CN101323545B - 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
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- CN101323545B CN101323545B CN2008101168767A CN200810116876A CN101323545B CN 101323545 B CN101323545 B CN 101323545B CN 2008101168767 A CN2008101168767 A CN 2008101168767A CN 200810116876 A CN200810116876 A CN 200810116876A CN 101323545 B CN101323545 B CN 101323545B
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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: William P.Moore (US4711659, US4804403, US4969947 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 (US5538531) 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 (US7018440B2 in its serial patent, US7018441B2, 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, US2006/0032282A1, US2004/0020254A1, US2004/0016276A1) simultaneously, its team has applied for relevant patent (CN101006032A) 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=∑ (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.
Embodiment 3
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.
Embodiment 4
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 (9)
1. the coated fertilizer of a 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;
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: 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.
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 2, 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, 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.
4. a 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 1-3, and described nuclear membrane quality is the 2%-10% of described nuclear core quality.
5. fertilizer according to claim 4 is characterized in that: the median size of described granulated fertilizer is 2-6mm.
6. the coating liquid of a 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 1-3; Described b) comprises the polyvalent alcohol in arbitrary described coated fertilizer, degradable function monomer and chainextender among the claim 1-3;
2) with described a) and b) mix, mixing time is 0.1-20 second, makes described coating liquid.
7. coating liquid according to claim 6 is characterized in that: the b in the described step 1)) also comprise the catalyzer in claim 2 or the 3 described coated fertilizers.
8. method for preparing claim 4 or 5 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 6 or 7 described coating liquids are atomized on particles preheated fertilizer surface, make film-coated controlled release fertilizer.
9. described according to Claim 8 method, 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.
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