrylic acid 0 ~ 20, the different monooctyl ester of vinylformic acid-2-0 ~ 50 part, n-methylolacrylamide 0 ~ 30 part, glycidyl acrylate 0 ~ 20 part, Viscoat 295 0 ~ 20 part, dimethylaminoethyl methacrylate 0 ~ 30 part and diethylaminoethyl methacrylate 0 ~ 20 part.
Described function monomer is made up of at least one material of following mass parts: vinylbenzene 0 ~ 60 part, vinyl acetate 0 ~ 30 part, 4-vinylpridine 0 ~ 25 part, 2-vinyl pyridine 0 ~ 25 part, Vinylstyrene 0 ~ 10 part.
Described emulsifying agent is selected from following at least one: OP-10(alkylphenol polyoxyethylene), sodium laurylsulfonate and Sodium dodecylbenzene sulfonate.
Described initiator is Potassium Persulphate and/or ammonium persulphate.
The film of polyurethanes described in the present invention material, the raw material 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 is 1:2 ~ 2:1, 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 one: tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), naphthalene diisocyanate (NDI), to phenylmethane vulcabond, Isosorbide-5-Nitrae-dicyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethyleterephthalate vulcabond, dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, the many phenyl isocyanate of many subunits (PAPI), liquefaction diphenylmethanediisocyanate, toluene diisocyanate dimer (liquefied mdi, 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 at least containing the polyvalent alcohol of 2 hydroxyls, its be selected from following a) and/or b) and/or c) at least one:
Described a) is at least one in following polyether glycol: polyoxyethylated polyols, polyoxypropyleneglycol, polyoxytrimethylene triol, polyether triol, polyether tetrols, quadrol polyether glycol, functionality be 3 polyether glycol, polytetrahydrofuran diol, containing side chain polytetrahydrofuran diol;
Described b) is at least one in following vegetable oil polyol: Viscotrol C, soybean oil polyol (at least containing 2 hydroxyls) and plam oil polyvalent alcohol (at least containing 2 hydroxyls);
Described c) is at least one in following polyester polyol: polyethylene glycol succinate, poly butylene succinate and polyethylene glycol adipate.
Described chainextender is selected from following at least one: 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 one: paraffin, clorafin, sulfonated olefins and rosin ester.
The raw material making described polyurethanes film material also comprises catalyzer, and consumption is 0.1% ~ 1% of monomer mass.
Described catalyzer is for being selected from following at least one: dibutyl tin laurate, stannous octoate, triethylamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, diethylenetriamine, triethylenediamine, tetramethyl butane diamine and N-Ethylmorphine quinoline.
Another 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 made up of water base polyacrylate(s) film material, the preparation method of described polymer coated controlled release granular pesticide comprises the steps:
1) in a kettle., add 100 ~ 150 parts, water in mass ratio, emulsifying agent 0.5 ~ 2 part, heating, stir, logical nitrogen, treats that temperature is increased to 70 ~ 90 DEG C, by 100 parts of monomers, 0.5 ~ 1 part of initiator to be added drop-wise in reactor under fully stirring, initiated polymerization, obtain emulsion polymer coating liquid, cooling discharging is for subsequent use;
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 μm, then again by being sprayed at the described pesticide granules surface after the preheating being in fluidized state after described emulsion polymer coating liquid atomization, coating is carried out; Wherein, in the emulsion polymer coating liquid used, the quality of effective constituent (referring to other component in addition to water) is 3% ~ 15% of described pesticide granules quality;
3), after coating completes, moisture in fully dry removing rete is carried out to the pesticide granules after coating, after cooling, namely obtains polymer coated controlled release granular pesticide.
Wherein, the reaction times of polyreaction described in step 1) is 2 ~ 7h.
Step 2) described in the condition of preheating be: preheating 10 ~ 15min at 75 ~ 90 DEG C.
Step 2) described in organism can be Viscotrol C or brown wet goods.Be coated with machine thing at pesticide granules, particle surface performance can be improved, increase the adhesivity of mould material, make film forming evenly.
Step 2) described in the atomization of emulsion polymer coating liquid realized by atomizing nozzle, described atomizing nozzle is pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015 ~ 0.0080MPa, and transfer rate is 5 ~ 200ml/min.
Step 2) described in coating equipment in sugar production line be rotary drum and the fluidized-bed of various routine.
Step 2) described in fluidized state preheating after described pesticide granules 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 made up of polyurethanes film material, the preparation method of described polymer coated controlled release granular pesticide comprises the steps:
1) a) and b) be preheating to molten state respectively by following, then mixed, obtained polymer capsule liquid; Describedly a) to be made up of described isocyanic ester and furtherance film; Describedly b) comprise described polyvalent alcohol and chainextender;
2) described pesticide granules being placed in coating equipment in sugar production line and carrying out preheating, then by being sprayed at the described pesticide granules surface after the preheating being in fluidized state after described polymer capsule liquid atomization, carrying out coating; Coating terminates rear cooling, obtains polymer coated controlled release granular pesticide.
Wherein, the time mixed described in step 1) is 0.1 ~ 20s.Described in step 1) b) in also comprise described catalyzer.
Step 2) described in the condition of preheating be: preheating 10 ~ 15min at 50 ~ 90 DEG C.
Step 2) described in the atomization of polymer capsule liquid realized by atomizing nozzle, described atomizing nozzle is pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015 ~ 0.8MPa, and transfer rate is 0.01 ~ 1kg/min.
Step 2) described in coating equipment in sugar production line be rotary drum and the fluidized-bed of various routine.
Step 2) described in fluidized state preheating after described pesticide granules by regulating rotary drum rotating speed 5 ~ 10r/min, or fluidized-bed centrifugal blower frequency 35 ~ 45Hz realizes.
Polymer coated controlled release granular pesticide prepared by the present invention can by controlling the molecular size range of macromolecular material and distribution and then reaching the effect controlling effective constituent release, and two class film materials are to all 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 materials application is high, and can degrade voluntarily in physical environment, belongs to environment-friendly materials.
2, by changing mould material formula, molecular size range and the distribution of film material can be regulated and controled, water tolerance, the performances such as hardness.By regulating in mould material formula and mould material consumption two, thus the good controlled-release effect of product can be realized.
3, effectively solve the losing issue of water soluble pesticide, preparation is with strong points, and can have lasting prevention effect to weeds, subterranean pest-insect, soil-borne disease, the lasting period is long, uses conveniently.
4, coating all adopts the traditional method such as ordinary fluidized bed or rotary drum coating, simple possible, and processing condition are advanced, and mould material consumption is few, and film forming is even, thin film thickness.
The present invention realizes agricultural chemicals granulation by compound fertilizer granulating technology, and realizes pesticide action-controlling by polymer capsule, extends drug effect, realizes dispenser one season effective, and reduces agricultural chemicals remaining in edatope, environmental friendliness.
Accompanying drawing explanation
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
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
At present, unified standard method be there is no to the evaluation of effective constituent release performance in pesticide slow-release formulation both at home and abroad, evaluate the controlled release properties of polymer capsule granular pesticide prepared by the present invention with reference to the flooding method reported.Following example all takes this method:
The mensuration of control-released agent Pesticides content: be dissolved in by 20mg sample particle in 50ml methyl alcohol, ultra sonic bath 15min, makes the complete disintegration of particle.Be settled to 100mL with ultrapure water, this solution be placed in tool plug Erlenmeyer flask and the 24h that vibrates in 25 ± 0.1 DEG C of thermostatic baths, then, by the syringe nylon filter filtration of gained extracting solution with 0.20 μm.The concentration of agricultural chemicals is measured by high performance liquid chromatography (HPLC), and various agricultural chemicals HPLC detection method is concrete with reference to standard GB/T/T5009.218-2008.
Detecting for slowly-releasing property: the agricultural chemicals coated release-controlled dose of about 1g(taking preparation claims to be accurate to 0.1mg) put into the pouch that 100 order nylon gauzes make, after sealing, pouch is put into 250mL vial or Plastic Bottle, add 200mL water, seal, be placed in the biochemical constant incubator of 25 DEG C or 40 DEG C respectively, sample time is 24h, 2d, 3d, 5d, 7d, 10d, 14d, 28d, the timed interval of later sampling is 28d, until accumulation effective constituent release rate reaches more than 80% be considered as release completely.During sampling, bottle is turned upside down three times, make the strength of fluid in bottle consistent, move in 250mL volumetric flask, be settled to scale after being cooled to room temperature, detect in order to HPLC.
Coated release-controlled agricultural chemicals film material degradation property is evaluated:
Accurately take the polymer capsule material of preparation, imbed in natural soil environments, length of embedment is 10cm.Got a sample every 1 month, clean up material surface earth, drying is weighed, 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
tfor the quality of materials that t is removed from soil.
The pesticide granules used in following embodiment, all standby according to below legal system:
1) at adjustable speed
in small-sized disc tablets press, auxiliary agent, commercially available various conventional powdered pesticide preparation or the former powder of pesticide soluble and commercially available various conventional powdered fertilizer are added by consumption, with 7r/min mixing 5min.
2), regulate 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 material surface, complete granulation.
3), by above-mentioned pesticide granules drying treatment in drying plant, sieve and obtain required 2 ~ 6mm grade pesticide granules core core.
Embodiment 1
Take particle diameter 3mm and make pesticide granules 10kg by oneself, 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 DEG C.Take tolylene diisocyanate (TDI) 100g, add sulfonated olefins (furtherance film) 60g, be placed in heating kettle melting constant temperature 70 DEG C.Take polyether glycol series (Long Hua oil company 635, Jing Zhou type) 220g, 1,6-hexylene glycol (chainextender) 20g, and add 0.1g stannous octoate (catalyzer), be placed in heating kettle melting constant temperature 80 DEG C.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 adjustment pump is 0.1Mpa, and total speed of spraying is 0.075L/min, starts spraying.Continuous spray 6 minutes, has sprayed completely to coating liquid, and 90 DEG C of insulation reaction, after 10 minutes, cool, and obtains 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: fertilizer (ammonium chloride: diammonium phosphate: potassium sulfate=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 preliminary solubility is 4.2%, and the controlled release phase (accumulation effective constituent release rate reaches more than 80%) is 18 days; Benbbensulfuronmethyl preliminary solubility is 5.3%, and the controlled release phase is 15 days, the degraded 11% in 12 months of polymeric membrane material.
Above-mentioned sample, carries 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 all there is favorable effect to several main weeds in rice field, survey product result during results to show: the check plot volume increase 25.75% of the nitrogen content composite fertilizer process such as sample preparation district ratio, has remarkable effect of increasing production.
Table 1 rice field main weeds preventive effect table
Note: in table 1, data are control of weeds effect, for: (the remaining careless number in careless number-treatment zone alive, blank district) * 100/ blank district careless number alive)
Contrast known with fresh weight preventive effect, weedicide of the present invention can effectively suppress weeds to emerge, and make its plant short and small, fresh weight preventive effect is obvious.
Embodiment 2
Add 100 parts of deionized waters in a kettle., 0.5 part of sodium laurylsulfonate, 0.5 part of OP-10, heating, stirring, logical nitrogen protection.Treat that temperature is elevated to 82 DEG C, by 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, drops in reactor, initiated polymerization.React and obtain emulsion polymer in 4 hours, cool stand-by.Be that 4mm makes by oneself in pesticide granules loading fluidized-bed by 1000g diameter, be heated to 90 DEG C.Viscotrol C is sprayed at self-control pesticide granules surface, spraying Viscotrol C thicknesses of layers is about 5 μm.Then, be 4kpa with two-fluid spray nozzle at atomizing pressure, with the speed of per minute 2g, polymer emulsion be sprayed at particulate state castor-oil plant oil reservoir surface, after fully dry, in removing rete, institute is moisture, is namely prepared into the coated release-controlled granular pesticide of polyacrylate(s).Wherein, polyacrylate(s) coating accounts for 4.1% of the coated release-controlled granular pesticide total mass of described polyacrylate(s).
The measuring method that mould material accounts for the per-cent of total particle agent is as follows: get 10g coated fertilizer sample, with high-speed grinder grinding, powder is loaded the 200 object nylon string bags, deionized water soaking and water washing, dry, weigh the quality of mould material, calculate the per-cent that mould material accounts for 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): 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.
Water-extraction method is adopted to measure the controlled release properties of this coated release-controlled granular pesticide, Chlorpyrifos 94 preliminary solubility is 7.7%, and the controlled release phase (accumulation effective constituent release rate reaches more than 80%) is 25 days, and acetochlor preliminary solubility 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 and make pesticide granules 10kg by oneself, be placed in rotary drum, open rotary drum heater switch, carry out the preheating of self-control pesticide granules, until homo(io)thermism is at 85 DEG C.Take diphenylmethanediisocyanate (MDI) 150g, add paraffin (furtherance film) 60g, be placed in heating kettle melting constant temperature to 75 DEG C.Take poly adipate succinic acid ester 210g, 2,3-butanediol (chainextender) 20g, be placed in heating kettle melting constant temperature 90 DEG C.Then open the venting valve of proportioning pump, then open and pump into valve, two component liquid is mixed, the pressure position 0.1Mpa of adjustment pump through Hi-mixer, total speed of spraying is 0.15 liter/min, opens spraying.Continuous spray is after 3 minutes, and stop spraying, 90 DEG C of insulations, react and cool after 8 minutes, obtain 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): 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 preliminary solubility is 4.2%, and the controlled release phase is 38 days, and hymexazol preliminary solubility 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 and make pesticide granules 10kg by oneself, be placed in rotary drum, open the heater switch of rotary drum, carry out the preheating of making pesticide granules by oneself, until homo(io)thermism is at 80 DEG C.Take polymethylene multi-phenenyl isocyanate (PAPI) 140g, add clorafin (furtherance film) 80g, be placed in heating kettle melting constant temperature 85 DEG C.Take polytetrahydrofuran diol 300g, glycerine (chainextender) 15g, and add 0.1g N-Ethylmorphine quinoline, be placed in heating kettle melting constant temperature 80 DEG C.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 adjustment pump is 0.1Mpa, and total speed of spraying is 0.065L/min, starts spraying.Continuous spray 4 minutes, has sprayed completely to coating liquid, and 80 DEG C of insulation reaction, after 8 minutes, cool, and obtains 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: 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 preliminary solubility is 6.3%, and the controlled release phase is 51 days, and benbbensulfuronmethyl preliminary solubility is 6.1%, and the controlled release phase is 53 days, the degraded 12% in 12 months of polymeric membrane material.
Embodiment 5
Take particle diameter 3mm and make pesticide granules 10kg by oneself, 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 DEG C.Take dicyclohexyl methane diisocyanate (HMDI) 165g, add petroleum resin (furtherance film) 90g, be placed in heating kettle melting constant temperature 80 DEG C.Take polyethylene glycol succinate 240g, sorbyl alcohol (chainextender) 25g, and add 0.1g triethylamine (catalyzer), be placed in heating kettle melting constant temperature 90 DEG C.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 adjustment pump is 0.1Mpa, and total speed of spraying is 0.075L/min, starts spraying.Continuous spray 5 minutes, has sprayed completely to coating liquid, and 90 DEG C 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: 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 preliminary solubility is 5.1%, and the controlled release phase is 34 days, thiram preliminary solubility is 4.7%, and the controlled release phase is 31 days, and jingganmycin preliminary solubility 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 a kettle., 0.5 part of sodium laurylsulfonate, 0.5 part of OP-10, heating, stirring, logical nitrogen protection.Treat that temperature is elevated to 78 DEG C, by 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, drops in reactor, initiated polymerization.React and obtain emulsion polymer in 2 hours, cool stand-by.Be that 2mm makes by oneself in pesticide granules loading fluidized-bed by 1500g diameter, be heated to 90 DEG C.Viscotrol C is sprayed at self-control pesticide granules surface, spraying Viscotrol C thicknesses of layers is about 5 μm.Then, be 4kpa with two-fluid spray nozzle at atomizing pressure, with the speed of per minute 2g, polymer emulsion be sprayed at particulate state castor-oil plant oil reservoir surface, after fully dry, in removing rete, institute is moisture, is namely prepared into coated release-controlled dose of polyacrylate(s) agricultural chemicals.Wherein, 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 preliminary solubility is 6.7%, and the controlled release phase is 25 days, and Chlorpyrifos 94 preliminary solubility is 8.9%, and the controlled release phase is 20 days.
Claims (7)
1. a polymer coated controlled release granular pesticide, is made up of the polymer layer of pesticide granules and the described pesticide granules of parcel; Wherein, the quality of described polymer layer is 2% ~ 7% of described polymer coated controlled release granular pesticide quality;
Described polymer layer is hydrophobic film layer, and it is made up of water base polyacrylate(s) film material or polyurethanes film material;
Described pesticide granules is made up of the following raw material of 100 mass parts: the auxiliary agent of commercially available various conventional powdered pesticide preparation or 0 ~ 45 part, the former powder of pesticide soluble, commercially available various conventional powdered fertilizer 0 ~ 75 part and commercially available various conventional liquid pesticide or agricultural chemicals stoste 0 ~ 20 part 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 0 time different, and the mass parts of described auxiliary agent is not 0;
The polymer layer of described polymer coated controlled release granular pesticide is made up of water base polyacrylate(s) film material, and described pesticide granules is the pesticide granules of Surface coating organic matter layer; The thickness of described organic matter layer is 2 ~ 10 μm; Described organism is Viscotrol C or palm fibre oil;
The second-order transition temperature of described water base polyacrylate(s) film material is 0 ~ 60 DEG C, 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: monomer 100 parts, initiator 0.5 ~ 1 part, 100 ~ 150 parts, water and emulsifying agent 0.5 ~ 2 part; 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;
Described polyurethanes film material, the raw material 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 is 1:2 ~ 2:1, 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 one: tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, to phenylmethane vulcabond, 1, 4-dicyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethyleterephthalate vulcabond, dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, the many phenyl isocyanate of many subunits, liquefaction diphenylmethanediisocyanate, toluene diisocyanate dimer, toluene diisocyanate trimer, tolylene diisocyanate-TriMethylolPropane(TMP) affixture, tolylene diisocyanate-hexamethylene diisocyanate biruet, isophorone diisocyanate trimer, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4-phenyl isocyanate) and dimethyl triphenyl methane tetraisocyanate,
Described polyvalent alcohol is at least containing the polyvalent alcohol of 2 hydroxyls, its be selected from following a) and/or b) and/or c) at least one:
Described a) is at least one in following polyether glycol: polyoxyethylated polyols, polyoxypropyleneglycol, polyoxytrimethylene triol, polyether triol, polyether tetrols, quadrol polyether glycol, functionality be 3 polyether glycol, polytetrahydrofuran diol, containing side chain polytetrahydrofuran diol;
Described b) is at least one in following vegetable oil polyol: Viscotrol C, soybean oil polyol and plam oil polyvalent alcohol;
Described c) is at least one in following polyester polyol: polyethylene glycol succinate, poly butylene succinate and polyethylene glycol adipate;
Described chainextender is selected from following at least one: 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 one: paraffin, clorafin, sulfonated olefins and rosin ester.
2. polymer coated controlled release granular pesticide according to claim 1, is characterized in that: described powdered pesticide preparation or the former powder of pesticide soluble are selected from following at least one: Provado, Chlorpyrifos 94, benbbensulfuronmethyl, Piao careless clean, benbbensulfuronmethyl, terbufos, thiram, jingganmycin and hymexazol;
Described liquid pesticide or agricultural chemicals stoste are selected from following at least one: alachlor, acetochlor, metolachlor, Butachlor technical 92 and Stam F-34;
Described fertilizer is selected from following at least one: nitrogen-phosphorus-potassium compound fertilizer, ammonium chloride, urea, volatile salt, ammonium nitrate, ammonium sulfate, monoammonium phosphate, diammonium phosphate, Repone K, potassium sulfate and Zinc Sulphate Heptahydrate;
Described auxiliary agent is selected from following at least one: 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, is characterized in that: described pesticide granules prepares according to the method comprised the steps:
1) auxiliary agent, powdered pesticide preparation or the former powder of pesticide soluble and fertilizer are added in tablets press, mixing;
2) upon mixing material surface spray add atomized water, then at the uniform velocity drip described liquid pesticide or agricultural chemicals stoste on described material surface, complete granulation;
3) pesticide granules obtained is carried out drying, screening, obtain pesticide granules core core;
Wherein, step 1) described in tablets press be specially adjustable rotating speed
granulating disc;
Step 1) rotating speed of granulating disc is 5 ~ 10r/min in described mixing process;
Step 2) in, described granulating disc rotating speed is 25 ~ 35r/min; Described atomized water is realized by atomizer; It adds with 10 ~ 500g/min flow with peristaltic pump.
4. polymer coated controlled release granular pesticide according to claim 1, it is characterized in that: described water base polyacrylate(s) film material prepares according to the method comprised the steps: in a kettle., add 100 ~ 150 parts, water in mass ratio, emulsifying agent 0.5 ~ 2 part, heating, stir, logical nitrogen, treat that temperature is increased to 70 ~ 90 DEG C, by described monomer 100 parts, initiator 0.5 ~ 1 part 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 made up of at least one material of following mass parts: vinylformic acid 0 ~ 30, methyl acrylate 0 ~ 30 part, ethyl propenoate 0 ~ 60 part, butyl acrylate 0 ~ 60 part, Hydroxyethyl acrylate 0 ~ 40, methyl methacrylate 0 ~ 70 part, butyl methacrylate 0 ~ 50 part, methacrylic acid 0 ~ 20, the different monooctyl ester of vinylformic acid-2-0 ~ 50 part, n-methylolacrylamide 0 ~ 30 part, glycidyl acrylate 0 ~ 20 part, Viscoat 295 0 ~ 20 part, dimethylaminoethyl methacrylate 0 ~ 30 part and diethylaminoethyl methacrylate 0 ~ 20 part,
Described function monomer is made up of at least one material of following mass parts: vinylbenzene 0 ~ 60 part, vinyl acetate 0 ~ 30 part, 4-vinylpridine 0 ~ 25 part, 2-vinyl pyridine 0 ~ 25 part, Vinylstyrene 0 ~ 10 part;
Described emulsifying agent is selected from following at least one: OP-10, sodium laurylsulfonate and Sodium dodecylbenzene sulfonate;
Described initiator is Potassium Persulphate and/or ammonium persulphate.
5. polymer coated controlled release granular pesticide according to claim 1, is characterized in that: the raw material making described polyurethanes film material also comprises catalyzer;
Described catalyzer is for being selected from following at least one: 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.
6. prepare the method for the polymer coated controlled release granular pesticide that the polymer layer described in claim 1 or 4 is made up of water base polyacrylate(s) film material, comprise the steps:
1) in a kettle., add 100 ~ 150 parts, water in mass ratio, described emulsifying agent 0.5 ~ 2 part, heating, stir, logical nitrogen, treats that temperature is increased to 70 ~ 90 DEG C, by 100 parts of described monomers, 0.5 ~ 1 part of described initiator to be added drop-wise in reactor under fully stirring, initiated polymerization, obtain emulsion polymer coating liquid, cooling discharging is for subsequent use;
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 μm, then again by being sprayed at the described pesticide granules surface after the preheating being in fluidized state after described emulsion polymer coating liquid atomization, coating is carried out; Wherein, in the emulsion polymer coating liquid used, the quality of component is in addition to water 3% ~ 15% of described pesticide granules quality;
3) after coating completes, drying is carried out to the pesticide granules after coating, after cooling, namely obtain described polymer coated controlled release granular pesticide;
Wherein, step 1) described in reaction times of polyreaction be 2 ~ 7h;
Step 2) described in the condition of preheating be: preheating 10 ~ 15min at 75 ~ 90 DEG C;
Step 2) described in organism be Viscotrol C or palm fibre oil;
Step 2) described in the atomization of emulsion polymer coating liquid realized by atomizing nozzle, described atomizing nozzle is pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015 ~ 0.0080MPa, and transfer rate is 5 ~ 200ml/min;
Step 2) described in coating equipment in sugar production line be rotary drum or fluidized-bed;
Step 2) described in fluidized state preheating after described pesticide granules by regulating rotary drum rotating speed 5 ~ 10r/min, or fluidized-bed centrifugal blower frequency 35 ~ 45Hz realizes.
7. prepare the method for the polymer coated controlled release granular pesticide that the polymer layer described in claim 1 or 5 is made up of polyurethanes film material, comprise the steps:
1) a) and b) be preheating to molten state respectively by following, then mixed, obtained polymer capsule liquid; Describedly a) to be made up of described isocyanic ester and furtherance film; Described b) described polyvalent alcohol and chainextender;
2) described pesticide granules being placed in coating equipment in sugar production line and carrying out preheating, then by being sprayed at the described pesticide granules surface after the preheating being in fluidized state after described polymer capsule liquid atomization, carrying out coating; Coating terminates rear cooling, 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;
Wherein, step 1) described in mixing time be 0.1 ~ 20s;
Step 2) described in the condition of preheating be: preheating 10 ~ 15min at 50 ~ 90 DEG C;
Step 2) described in the atomization of polymer capsule liquid realized by atomizing nozzle, described atomizing nozzle is pressure type atomizing nozzle, and its atomizing pressure scope is 0.0015 ~ 0.8MPa, and transfer rate is 0.01 ~ 1kg/min;
Step 2) described in coating equipment in sugar production line be rotary drum or fluidized-bed;
Step 2) described in fluidized state preheating after described pesticide granules by regulating rotary drum rotating speed 5 ~ 10r/min, or fluidized-bed centrifugal blower frequency 35 ~ 45Hz realizes.
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Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105121490A (en) * | 2013-04-26 | 2015-12-02 | 陶氏环球技术有限责任公司 | Polyurethane encapsulate |
| CN103772646B (en) * | 2013-12-31 | 2016-07-20 | 山东茂施生态肥料有限公司 | A kind of containing soybean oil polyol biodegradable slow-release or control-release fertilizer coating material and preparation technology thereof |
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| CN104291935A (en) * | 2014-09-19 | 2015-01-21 | 成都新柯力化工科技有限公司 | Application of polymer microspheres in controlled-release fertilizer |
| FR3027024B1 (en) * | 2014-10-09 | 2016-11-25 | Roquette Freres | PROCESS FOR THE PREPARATION OF THERMOPLASTIC POLYURETHANE PELLETS |
| CN104262019B (en) * | 2014-10-11 | 2016-07-06 | 辽宁芦田肥业有限公司 | A kind of peplos degrading slow release potash fertilizer |
| CN104430322A (en) * | 2014-11-14 | 2015-03-25 | 中国农业科学院植物保护研究所 | Preparation method and application of metalaxyl or mefenoxam controlled-release granules |
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| CN106417280A (en) * | 2016-05-09 | 2017-02-22 | 张伟汉 | High-content coated pesticide granules and preparation method thereof |
| US20190225734A1 (en) * | 2016-07-08 | 2019-07-25 | Resinate Materials Group, Inc. | Sustainable polyol blends for high-performance coatings |
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| BR112020006320A2 (en) * | 2017-09-27 | 2020-09-24 | Pioneer Hi-Bred International, Inc. | agricultural composition, methods for producing an agricultural composition, method for increasing the absorption of a crop protection agent in a crop plant, method for increasing the yield of a crop in a field, method of providing a plurality of agricultural microspheres of prolonged release to a crop field comprising a plurality of crop seeds and method of increasing yield of a crop plant |
| CN108935457A (en) * | 2018-07-26 | 2018-12-07 | 广西田园生化股份有限公司 | Application and method that controlled release pesticide as matrix is prepared using beeswax of the beeswax in realizing controlled-release pesticide |
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| CN110700808B (en) * | 2019-10-23 | 2021-06-25 | 克拉玛依科美利化工有限责任公司 | End sand-removing fracturing method |
| CN110876378A (en) * | 2019-12-11 | 2020-03-13 | 利民化学有限责任公司 | Intelligent microcapsule suspending agent and preparation method thereof |
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| CN112939662A (en) * | 2021-02-26 | 2021-06-11 | 江西农业大学 | Spike fertilizer for large-area balanced yield increase of rice and application method thereof |
| CN114794114B (en) * | 2022-05-31 | 2023-06-09 | 浙江威尔达化工有限公司 | Pesticide microcapsule suspending agent for preventing and treating rice diseases and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL195763B1 (en) * | 1997-06-30 | 2007-10-31 | Monsanto Technology Llc | Microparticles containing a chemical agent used in agriculture |
| EP1148107B1 (en) * | 1998-12-14 | 2005-03-02 | Chisso Corporation | Coated biologically active grains |
| ATE258824T1 (en) * | 2000-03-17 | 2004-02-15 | Bayer Cropscience Ag | MICRO CAPSULE SUSPENSIONS |
| CN100491297C (en) * | 2008-03-10 | 2009-05-27 | 山东金正大生态工程股份有限公司 | Multi-nutrition release-controllable special-purpose fertilizer for clivia and preparation method thereof |
| CN102276356B (en) * | 2011-07-11 | 2014-06-18 | 广西田园生化股份有限公司 | Stable controlled release particle pesticide-containing fertilizer |
| CN102924164B (en) * | 2012-04-24 | 2014-07-09 | 中国科学院南京土壤研究所 | Water-based polymer polyacrylate coated fertilizer modified based on biochar, and preparation method thereof |
| CN102823619A (en) * | 2012-09-20 | 2012-12-19 | 贵州大学 | Imidacloprid sustained-release granules and preparation and application thereof |
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