CN101323545A - Degradable polymer filmcoated controlled release fertilizer, preparation thereof and special filmcoated material - Google Patents
Degradable polymer filmcoated controlled release fertilizer, preparation thereof and special filmcoated material Download PDFInfo
- Publication number
- CN101323545A CN101323545A CNA2008101168767A CN200810116876A CN101323545A CN 101323545 A CN101323545 A CN 101323545A CN A2008101168767 A CNA2008101168767 A CN A2008101168767A CN 200810116876 A CN200810116876 A CN 200810116876A CN 101323545 A CN101323545 A CN 101323545A
- Authority
- CN
- China
- Prior art keywords
- fertilizer
- diisocyanate
- coated
- controlled release
- following
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Fertilizers (AREA)
Abstract
The invention discloses a polymer coated released fertilizer and a preparation method thereof and a special coating material thereof. The coating material comprises isocyanate, polyol, degradable functional monomer, an aid agent of coating and a chain extender, wherein, the mol ratio between the isocyano group in the isocyanate and the hydroxyl group in the polyol is 1:2 to 2:1 and the mass of the degradable functional monomer is 1 percent to 20 percent of the mass of the coating material. The coated released fertilizer provided by the invention consists of a core and a karyotheca, wherein, the core is granule fertilizer and the karyotheca is prepared from the coating material, and the mass of the karyotheca is 2 percent to 10 percent of the mass of the core. The coating material has good film forming and water resisting performance and can be degraded in nature. The hardness and the elasticity of the material can be adjusted by changing the mixure ratio of the coating material so as to prepare released fertilizers with different releasing periods.
Description
Technical field
The present invention relates to a kind of novel degradable type polymer coating controlled release fertilizer and preparation method thereof and dedicated capsule material.
Background technology
China is a large agricultural country, and the ratio of chemical fertilizer in the agriculture production investment accounts for 50%, but China's fertilizer utilization ratio but has only 30%, causes the huge waste on the economical energy resources thus and has caused various environmental problems.Therefore release and release control fertilizer becomes the developing direction of the future of agriculture fertilizer, and the polymer coated fertilizer then is called real release and release control fertilizer by relevant expert.It is to utilize macromolecular material to form thin film on the fertilizer surface, the dissolution rate of control fertilizer in soil, make its dissolution rate consistent, thereby reach the purpose of saving fertilizer, improving utilization rate of fertilizer and increase agricultural performance with the growth demand of plant.
The polymer capsule material can be divided into organic solvent type, aqueous-based polymers and small molecule monomer in-situ polymerization three kinds of principal modes such as film forming on the fertilizer surface.What domestic research was more is the organic solvent type polymer materials, and many old plastics with polyolefine or recovery are the film material, are dissolved in and are sprayed on the fertilizer surface filming in the organic solvent.But it exists production cost higher, the environmental pollution that Recovery of Organic Solvent not exclusively causes in the production process is serious, coated fertilizer is difficult for being degraded by microorganisms, cause so-called problems such as " white pollutions " easily, life-time service can have serious consequences to soil, thereby has limited its large-scale promotion application.
Agent has significant advantage as coating to adopt the aqueous-based polymers material, and it does not have environmental pollution problems with water as solvent, does not have expensive solvent recovery unit, and the coat fertilizer price also has tangible reduction than the solvent-borne type coat fertilizer.At present, domestic water-based polymer coated controlled release fertilizer research emphasis is to seek existing commercial polymer material and is applied on the film-coated controlled release fertilizer, and be rareness very at the investigation of materials of release and release control fertilizer specially, therefore in the process of using water-based polymer coated material ubiquity because the thawing of the fertilizer that the high humidity environment of coating causes, thereby do not reach the problem of ideal controlled-release effect, seriously restricted water-based polymer coated Development of Materials.
In recent years, external increasing research unit focuses on the in-situ polymerization: be about to small molecule monomer and directly become the membrane prepare coating controlled-release fertilizer in the fertilizer surface reaction, can further reduce the cost of coat fertilizer like this, make coating controlled-release fertilizer large-scale promotion application on field crop become possibility.Being reacted into the material of main part that the membranous type coating controlled-release fertilizer adopts is materials such as urethane and Synolac, comprises the scientific research personnel of countries such as the U.S., Japan, Israel and Canada, has applied for many relevant United States Patent (USP)s.For example: (US 4711659 for William P.Moore, US 4804403, US 4969947 etc.) in a series of patents, describe first employing and fertilizer and carried out chemical bond and combine and form the first layer coating, adopted polyurethane material to carry out the release and release control fertilizer of second layer coating then.In Alice P.Hudson (US 5538531) patent clear and definite description employing isocyanic ester and polyvalent alcohol, it has adopted, and to purchase in the trade(brand)name of Dow Chemical be Monder TD, TDS, and the tolylene diisocyanate of TD-80 etc. and comprise Viscotrol C and the multiple polyvalent alcohol of hydrogenated castor oil is the making method of the polyurethane coated controlled-release fertilizer of raw material.Bayer Corporation is at its United States Patent (USP) (US5851261, US6358296B1, US6503288B1) by remaining on the slow mixing process of fertiliser granulates in the coated fertilizer application, improve the homogeneous integrity of polyurethanes coated fertilizer coating on fertiliser granulates in.Nobuaki Tabei is (US7018440 B2 in its serial patent, US7018 441 B2, US2003/003843A1, US2003/0051523A1) described and utilize polyurethane material to carry out the manufacturing of release and release control fertilizer, be characterized in adopting the mode of multilayer coating, reach the homogenization of mould material, thereby improved controlled-release effect.Nick P.Wynnyk etc. has delivered series about optimizing the patent (US2007/0137274A1 of polyurethane coated controlled-release fertilizer method after 2004, US2007/0169527A1, US 2006/0032282A1, US2004/0020254A1, US2004/0016276A1) simultaneously, its team has applied for relevant patent (CN 101006032A) with the polyurethanes coating process of its optimization in China: the method and apparatus of producing coated article, and the method and apparatus that in rotating drum, coats controlled release product, in these relevant patents, methods and relevant equipment have been announced about the coating percentage of head rice that improves polyurethane material.
Though the thermohardening resin coated material of polyurethanes has been carried out a large amount of research, but the problem that in use also exists some never to solve fully: isocyanate component and the polyol component degree of mixing on fertiliser granulates is lower, and the coating utilization ratio of raw materials is low; Because raw material monomer is from the increase of liquid state to solid-state transition process medium viscosity, simultaneously owing to there is not the antiseized effect of solvent, cause raw material monomer after evenly coating granulated fertilizer, in solidification process, can occur tearing, pin hole, the homogeneous degree is relatively poor to wait the macroscopic defective, thereby has seriously influenced controlled release properties.That mentions in the Chinese patent of applications such as Nick P.Wynnyk takes cured in stages, make the fertilizer cure stage contact minimized various measure, improved the integrity of coating process to a great extent, but there is the comparatively complicated defective of technology in it, and it is not advocated urethane raw and arrives fertilizer thorough mixing before, thereby reduced the homogeneity of the chemical ingredients of coated fertilizer, therefore, relying on the contact between the fertilizer to make two big class raw materials of urethane mix on the fertiliser granulates, its degree of mixing is limited, certainly will influence final film forming film properties.
On the other hand, because the high chemical stability of polyurethane material, if this type of release and release control fertilizer is widely used in field crop, the problem that must solve is the biodegradability problem of coated fertilizer.Because if the film material that life-time service is difficult to degrade, residual film material must bring serious environmental problem to soil.Therefore, the polyurethanes film-coated controlled release fertilizer still is the space that all is significantly improved, the aspects such as novelty of mould material from preparation technology.
Summary of the invention
The purpose of this invention is to provide a kind of novel degradable type polymer coating controlled release fertilizer and preparation method thereof and dedicated capsule material.
The dedicated capsule material of release and release control fertilizer provided by the present invention comprises: isocyanic ester, polyvalent alcohol, degradable function monomer, furtherance film and chainextender; Wherein, in the described isocyanic ester in contained isocyano group and the polyvalent alcohol mol ratio of institute's hydroxyl group be 1: 2～2: 1, the quality of described degradable function monomer is the 1%-20% of described coated fertilizer quality, the quality of described furtherance film and the mass ratio of described coated fertilizer are greater than 0 smaller or equal to 30%, and the quality of described chainextender and the mass ratio of described coated fertilizer are smaller or equal to 15% greater than 0.
The composition of described coated fertilizer also comprises catalyzer, and the quality of described catalyzer and the mass ratio of described coated fertilizer are smaller or equal to 0.05% greater than 0.
What described coated fertilizer was made is to have the good controlled capability and the urethane of biodegradability.
Polymer coating controlled release fertilizer provided by the present invention is made up of nuclear core and nuclear membrane, and wherein, described nuclear core is a granulated fertilizer, and described nuclear membrane is made by coated fertilizer provided by the present invention, and described nuclear membrane quality is the 2%-10% of described nuclear core quality.
Wherein, the median size of described granulated fertilizer is 2-6mm.
Another object of the present invention provides a kind of coating liquid (having the good controlled capability and the polyurethane solution of biodegradability) of coated fertilizer.
Coating liquid provided by the present invention is prepared according to following method:
1) with following a) and b) be preheated to molten state respectively, described a) is isocyanic ester and furtherance film in the coated fertilizer provided by the present invention; Described b) comprises polyvalent alcohol, degradable function monomer and chainextender in the coated fertilizer provided by the present invention;
2) with described a) and b) mix, mixing time is 0.1-20 second, makes described coating liquid.
B in the described step 1)) also can comprise catalyzer in the coated fertilizer provided by the present invention.
Wherein, the preheating temperature that contains isocyanate component in the described step 1) can be 50～100 ℃, and the preheating temperature that contains polyol component can be 65～95 ℃, and transport pipe is utilidor; Described step 2) mixing can realize the quick well blend of high-viscous liquid by mixing apparatus in.
The method of the above-mentioned polymer coating controlled release fertilizer of preparation provided by the present invention may further comprise the steps:
1) granulated fertilizer is placed rotary drum or fluidized-bed carry out preheating;
2) coating liquid provided by the present invention is atomized on particles preheated fertilizer surface, makes film-coated controlled release fertilizer.
Wherein, fertiliser granulates preheating temperature in rotary drum or fluidized-bed can be 50～90 ℃ in the described step 1); Described step 2) in described coating solution atomization is realized that by atomizer described atomizer is the pressure type shower nozzle in the fertiliser granulates surface of preheating, the atomizing pressure scope is 0.0015MPa～0.8MPa; The atomizing flow velocity of described coating solution is 0.01～1kg/ minute, by adjusting the scope of atomizing flow velocity, realizes that droplet arrives the fertiliser granulates surface of rotation to greatest extent, mixes film-forming rapidly.
Isocyanic ester described in the present invention is a kind of or its arbitrary combination in following 27 kinds of isocyanic ester: tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), naphthalene diisocyanate (NDI), to the phenylmethane vulcabond, 1,4-bicyclohexane vulcabond, xylylene diisocyanate, the cyclohexanedimethyleterephthalate vulcabond, trimethylammonium-1, the 6-hexamethylene diisocyanate, tetramethyl-mphenylenedimethylim-vulcabond, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, polymethylene multi-phenenyl isocyanate (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 (TDI-HDI) mixes polymer, hexamethylene diisocyanate (HDI) tripolymer, 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 be following a) and/or b) and/or c) and/or d):
Described a) at least a in following 14 kinds of polyether glycols: polyoxyethylene polyvalent alcohol, polyoxypropyleneglycol, polyoxytrimethylene triol, high activity polyether triol, polyether tetrols, quadrol polyether glycol, high functionality polyether glycol, polytetrahydrofuran diol, contain side chain polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolyether glycol, tetrahydrofuran (THF)-ethylene oxide copolymerization glycol, polyurea polylol, polyacrylate polyol and polyethylene polyvalent alcohol;
Described b) is at least a in the following three vegetable oil polyvalent alcohols: Viscotrol C, soybean oil polyvalent alcohol and plam oil polyvalent alcohol;
Described c) is at least a in following eight kinds of polyester polyols: polyethylene glycol succinate, poly butylene succinate, polyethylene glycol adipate, poly adipate succinic acid ester, Aromatic Polyester Polyols, polymerized thylene carbonate ethyl ester, polycarbonate diol and polycaprolactone polyol;
Described d) is at least a in following five kinds of materials: polysuccinimide, polyglycolic acid, poly(lactic acid), polycaprolactone and poly-(ε-ketone in oneself) glycol.
Described degradable function monomer is at least a in the following substances:
Tannin, xylogen, chitosan, Mierocrystalline cellulose, polyamino acid, molasses, modified-cellulose, chitin, take off second phthalein chitin and other carbohydrate and theirs is material modified;
From gelatin modified resin, sericin modified resins, lignin modified resin and other protein modified resin and from the natural high polymer of vegetables oil;
Monose, disaccharides, oligosaccharides, polysaccharide and their derivative and modified compound;
Nitrocellulose, cellulose acetate, ethyl cellulose, match fine jade Lip river viscose rayon, regenerated cellulose, glassine paper, copper are by silk, cuprophane, Bemberg silk, hemicellulose, starch, Sudan Gum-arabic, birds droppings glue, chitin, chitose and their modified material;
Described monose is at least a in the following sugar: erythrose, ribose, pectinose, wood sugar, lyxose, allose, altrose, glucose, seminose, gulose, her shut out sugar, semi-lactosi, talose, fructose, Glucopyranose, glucofuranose, galactofuranose, arabopyranose, pyranofructose, xylulose, ribulose, sedoheptulose, rhamnosyl, Fucose, glycosamine and GalN;
Described polysaccharide is at least a in the following sugar: chitosan, molasses, chitin, take off second phthalein chitin, Mierocrystalline cellulose, modified-cellulose, starch and Sudan Gum-arabic;
Described Mierocrystalline cellulose is at least a in the following substances: nitrocellulose, cellulose acetate, ethyl cellulose, regenerated cellulose, match fine jade Lip river viscose rayon, glassine paper, copper are by silk, cuprophane, hemicellulose and lignin;
Described catalyzer is a kind of or its arbitrary combination in following 18 kinds of materials: dibutyl tin laurate, stannous octoate, triethylamine, dimethyl cetylamine, two dimethyl amine benzyl ethyl ether, diethylenetriamine, triethylenediamine, tetramethyl butane diamine, N-Ethylmorphine quinoline, N, N-dimethylcyclohexylamine, trolamine, methyldiethanolamine, dimethylethanolamine, pyridine, N, N '-lutidine, 1,2,4-tri methyl piperazine, two ketoimines and α-Qiu Jibenbingmizuo.
Described chainextender is 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1, a kind of or its arbitrary combination in 6-hexylene glycol, glycerine, TriMethylolPropane(TMP) and the sorbyl alcohol.
Described furtherance film is a kind of or its arbitrary combination in paraffin, clorafin, sulfonation paraffin, rosin ester, petroleum resin, terpine resin and the pitch.
Granulated fertilizer described in the present invention can be various water miscible granulated fertilizers, comprises urea, volatile salt, ammonium nitrate, ammonium sulfate, vitriolate of tartar, Repone K, saltpetre, Secondary ammonium phosphate, primary ammonium phosphate etc., also comprise various trace elements (iron, manganese, boron, zinc, copper, molybdenum) fertilizer; Can be straight fertilizer, also can be the composite fertilizer of various ratios.Described water soluble fertilizer is a particulate state, can be the uniform granular urea of granulation, also can be the uneven composite fertilizer of granulation, particle diameter is at 2～6mm, if granular urea or composite fertilizer, granular urea sieves earlier and removes powder, particle diameter is controlled at 2-6mm, and preheating is used then.
The invention discloses a kind of thermoset resin material with biological degradability that is applied to film-coated controlled release fertilizer, this material has favorable biological degradability in physical environment.By in the preparation process of polymeric film material, introduce biodegradable chemical group, make the film material to be discarded in safely in the physical environment, this kind polymeric film material can obtain under the reaction conditions of gentleness, and have good environment degradable ability, can hydrolysis ability and biodegradability.Preparation technology of the present invention compares with common process, adopted and a kind ofly can realize isocyanate component and the well-mixed micro-spraying coating process of polyol component, this technology has improved the utilization ratio of coated fertilizer greatly, and realized the thorough mixing of isocyanate component and polyol component, improved the controlled release properties of fertilizer, can be widely used in thermosetting resins such as urethane in the film forming technological process of particle surface reaction in.Degraded type polymer capsule material involved in the present invention and preparation technology's economically feasible of film-coated controlled release fertilizer thereof, stable degree height.Degradable type polymer coating controlled release fertilizer of the present invention and preparation process thereof at home and abroad do not appear in the newspapers, and do not see use at home.
Compare with film-coated controlled release fertilizer in the past, the present invention adopts biodegradable urethane as coated fertilizer, and has adopted the method that mixes raw material and trace spraying fast, has following tangible advantage:
1) in the forming process of polyurethane coated material, introduced biodegradable group, make coated fertilizer have the ability of environment degradable, guarantee when using this film-coated controlled release fertilizer, can not bring so-called " white pollution ", realized environmental friendliness to soil;
2) this technical process has realized isocyanic ester and the uniform mixing of polyol component before arriving fertiliser granulates, has improved to arrive the chemical ingredients homogeneity of the mould material of fertiliser granulates, thereby has improved the controlled release properties of mould material;
3) method of micro-spraying has been adopted in this technical process, makes mixed uniformly mould material at utmost directly arrive the surface of fertilizer, film-forming, thus improved the homogeneity that mould material distributes greatly on fertiliser granulates, improved the over-all properties of release-controlled film.
Description of drawings
Fig. 1 produces the process flow sheet of film-coated controlled release fertilizer for the present invention, and wherein, 1 and 2 is reactor, and 3 is proportioning pump, and 4 is mixing tank, and 5 is rotary drum or fluidized-bed.
Embodiment
It is as follows that the present invention produces the processing step of film-coated controlled release fertilizer:
1, takes by weighing quantitative fertiliser granulates and be positioned in rotary drum or the fluidized-bed (among Fig. 1 shown in 5) and carry out preheating, keep preheating temperature within 50～90 ℃ scope.
2, calculate the consumption of coated fertilizer according to 2%～10% of core fertilizer granular mass.With fertilizer amount 10kg is example, then the amount ranges of coated fertilizer is 200g～1000g, the ratio that guarantees the amount of substance of isocyano group and OH (hydroxyl) group when calculating the content of isocyanic ester and polyvalent alcohol two components is 1: 2～2: 1, and degradable function monomer content is 1%～20% of mould material total amount; The content of furtherance film is 0%～30% of mould material total amount; Chainextender content is 0%～15% of mould material total amount; Catalyst content is 0%～0.05% of a film material gross weight.Respectively as for preheating in the thermostatically heating reactor (among Fig. 1 shown in 1 and 2), the preheating temperature of isocyanate component is 50～100 ℃ with isocyanic ester and polyol component, and the preheating temperature of polyvalent alcohol component is 65～95 ℃.
3, open proportioning pump (among Fig. 1 shown in 3), the ratio of this proportioning pump adjustable volume ratio and output pressure, (pressure is 0.0015～8MPa), after two ingredient liquids is mixed through Hi-mixer to adjust flow and atomizing pressure, begin spraying, the time of spraying is 1～30 minute.After spraying is finished, keep 50-90 ℃ temperature, close heating system after 10 minutes, cooling obtains film-coated controlled release fertilizer.
Above-mentioned film-coated controlled release fertilizer is carried out controlled release properties to be detected:
Adopt water-extraction method to measure the release period of film-coated controlled release fertilizer, promptly take by weighing the fertilizer sample 10.00g that develops, put into nylon net bag, immersion contains in the Plastic Bottle of 200mL distilled water then, and sealing places 25 ℃ of constant incubators to leave standstill, lixiviate, each sample are provided with three repetitions.Guarantee during sampling that nylon net bag in Plastic Bottle, shakes up taking-up with vat liquor, be used for the mensuration of N, P, K, adding distil water 200mL continues to cultivate in constant incubator simultaneously, and the sampling and measuring time is 1 day, and 7 days, 10 days, 14 days, 21 days, 28 days.Wherein, GB/T 8572-2001 standard is adopted in the N element determination; GB/T 8573-1999 standard is adopted in the P element determination; GB/T 8574-1988 standard is adopted in the K element determination.
The controlled release properties evaluation index of film-coated controlled release fertilizer:
Initial stage solubility rate η
T1=M
T1/ M * 100%, differential solubility rate η
Δ t=(η
Tn-η
T1)/(t
n-t
1) * 100%, cumulative release rate η=Σ (η
Tn), fertilizer releasing period T=1+ (80%-η
T1)/η
Δ tt
nBe n days, t
1Be the 1st day, η
TnBe n-i days accumulative total release rates, η
T1Be initial stage solubility rate, M
T1Be the amount of nutrients of stripping in the 1st day, M is the total nutrient content in the coat fertilizer.
Biological degradability is estimated: with the film material of different polymer coated controlled release fertilizer, in accurately placing into the soil after the weighing, every sampling in 1 month, wash the earth after drying on surface, weighing once more calculates the sample weight rate of loss.
Enumerating object lesson is below further specified the present invention.
Embodiment 1,
Take by weighing the granular urea 10kg of particle diameter 3mm, place rotary drum, open the heater switch of rotary drum, carry out the preheating of fertilizer, until homo(io)thermism at 85 ℃.Take by weighing diphenylmethanediisocyanate (MDI) 150g, add paraffin (furtherance film) 60g, place heating kettle fusion constant temperature to 75 ℃.Take by weighing polyether glycol series (Jing Zhou Long Hua petro-chemical corporation 635 types) 210g, 2,3-butyleneglycol (chainextender) 20g, tannin 20g (degradable function monomer) places 90 ℃ of heating kettle fusion constant temperature.Open the venting valve of proportioning pump then, 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 0.15 liter/minute, begins spraying.Spraying stopped spraying after 3 minutes continuously, and postcooling cooling in 8 minutes is reacted in 90 ℃ of insulations, obtains film-coated controlled release fertilizer.Adopt water-extraction method to measure its controlled release properties, the initial stage solubility rate is 1.2%, and the controlled release phase is 48 days, the degraded 12% in 12 months of polymeric membrane material.
Embodiment 2
The 16-16-16 that takes by weighing Russia A Kang composite fertilizer 10Kg places rotary drum, opens the heater switch of rotary drum, carries out the preheating of fertilizer, until homo(io)thermism at 85 ℃.Take by weighing hexamethylene diisocyanate (HDI) 100g, add rosin ester (furtherance film) 80g, place 75 ℃ of heating kettle fusion constant temperature.Take by weighing Viscotrol C 260g, 1,4-butyleneglycol 20g (chainextender), regenerated cellulose 30g (degradable function monomer), and add 0.1g diethylenetriamine (catalyzer), place 80 ℃ of heating kettle fusion constant temperature.Open the venting valve of proportioning pump then, then open and pump into valve, two ingredient liquids is mixed, after Hi-mixer mixes, adjust the pressure 0.1MPa of pump, total speed of spraying is 0.15 liter/minute, begins spraying.Each spraying continuously 12 minutes continues spraying after being incubated 4 minutes then, has sprayed fully until coating liquid, stops spraying, and 85 ℃ of insulation reaction cooled after 10 minutes, obtained film-coated controlled release fertilizer.Adopt water-extraction method to measure its controlled release properties, the initial stage solubility rate is 0.9%, and the controlled release phase is 63 days, the degraded 9% in 12 months of polymeric membrane material.
Taking by weighing that 15-15-15 spreads can rich composite fertilizer composite fertilizer 10Kg, places rotary drum, opens the heater switch of rotary drum, carries out the preheating of fertilizer, until homo(io)thermism at 85 ℃.Take by weighing tolylene diisocyanate (TDI) 200g, add sulfonation paraffin (furtherance film) 140g, place 70 ℃ of heating kettle fusion constant temperature.Take by weighing poly adipate succinic acid ester 420g, 1,6-hexylene glycol (chainextender) 40g, chitosan (degradable function monomer) 65g, and add 0.1g stannous octoate (catalyzer), place 80 ℃ of heating kettle fusion constant temperature.Open the venting valve of proportioning pump then, 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 0.075 liter/minute, begins spraying.Spraying is 6 minutes continuously, has sprayed fully until coating liquid, stops spraying, and 90 ℃ of insulation reaction cooled after 10 minutes, obtained film-coated controlled release fertilizer.Adopt water-extraction method to measure its controlled release properties, the initial stage solubility rate is 0.3%, and the controlled release phase is 89 days, the degraded 7% in 12 months of polymeric membrane material.
Taking by weighing particle diameter is the granular urea 10Kg of 3mm, places rotary drum, opens the heater switch of rotary drum, carries out the preheating of fertilizer, until homo(io)thermism at 85 ℃.Take by weighing dicyclohexyl methane diisocyanate (HMDI) 165g, add petroleum resin (furtherance film) 90g, place 80 ℃ of heating kettle fusion constant temperature, take by weighing polyethylene glycol succinate 240g, sorbyl alcohol (chainextender) 35g, glucose (degradable function monomer) 60g, and add 0.1g triethylamine (catalyzer), place 90 ℃ of heating kettle fusion constant temperature.Open the venting valve of proportioning pump then, 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/ minute, begins spraying.Spraying is 6 minutes continuously, has sprayed fully until coating liquid, stops spraying, and 90 ℃ of insulation reaction cooled after 10 minutes, obtained film-coated controlled release fertilizer.Adopt water-extraction method to measure its controlled release properties, the controlled release phase is 79 days, the degraded 8% in 12 months of polymeric membrane material.
Taking by weighing that 15-15-15 spreads can rich composite fertilizer 10Kg, places rotary drum, opens the heater switch of rotary drum, carries out the preheating of fertilizer, until homo(io)thermism at 85 ℃.Take by weighing tolylene diisocyanate (TDI) 150g, add rosin ester (furtherance film) 90g, place 85 ℃ of heating kettle fusion constant temperature.Take by weighing polyolefin polyhydric alcohol 320g, TriMethylolPropane(TMP) (chainextender) 23g, sucrose (degradable function monomer) 30g, and add 0.05g trolamine (catalyzer), place 80 ℃ of heating kettle fusion constant temperature.Open the venting valve of proportioning pump then, 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/ minute, begins spraying.Spraying is 6 minutes continuously, has sprayed fully until coating liquid, stops spraying, and the postcooling cooling in 10 minutes of 90 ℃ of insulation reaction obtains film-coated controlled release fertilizer.Adopt water-extraction method to measure its controlled release properties, the initial stage solubility rate is 0.5%, and the controlled release phase is 92 days, the degraded 7% in 12 months of polymeric membrane material.
Embodiment 6
Take by weighing Russian A Kang 16-16-16 composite fertilizer 10Kg, place rotary drum, open the heater switch of rotary drum, carry out the preheating of fertilizer, until homo(io)thermism at 80 ℃.Take by weighing polymethylene multi-phenenyl isocyanate (PAPI) 240g, add clorafin (furtherance film) 100g, place 85 ℃ of heating kettle fusion constant temperature.Take by weighing polytetrahydrofuran diol 390g, glycerine (chainextender) 15g, cellulose acetate (degradable function monomer) 50g, and add 0.1g N-Ethylmorphine quinoline, place 80 ℃ of heating kettle fusion constant temperature.Open the venting valve of proportioning pump then, 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/ minute, begins spraying.Spraying is 5 minutes continuously, has sprayed fully until coating liquid, stops, and 80 ℃ of insulation reaction cooled after 8 minutes, obtained film-coated controlled release fertilizer.Adopt water-extraction method to measure its controlled release properties, the controlled release phase is 88 days, the degraded 8% in 12 months of polymeric membrane material.
Claims (10)
1, a kind of coated fertilizer of polymer coating controlled release fertilizer comprises: isocyanic ester, polyvalent alcohol, degradable function monomer, furtherance film and chainextender; Wherein, the mol ratio of oh group is 1: 2～2: 1 in isocyano group in the described isocyanic ester and the polyvalent alcohol, the quality of described degradable function monomer is the 1%-20% of described coated fertilizer quality, the quality of described furtherance film and the mass ratio of described coated fertilizer are greater than 0 smaller or equal to 30%, and the quality of described chainextender and the mass ratio of described coated fertilizer are smaller or equal to 15% greater than 0.
2, coated fertilizer according to claim 1 is characterized in that: described coated fertilizer also comprises catalyzer, and the quality of described catalyzer and the mass ratio of described coated fertilizer are smaller or equal to 0.05% greater than 0.
3, coated fertilizer according to claim 1 and 2 is characterized in that:
Described isocyanic ester is a kind of or its arbitrary combination in following 27 kinds of isocyanic ester: 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, trimethylammonium-1, the 6-hexamethylene diisocyanate, tetramethyl-mphenylenedimethylim-vulcabond, the dimethyl diphenyl vulcabond, Methylcyclohexyl diisocyanate, norbornene alkyl diisocyanate, polymethylene multi-phenenyl isocyanate, the liquefaction diphenylmethanediisocyanate, toluene diisocyanate dimer, toluene diisocyanate trimer, tolylene diisocyanate-TriMethylolPropane(TMP) affixture, tolylene diisocyanate-hexamethylene diisocyanate mixing polymer, hexamethylene diisocyanate trimer, the hexamethylene diisocyanate biuret, isophorone diisocyanate trimer, triphenylmethane triisocyanate, tri o cresyl thiophosphate (4-phenyl isocyanate) and dimethyl triphenyl methane tetraisocyanate;
Described polyvalent alcohol be following a) and/or b) and/or c) and/or d):
Described a) at least a in following 14 kinds of polyether glycols: polyoxyethylene polyvalent alcohol, polyoxypropyleneglycol, polyoxytrimethylene triol, high activity polyether triol, polyether tetrols, quadrol polyether glycol, high functionality polyether glycol, polytetrahydrofuran diol, contain side chain polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolyether glycol, tetrahydrofuran (THF)-ethylene oxide copolymerization glycol, polyurea polylol, polyacrylate polyol and polyethylene polyvalent alcohol;
Described b) is at least a in the following three vegetable oil polyvalent alcohols: Viscotrol C, soybean oil polyvalent alcohol and plam oil polyvalent alcohol;
Described c) is at least a in following eight kinds of polyester polyols: polyethylene glycol succinate, poly butylene succinate, polyethylene glycol adipate, poly adipate succinic acid ester, Aromatic Polyester Polyols, polymerized thylene carbonate ethyl ester, polycarbonate diol and polycaprolactone polyol;
Described d) is at least a in following five kinds of materials: polysuccinimide, polyglycolic acid, poly(lactic acid), polycaprolactone and poly-(ε-ketone in oneself) glycol.
Described degradable function monomer is at least a in the following substances: tannin, xylogen, polyamino acid, gelatin modified resin, sericin modified resins, lignin modified resin, birds droppings glue, the natural high polymer from vegetables oil, monose, disaccharides, oligosaccharides, polysaccharide;
Described monose is at least a in the following sugar: erythrose, ribose, pectinose, wood sugar, lyxose, allose, altrose, glucose, seminose, gulose, her shut out sugar, semi-lactosi, talose, fructose, Glucopyranose, glucofuranose, galactofuranose, arabopyranose, pyranofructose, xylulose, ribulose, sedoheptulose, rhamnosyl, Fucose, glycosamine and GalN;
Described polysaccharide is at least a in the following sugar: chitosan, molasses, chitin, take off second phthalein chitin, Mierocrystalline cellulose, modified-cellulose, starch and Sudan Gum-arabic;
Described Mierocrystalline cellulose is at least a in the following substances: nitrocellulose, cellulose acetate, ethyl cellulose, regenerated cellulose, match fine jade Lip river viscose rayon, glassine paper, copper are by silk, cuprophane, hemicellulose and lignin;
Described furtherance film is a kind of or its arbitrary combination in paraffin, clorafin, sulfonation paraffin, rosin ester, petroleum resin, terpine resin and the pitch;
Described chainextender is 1,4-butyleneglycol, 2,3-butyleneglycol, glycol ether, 1, a kind of or its arbitrary combination in 6-hexylene glycol, glycerine, TriMethylolPropane(TMP) and the sorbyl alcohol.
4, according to claim 2 or 3 described coated fertilizers, it is characterized in that: described catalyzer is a kind of or its arbitrary combination in following 18 kinds of materials: dibutyl tin laurate, stannous octoate, triethylamine, the dimethyl cetylamine, two dimethyl amine benzyl ethyl ethers, diethylenetriamine, triethylenediamine, tetramethyl butane diamine, N-Ethylmorphine quinoline, N, the N-dimethylcyclohexylamine, trolamine, methyldiethanolamine, dimethylethanolamine, pyridine, N, N '-lutidine, 1,2, the 4-tri methyl piperazine, two ketoimines and α-Qiu Jibenbingmizuo.
5, a kind of polymer coating controlled release fertilizer is made up of nuclear core and nuclear membrane, and wherein, described nuclear core is a granulated fertilizer, and described nuclear membrane is made by arbitrary described coated fertilizer among the claim 1-4, and described nuclear membrane quality is the 2%-10% of described nuclear core quality.
6, fertilizer according to claim 5 is characterized in that: the median size of described granulated fertilizer is 2-6mm.
7, a kind of coating liquid of coated fertilizer is prepared according to following method:
1) with following a) and b) be preheated to molten state respectively, described a) is isocyanic ester in arbitrary described coated fertilizer and furtherance film among the claim 1-5; Described b) comprises the polyvalent alcohol in arbitrary described coated fertilizer, degradable function monomer and chainextender among the claim 1-5;
2) with described a) and b) mix, mixing time is 0.1-20 second, makes described coating liquid.
8, coating liquid according to claim 7 is characterized in that: the b in the described step 1)) also comprise the catalyzer in arbitrary described coated fertilizer among the claim 2-4.
9, a kind of method for preparing claim 5 or 6 described polymer coating controlled release fertilizers may further comprise the steps:
1) granulated fertilizer is placed rotary drum or fluidized-bed carry out preheating;
2) claim 7 or 8 described coating liquids are atomized on particles preheated fertilizer surface, make film-coated controlled release fertilizer.
10, according to the described method of claim 9, it is characterized in that: realize by atomizer on the fertiliser granulates surface that described step 2) described coating liquid is atomized on preheating, described atomizer is the pressure type shower nozzle, the atomizing pressure scope is 0.0015MPa～0.8MPa, and the atomizing flow velocity of described coating solution is 0.01～1kg/ minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101168767A CN101323545B (en) | 2008-07-18 | 2008-07-18 | Degradable polymer filmcoated controlled release fertilizer, preparation thereof and special filmcoated material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101168767A CN101323545B (en) | 2008-07-18 | 2008-07-18 | Degradable polymer filmcoated controlled release fertilizer, preparation thereof and special filmcoated material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101323545A true CN101323545A (en) | 2008-12-17 |
| CN101323545B CN101323545B (en) | 2010-08-11 |
Family
ID=40187274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101168767A Active CN101323545B (en) | 2008-07-18 | 2008-07-18 | Degradable polymer filmcoated controlled release fertilizer, preparation thereof and special filmcoated material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101323545B (en) |
Cited By (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002142A (en) * | 2010-09-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Biodegradable polyurethane and preparation method thereof |
| CN102260123A (en) * | 2010-05-28 | 2011-11-30 | 中国科学院沈阳应用生态研究所 | Biodegradable coated urea and its preparation method |
| CN101671425B (en) * | 2009-09-11 | 2012-02-22 | 中国海洋石油总公司 | Polyurethane coated controlled-release fertilizer with improved mechanical property, preparation method thereof and special coating material |
| CN102482170A (en) * | 2009-06-24 | 2012-05-30 | 巴斯夫欧洲公司 | An encapsulated particle |
| CN101648837B (en) * | 2009-09-11 | 2012-09-05 | 中国海洋石油总公司 | Polyurethane filmcoated controlled release fertilizer and preparation method thereof |
| CN102690142A (en) * | 2012-03-28 | 2012-09-26 | 河南力浮科技有限公司 | Method for producing sustained-release granular potassium chloride fertilizer |
| CN103524699A (en) * | 2013-09-22 | 2014-01-22 | 蔡小伶 | Coating film and production method of coated controlled-release fertilizer |
| CN103571020A (en) * | 2013-11-18 | 2014-02-12 | 广东树业环保科技股份有限公司 | Environment-friendly plastic and preparation method thereof |
| CN103626569A (en) * | 2012-08-30 | 2014-03-12 | 北京东辰瑞丰化工有限公司 | Preparation method for slow-release fertilizer |
| CN103819754A (en) * | 2014-02-19 | 2014-05-28 | 福建工程学院 | High toughness starch based thermoplastic plastic and its preparation method |
| CN103833490A (en) * | 2012-11-22 | 2014-06-04 | 苏斌 | Green and environment friendly polyurethane coated controlled release fertilizer |
| CN104031383A (en) * | 2014-04-30 | 2014-09-10 | 中国科学院化学研究所 | 3D printing modified polyamino acid material and preparation method thereof |
| WO2014176390A1 (en) * | 2013-04-26 | 2014-10-30 | Dow Global Technologies Llc | Polyurethane encapsulate |
| CN104151520A (en) * | 2014-07-22 | 2014-11-19 | 武汉诺唯凯生物材料有限公司 | Preparation method of modified starch on basis of vegetable fat plasticizer |
| CN104151073A (en) * | 2014-08-11 | 2014-11-19 | 中国地质大学（武汉） | Preparation method of coated sustained-release fertilizer |
| CN104262019A (en) * | 2014-10-11 | 2015-01-07 | 辽宁芦田肥业有限公司 | Coated degradation type slow release potassium fertilizer |
| CN104355824A (en) * | 2014-11-03 | 2015-02-18 | 领先生物农业股份有限公司 | Coated controlled release fertilizer and production method thereof |
| CN104387213A (en) * | 2014-10-21 | 2015-03-04 | 金正大生态工程集团股份有限公司 | Biodegradable controlled-release coated urea and preparation method thereof |
| CN104649806A (en) * | 2013-11-21 | 2015-05-27 | 中国科学院大连化学物理研究所 | Sodium alginate oligosaccharide coated slow-release fertilizer and preparation and application thereof |
| CN105061095A (en) * | 2015-09-16 | 2015-11-18 | 福建师范大学 | Method for preparing film special for slow/controlled release fertilizer by virtue of camellia oleifera polyphenols and application of film to granulated fertilizer |
| CN105061083A (en) * | 2015-08-21 | 2015-11-18 | 湖南农业大学 | Potash fertilizer controlled release coating agent |
| CN106187641A (en) * | 2016-07-18 | 2016-12-07 | 郑州富谊联科技有限公司 | A kind of synergistic urea by composite plant oil peplos and production method thereof |
| CN106316620A (en) * | 2016-08-24 | 2017-01-11 | 美稼农业科技（上海）有限公司 | Polymer sulfur coated controlled release fertilizer and preparing method thereof |
| CN106800472A (en) * | 2017-03-07 | 2017-06-06 | 上海永通化工有限公司 | A kind of composite modified polyurethane coated liquid, release and release control fertilizer and preparation method thereof |
| CN107011058A (en) * | 2017-05-09 | 2017-08-04 | 中国农业大学 | A kind of anti-salt type function coating slowly/controlled releasing fertilizer and preparation method thereof |
| WO2018009355A1 (en) * | 2016-07-08 | 2018-01-11 | Resinate Materials Group, Inc. | Sustainable polyol blends for high-performance coatings |
| CN107652091A (en) * | 2017-11-17 | 2018-02-02 | 北京市农林科学院 | Controlled release polyglutamic acid coated compound fertilizer and preparation method and application |
| CN108516889A (en) * | 2018-04-28 | 2018-09-11 | 陈建峰 | A kind of coating agent and preparation method thereof |
| CN108794143A (en) * | 2018-04-24 | 2018-11-13 | 百色学院 | A kind of soil conditioner and preparation method thereof |
| CN109504391A (en) * | 2018-11-22 | 2019-03-22 | 四川大学 | A kind of copper polluted soil long-acting repair materials in situ |
| CN109511516A (en) * | 2019-01-17 | 2019-03-26 | 钦州学院 | A kind of rice seedling raising ground substance and preparation method thereof |
| CN110172000A (en) * | 2019-05-29 | 2019-08-27 | 湖北大学 | A kind of preparation method of the degradable coated fertilizer of photo-thermal |
| CN110218121A (en) * | 2019-06-26 | 2019-09-10 | 中国农业科学院农业资源与农业区划研究所 | A kind of release and release control fertilizer and its preparation method and application |
| CN110549717A (en) * | 2019-08-27 | 2019-12-10 | 广西华沃特生态肥业股份有限公司 | packaging material of environment-friendly forest fertilizer, preparation method and packaging method thereof |
| TWI682917B (en) * | 2014-05-05 | 2020-01-21 | 荷蘭商薩比克環球科技公司 | Coated granular fertilizers, methods of manufacture thereof, and uses |
| CN110981602A (en) * | 2019-12-17 | 2020-04-10 | 中盐安徽红四方肥业股份有限公司 | Coated slow-release fertilizer for rice and preparation method and application thereof |
| CN110981603A (en) * | 2019-12-17 | 2020-04-10 | 中盐安徽红四方肥业股份有限公司 | Coated slow-release fertilizer for wheat and preparation method and application thereof |
| US10640430B2 (en) | 2014-01-31 | 2020-05-05 | Saudi Basic Industries Corporation | Fertilizer capsule comprising one or more cores and method of making same |
| US10689306B2 (en) | 2015-07-20 | 2020-06-23 | Sabic Global Technologies B.V. | Fertilizer composition and methods of making and using same |
| CN111574282A (en) * | 2020-05-08 | 2020-08-25 | 徐州莫大新材料科技有限公司 | Solid fertilizer capable of preventing soil swampiness and preparation process thereof |
| CN112048055A (en) * | 2020-09-15 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Polyether ester type polyurethane coating material and controlled release fertilizer prepared from same |
| US10865159B2 (en) | 2015-11-16 | 2020-12-15 | Sabic Global Technologies B.V. | Methods of manufacture for coated granular fertilizers |
| US11001539B2 (en) | 2015-09-11 | 2021-05-11 | Sumitomo Chemical Company, Limited | Coated granular fertilizer, method for producing coated granular fertilizer, and fertilizer compostion |
| US11021409B2 (en) | 2017-08-09 | 2021-06-01 | Sabic Global Technologies B.V. | Extruded fertilizer granules with urease and/or nitrification inhibitors |
| US11104618B2 (en) | 2015-07-20 | 2021-08-31 | Sabic Global Technologies B.V. | Fertilizer composition and methods of making and using same |
| US11124463B2 (en) | 2015-11-16 | 2021-09-21 | Sabic Global Technologies B.V. | Coated granular fertilizers, methods of manufacture thereof, and uses thereof |
| CN114133298A (en) * | 2021-12-20 | 2022-03-04 | 江苏省农业科学院 | One-time fertilization and industrial seedling raising method for rice |
| US11306037B2 (en) | 2017-04-19 | 2022-04-19 | Sabic Global Technologies B.V. | Enhanced efficiency fertilizer with urease inhibitor and nitrification separated within the same particle |
| US11345645B2 (en) | 2017-04-20 | 2022-05-31 | Sabic Global Technologies B.V. | Enhanced efficiency fertilizer with embedded powder composition |
| US11358908B2 (en) | 2017-04-19 | 2022-06-14 | Sabic Global Technologies B.V. | Enhanced efficiency fertilizer with urease inhibitor and nitrification inhibitor in separate particles |
| CN115044010A (en) * | 2022-06-06 | 2022-09-13 | 青海国润农业科技有限公司 | Biodegradable polyurethane sustained and controlled release fertilizer coating material containing amino acid and preparation process thereof |
| GB2616332A (en) * | 2021-12-20 | 2023-09-06 | Jiangsu Acad Agricultural Sci | One-step fertilization and industrial seedling raising method for rice |
| WO2023183236A1 (en) * | 2022-03-21 | 2023-09-28 | Dow Global Technologies Llc | Coated fertilizer granule compositions |
| US11806689B2 (en) | 2016-02-08 | 2023-11-07 | Sabic Global Technologies B.V. | Method of making a fertilizer seed core |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795933B (en) * | 2012-08-27 | 2013-11-06 | 天津市施易得肥料有限公司 | Slow-release degradable coating material and preparation method thereof |
| CN103242086B (en) * | 2013-01-17 | 2014-06-11 | 山东农业大学 | Starch-liquefying modified thermosetting resin film-coated controlled release fertilizer and preparation method thereof |
-
2008
- 2008-07-18 CN CN2008101168767A patent/CN101323545B/en active Active
Cited By (72)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482170A (en) * | 2009-06-24 | 2012-05-30 | 巴斯夫欧洲公司 | An encapsulated particle |
| CN102482170B (en) * | 2009-06-24 | 2014-10-08 | 巴斯夫欧洲公司 | An encapsulated particle |
| CN101671425B (en) * | 2009-09-11 | 2012-02-22 | 中国海洋石油总公司 | Polyurethane coated controlled-release fertilizer with improved mechanical property, preparation method thereof and special coating material |
| CN101648837B (en) * | 2009-09-11 | 2012-09-05 | 中国海洋石油总公司 | Polyurethane filmcoated controlled release fertilizer and preparation method thereof |
| CN102260123A (en) * | 2010-05-28 | 2011-11-30 | 中国科学院沈阳应用生态研究所 | Biodegradable coated urea and its preparation method |
| CN102002142A (en) * | 2010-09-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Biodegradable polyurethane and preparation method thereof |
| CN102690142A (en) * | 2012-03-28 | 2012-09-26 | 河南力浮科技有限公司 | Method for producing sustained-release granular potassium chloride fertilizer |
| CN103626569A (en) * | 2012-08-30 | 2014-03-12 | 北京东辰瑞丰化工有限公司 | Preparation method for slow-release fertilizer |
| CN103833490A (en) * | 2012-11-22 | 2014-06-04 | 苏斌 | Green and environment friendly polyurethane coated controlled release fertilizer |
| CN105121490A (en) * | 2013-04-26 | 2015-12-02 | 陶氏环球技术有限责任公司 | Polyurethane encapsulate |
| WO2014176390A1 (en) * | 2013-04-26 | 2014-10-30 | Dow Global Technologies Llc | Polyurethane encapsulate |
| CN103524699A (en) * | 2013-09-22 | 2014-01-22 | 蔡小伶 | Coating film and production method of coated controlled-release fertilizer |
| CN103571020A (en) * | 2013-11-18 | 2014-02-12 | 广东树业环保科技股份有限公司 | Environment-friendly plastic and preparation method thereof |
| CN104649806A (en) * | 2013-11-21 | 2015-05-27 | 中国科学院大连化学物理研究所 | Sodium alginate oligosaccharide coated slow-release fertilizer and preparation and application thereof |
| CN104649806B (en) * | 2013-11-21 | 2017-10-31 | 中国科学院大连化学物理研究所 | A kind of sodium alginate oligosaccharide enveloped slow release fertilizer and its preparation and application |
| US10640430B2 (en) | 2014-01-31 | 2020-05-05 | Saudi Basic Industries Corporation | Fertilizer capsule comprising one or more cores and method of making same |
| CN103819754A (en) * | 2014-02-19 | 2014-05-28 | 福建工程学院 | High toughness starch based thermoplastic plastic and its preparation method |
| CN103819754B (en) * | 2014-02-19 | 2015-10-28 | 福建工程学院 | A kind of high tenacity starch-based thermoplastic plastics and preparation method thereof |
| CN104031383A (en) * | 2014-04-30 | 2014-09-10 | 中国科学院化学研究所 | 3D printing modified polyamino acid material and preparation method thereof |
| CN104031383B (en) * | 2014-04-30 | 2015-10-21 | 中国科学院化学研究所 | A kind of 3D prints modification polyamino acid material and preparation method thereof |
| TWI682917B (en) * | 2014-05-05 | 2020-01-21 | 荷蘭商薩比克環球科技公司 | Coated granular fertilizers, methods of manufacture thereof, and uses |
| CN110981585A (en) * | 2014-05-05 | 2020-04-10 | 赛贝克环球科技公司 | Coated granular fertilizer, method for producing same and method for fertilizing same |
| US11401218B2 (en) | 2014-05-05 | 2022-08-02 | Sabic Global Technologies B.V. | Coated granular fertilizers, methods of manufacture thereof, and uses |
| CN104151520A (en) * | 2014-07-22 | 2014-11-19 | 武汉诺唯凯生物材料有限公司 | Preparation method of modified starch on basis of vegetable fat plasticizer |
| CN104151073A (en) * | 2014-08-11 | 2014-11-19 | 中国地质大学（武汉） | Preparation method of coated sustained-release fertilizer |
| CN104151073B (en) * | 2014-08-11 | 2016-04-27 | 中国地质大学（武汉） | A kind of preparation method of film-coated and slow release fertilizer |
| CN104262019A (en) * | 2014-10-11 | 2015-01-07 | 辽宁芦田肥业有限公司 | Coated degradation type slow release potassium fertilizer |
| CN104387213A (en) * | 2014-10-21 | 2015-03-04 | 金正大生态工程集团股份有限公司 | Biodegradable controlled-release coated urea and preparation method thereof |
| CN104355824A (en) * | 2014-11-03 | 2015-02-18 | 领先生物农业股份有限公司 | Coated controlled release fertilizer and production method thereof |
| US11104618B2 (en) | 2015-07-20 | 2021-08-31 | Sabic Global Technologies B.V. | Fertilizer composition and methods of making and using same |
| US10689306B2 (en) | 2015-07-20 | 2020-06-23 | Sabic Global Technologies B.V. | Fertilizer composition and methods of making and using same |
| CN105061083B (en) * | 2015-08-21 | 2018-09-18 | 湖南农业大学 | Potash fertilizer controlled release coated agent |
| CN105061083A (en) * | 2015-08-21 | 2015-11-18 | 湖南农业大学 | Potash fertilizer controlled release coating agent |
| US11001539B2 (en) | 2015-09-11 | 2021-05-11 | Sumitomo Chemical Company, Limited | Coated granular fertilizer, method for producing coated granular fertilizer, and fertilizer compostion |
| TWI756183B (en) * | 2015-09-11 | 2022-03-01 | 日商住友化學股份有限公司 | Coated granular fertilizer, method for producing coated granular fertilizer, and fertilizer composition |
| CN105061095A (en) * | 2015-09-16 | 2015-11-18 | 福建师范大学 | Method for preparing film special for slow/controlled release fertilizer by virtue of camellia oleifera polyphenols and application of film to granulated fertilizer |
| US11124463B2 (en) | 2015-11-16 | 2021-09-21 | Sabic Global Technologies B.V. | Coated granular fertilizers, methods of manufacture thereof, and uses thereof |
| US10865159B2 (en) | 2015-11-16 | 2020-12-15 | Sabic Global Technologies B.V. | Methods of manufacture for coated granular fertilizers |
| US11806689B2 (en) | 2016-02-08 | 2023-11-07 | Sabic Global Technologies B.V. | Method of making a fertilizer seed core |
| WO2018009355A1 (en) * | 2016-07-08 | 2018-01-11 | Resinate Materials Group, Inc. | Sustainable polyol blends for high-performance coatings |
| CN106187641A (en) * | 2016-07-18 | 2016-12-07 | 郑州富谊联科技有限公司 | A kind of synergistic urea by composite plant oil peplos and production method thereof |
| CN106316620A (en) * | 2016-08-24 | 2017-01-11 | 美稼农业科技（上海）有限公司 | Polymer sulfur coated controlled release fertilizer and preparing method thereof |
| CN106800472A (en) * | 2017-03-07 | 2017-06-06 | 上海永通化工有限公司 | A kind of composite modified polyurethane coated liquid, release and release control fertilizer and preparation method thereof |
| CN106800472B (en) * | 2017-03-07 | 2021-05-04 | 上海永通生态工程股份有限公司 | Composite modified polyurethane coating liquid, controlled-release fertilizer and preparation method thereof |
| US11306037B2 (en) | 2017-04-19 | 2022-04-19 | Sabic Global Technologies B.V. | Enhanced efficiency fertilizer with urease inhibitor and nitrification separated within the same particle |
| US11802097B2 (en) | 2017-04-19 | 2023-10-31 | Sabic Global Technologies B.V. | Enhanced efficiency fertilizer with urease inhibitor and nitrification separated within the same particle |
| US11358908B2 (en) | 2017-04-19 | 2022-06-14 | Sabic Global Technologies B.V. | Enhanced efficiency fertilizer with urease inhibitor and nitrification inhibitor in separate particles |
| US11345645B2 (en) | 2017-04-20 | 2022-05-31 | Sabic Global Technologies B.V. | Enhanced efficiency fertilizer with embedded powder composition |
| CN107011058B (en) * | 2017-05-09 | 2020-06-09 | 中国农业大学 | Salt-resistant functional coated slow/controlled release fertilizer and preparation method thereof |
| CN107011058A (en) * | 2017-05-09 | 2017-08-04 | 中国农业大学 | A kind of anti-salt type function coating slowly/controlled releasing fertilizer and preparation method thereof |
| US11021409B2 (en) | 2017-08-09 | 2021-06-01 | Sabic Global Technologies B.V. | Extruded fertilizer granules with urease and/or nitrification inhibitors |
| CN107652091A (en) * | 2017-11-17 | 2018-02-02 | 北京市农林科学院 | Controlled release polyglutamic acid coated compound fertilizer and preparation method and application |
| CN108794143A (en) * | 2018-04-24 | 2018-11-13 | 百色学院 | A kind of soil conditioner and preparation method thereof |
| CN108516889A (en) * | 2018-04-28 | 2018-09-11 | 陈建峰 | A kind of coating agent and preparation method thereof |
| CN109504391B (en) * | 2018-11-22 | 2021-02-23 | 四川大学 | In-situ long-acting repair material for copper-polluted soil |
| CN109504391A (en) * | 2018-11-22 | 2019-03-22 | 四川大学 | A kind of copper polluted soil long-acting repair materials in situ |
| CN109511516A (en) * | 2019-01-17 | 2019-03-26 | 钦州学院 | A kind of rice seedling raising ground substance and preparation method thereof |
| CN110172000A (en) * | 2019-05-29 | 2019-08-27 | 湖北大学 | A kind of preparation method of the degradable coated fertilizer of photo-thermal |
| CN110218121A (en) * | 2019-06-26 | 2019-09-10 | 中国农业科学院农业资源与农业区划研究所 | A kind of release and release control fertilizer and its preparation method and application |
| CN110218121B (en) * | 2019-06-26 | 2021-11-02 | 中国农业科学院农业资源与农业区划研究所 | Controlled release fertilizer and preparation method and application thereof |
| CN110549717B (en) * | 2019-08-27 | 2021-12-31 | 广西壮族自治区林业科学研究院 | Packaging material of environment-friendly forest fertilizer, preparation method and packaging method thereof |
| CN110549717A (en) * | 2019-08-27 | 2019-12-10 | 广西华沃特生态肥业股份有限公司 | packaging material of environment-friendly forest fertilizer, preparation method and packaging method thereof |
| CN110981602A (en) * | 2019-12-17 | 2020-04-10 | 中盐安徽红四方肥业股份有限公司 | Coated slow-release fertilizer for rice and preparation method and application thereof |
| CN110981602B (en) * | 2019-12-17 | 2022-05-03 | 中盐安徽红四方肥业股份有限公司 | Coated slow-release fertilizer for rice and preparation method and application thereof |
| CN110981603A (en) * | 2019-12-17 | 2020-04-10 | 中盐安徽红四方肥业股份有限公司 | Coated slow-release fertilizer for wheat and preparation method and application thereof |
| CN111574282A (en) * | 2020-05-08 | 2020-08-25 | 徐州莫大新材料科技有限公司 | Solid fertilizer capable of preventing soil swampiness and preparation process thereof |
| CN112048055A (en) * | 2020-09-15 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Polyether ester type polyurethane coating material and controlled release fertilizer prepared from same |
| CN114133298A (en) * | 2021-12-20 | 2022-03-04 | 江苏省农业科学院 | One-time fertilization and industrial seedling raising method for rice |
| WO2023115323A1 (en) * | 2021-12-20 | 2023-06-29 | 江苏省农业科学院 | One-step fertilization and industrial seedling raising method for rice |
| GB2616332A (en) * | 2021-12-20 | 2023-09-06 | Jiangsu Acad Agricultural Sci | One-step fertilization and industrial seedling raising method for rice |
| WO2023183236A1 (en) * | 2022-03-21 | 2023-09-28 | Dow Global Technologies Llc | Coated fertilizer granule compositions |
| CN115044010A (en) * | 2022-06-06 | 2022-09-13 | 青海国润农业科技有限公司 | Biodegradable polyurethane sustained and controlled release fertilizer coating material containing amino acid and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101323545B (en) | 2010-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101323545B (en) | Degradable polymer filmcoated controlled release fertilizer, preparation thereof and special filmcoated material | |
| CN103387456B (en) | Polymer-coated controlled release pesticide granule and preparation method thereof | |
| CN102320883B (en) | Polyurethane/epoxy resin compound material coated controlled release fertilizer and preparation method thereof | |
| US6364925B1 (en) | Polyurethane encapsulated fertilizer having improved slow-release properties | |
| US6358296B1 (en) | Slow-release polyurethane encapsulated fertilizer using oleo polyols | |
| Yang et al. | Biobased polymer composites derived from corn stover and feather meals as double-coating materials for controlled-release and water-retention urea fertilizers | |
| CA2275887C (en) | A process for the production of polyurea encapsulated fertilizer particles and the encapsulated fertilizer particles produced by this process | |
| CN102482170B (en) | An encapsulated particle | |
| CN101282919B (en) | Controlled release fertilizer employing epoxidized fatty acid triglyceride oil as a coating additive | |
| CN103772646A (en) | Biodegradation sustained-release fertilizer coating material containing soybean oil polyhydric alcohol and preparation process thereof | |
| CN101328097B (en) | Compound film controlled release fertilizer and organic polymer coating material thereof | |
| CN108586060B (en) | Functional composite coated controlled-release fertilizer with polyolefin wax as base coat and production method thereof | |
| CN106518339B (en) | In-situ reaction film-forming controlled-release fertilizer and production method thereof | |
| CN103319252B (en) | A kind of polyurethane coated controlled-release fertilizer containing weedicide and preparation method thereof | |
| CN1307125C (en) | Release-controlled coated urea and its preparation method | |
| CN106800472B (en) | Composite modified polyurethane coating liquid, controlled-release fertilizer and preparation method thereof | |
| WO2013030118A1 (en) | Process for producing a coated fertilizer | |
| US20220186072A1 (en) | System for coatings for granular materials | |
| CN105418884A (en) | Polyurethane combined polyether used for slowly-controlled-release fertilizer coating film, preparation method and application thereof | |
| WO2023109674A1 (en) | Bio-based polyol for polyurethane, coating liquid and coated controlled release fertilizer thereof | |
| CN113788711A (en) | Biological basal membrane with self-repairing function, coated controlled-release fertilizer and preparation method | |
| CN103058797B (en) | Production method of slow release fertilizer | |
| CN107011058B (en) | Salt-resistant functional coated slow/controlled release fertilizer and preparation method thereof | |
| CN109867563A (en) | A kind of sustained-controll-release fertiliser and preparation method thereof with water retaining function | |
| US20220153654A1 (en) | Polyester polyol with high biomass ratio for polyurethane controlled-release fertilizer envelope, preparation method thereof and envelope |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220601 Address after: 231602 north of Weiwu Road, circular economy demonstration park, Feidong County, Hefei City, Anhui Province Patentee after: CNSG ANHUI HONGSIFANG FERTILIZER CO.,LTD. Address before: 100094 No. 2 Old Summer Palace West Road, Beijing, Haidian District Patentee before: CHINA AGRICULTURAL University |
|
| TR01 | Transfer of patent right |