CN101289352B - Polymer emulsion coating agent, coating release-controlling fertilizer and method for preparing same polymer emulsion - Google Patents
Polymer emulsion coating agent, coating release-controlling fertilizer and method for preparing same polymer emulsion Download PDFInfo
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- CN101289352B CN101289352B CN 200810108190 CN200810108190A CN101289352B CN 101289352 B CN101289352 B CN 101289352B CN 200810108190 CN200810108190 CN 200810108190 CN 200810108190 A CN200810108190 A CN 200810108190A CN 101289352 B CN101289352 B CN 101289352B
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Abstract
The invention relates to a polymer emulsion coated agent, a coated controlled release fertilizer that contains a coated agent and a preparation method thereof. The polymer emulsion coated agent of the invention is characterized in that the coated agent contains alkyd resin prepolymer in a way of neutralization. The invention also relates to the coated controlled release fertilizer, and the fertilizer consists of a fertilizer core and a capsule which is outside the fertilizer core; wherein, the capsule contains a polymer film that contains the polymer emulsion coated agent, and an inorganic layer that is arbitrarily arranged outside the polymer film and contains inorganic powders.
Description
Technical field
The present invention relates to the agent of a kind of polymer emulsion coating and comprise film-coated controlled release fertilizer of this coating agent and preparation method thereof, belong to material and technical field of fertilizers.
Background technology
Therefore release and release control fertilizer is the main development direction of fertilizer field because the releasing rule of its nutrient can be complementary with the demand of Plant To Nutrient.Polymer coating controlled release fertilizer worldwide is subject to extensive concern because having excellent nutrient controlled release properties, and has become the main Types in the release and release control fertilizer.
The relevant technology of preparing of polymer coating controlled release fertilizer is existing the description in patent, for example sees US3, and 223,518, US 3,475,154, US 4,019,890, US 6,391,454, ZL 00122658.4, CN1569773, CN 1603288 etc.Some technology has realized industrialization, and wherein the thermoplastic resin membrane wrapping control-releasing fertilizer material of the thermohardening resin coated controlled-release fertilizer material of U.S. Scotts company and Japanese Chisso-Asahi fertilizer company is its Typical Representative.Yet thermohardening resin coated controlled-release fertilizer material product cost is too high, is difficult to apply in field crop.For the thermoplastic resin membrane wrapping control-releasing fertilizer material, its main preparation methods is linear macromolecule to be dissolved in to make Dilute Polymer Solutions in the organic solvent first, then it is coated in the fertiliser granulates surface, along with the volatilization macromolecular material of solvent has formed the one layer of polymeric film on the fertiliser granulates surface.Obviously there is following shortcoming in this class release and release control fertilizer: polymer capsule material price and production cost are high; The use of a large amount of organic solvents is the serious waste energy and resource not only, and health of human body and environment worked the mischief, although the plus solvent recovery system can partly reduce above-mentioned consumption and harm, but except the disposable input height of equipment and complex process, a small amount of organic solvent that remains in the product still can volatilize and contaminate environment in storage and use procedure gradually.In addition, polymer coating controlled release fertilizer is after fertilizer nutrient releases, and the residual film of polymkeric substance is difficult for degraded, and life-time service can pollute soil.
Agent prepares polymer coating controlled release fertilizer and has low the pollution and advantage cheaply as coating to utilize waterborne polymeric, and relevant technology of preparing is existing the description in patent, for example sees US 4,549,897, US 5,022,182, US 6,176, and 893, CN 1939878A etc.Some investigator has also reported with the result of study of polyvinylidene dichloride suspension as fertilizer sources coating agent and (has seen: Shavia A etc., FertilizerResearch, 1993,35:1; Tzika M etc., Powder Technology, 2003,132:16).Also has in the recent period the report for preparing the waterborne polymeric fertilizer envelope agent take waste plastic as main raw material.The inventor also is studied emulsion type water-base polymer coating agent and film-coated controlled release fertilizer, sees Chinese invention patent application numbers 200710141886.1, application number 200710141889.5.Above-mentioned technology has partly overcome the shortcoming of solvent based polymer film-coated controlled release fertilizer, but because the raw material of synthetic this class coating agent depends on oil, high expensive, polymkeric substance in the coating agent is thermoplastic synthetic resin in addition, the residual film of polymkeric substance after nutrient discharges is difficult to degraded in soil, the pollution problem of soil is not still solved well.
Summary of the invention
The film-coated controlled release fertilizer that the purpose of this invention is to provide a kind of low cost, the agent of eco-friendly polymer emulsion coating and comprise this coating agent, the residual film of polymkeric substance after this film-coated controlled release fertilizer nutrient discharges can biological degradation in soil.
Purpose of the present invention realizes that by the agent of a kind of polymer emulsion coating this coating agent comprises the Synolac performed polymer with the form of neutralization.
The present invention also provides a kind of method for preparing the agent of described polymer emulsion coating, and it comprises the steps:
The Synolac performed polymer is neutralized with alkali,
Randomly add emulsifying agent,
Randomly add entry, and
Add siccative.
The present invention also provides the preparation method of a kind of film-coated controlled release fertilizer and described fertilizer.This film-coated controlled release fertilizer is comprised of the coating of fertilizer core and fertilizer core outside, and described coating comprises the polymeric film that contains polymer emulsion coating of the present invention agent and chooses the inorganic layer that contains inorganic powder outside polymeric film wantonly.
The present invention further provides the method for the described film-coated controlled release fertilizer of preparation, it is included in the fluidized-bed, polymer emulsion coating of the present invention agent is coated on the fertiliser granulates, and chooses on polymeric film coated inorganic powder wantonly to form the coating process of inorganic layer.
In polymer emulsion coating of the present invention agent, because medium is water, eliminated the harm that organic solvent causes environment in the agent of traditional polymer coating fully; Compare with other synthetic polymer coated fertilizers and since the present invention in its main raw material of Synolac from the reproducible vegetables oil of nature, not only the dependency degree to oil is low for it, and with low cost; Because vegetables oil and lipid acid fragment on the polymer chain are given polymeric film with the biodegradable performance, make the residual film of polymkeric substance in the soil can biological degradation; Because preparation process is from the small molecules raw material, the Nomenclature Composition and Structure of Complexes that can be adjusted to membrane polymer by composition and the technique of adjustment polymer raw composition, thus reach the purpose that regulation and control release and release control fertilizer nutrient discharges.In addition since contain in the polymer capsule material of the present invention can with the functional group of water molecules generation association, so such material also has certain water retaining function concurrently.
In further preferred embodiment of the present invention, the coating of film-coated controlled release fertilizer of the present invention comprises the polymeric film that contains polymer emulsion coating of the present invention agent and the inorganic layer that contains inorganic powder outside polymeric film.In this preferred embodiment, the outermost layer that contains inorganic powder not only can be antiseized and wear-resistant, also partly plays the effect that nutrient discharges of regulating.
Polymer emulsion film-coated controlled release fertilizer of the present invention has in production, storage and use procedure nontoxic pollution-free, cost is low, nutrient-lapsed time is controlled and the residual film of polymkeric substance advantage such as biodegradable in soil.
Embodiment
Polymer emulsion coating of the present invention agent is take the Synolac performed polymer as main raw material.In specific embodiments of the present invention, at first prepare the Synolac performed polymer, then through with alkali neutralization, randomly add emulsifying agent, randomly add entry, and add siccative and obtain polymer emulsion coating of the present invention agent.
(1) preparation Synolac performed polymer
Used Synolac performed polymer is preferably by comprising vegetables oil and/or deriving from the lipid acid of plant, polyvalent alcohol, at least a C that is selected among the present invention
4-C
22Synthetic fatty acid, C
4-C
22The feedstock composition of the component of the acid anhydrides of the acid anhydrides of synthetic fatty acid, aromatic acid, aromatic acid obtains by copolycondensation.
In a preferred embodiment of the invention, the used vegetables oil of preparation Synolac performed polymer for example is selected from one or more in siccative oil and the semi-drying oil, and the example comprises oleum lini, tung oil, synourin oil, soya-bean oil, Oleum Gossypii semen, Na Sikeer wet goods.The described lipid acid that derives from plant for example is selected from one or more in oleic acid, linolic acid, linolenic acid, Yatall MA, the rosin.Because some lipid acid is to get from grease such as oleic acid, linolic acid, linolenic acid etc., therefore in actually operating, these lipid acid can obtain on the spot by the alcoholysis of corresponding grease.Described polyvalent alcohol for example is selected from one or more in glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol and the glycol ether, preferably glycerine, TriMethylolPropane(TMP) and tetramethylolmethane.Described C
4-C
22The preferred carbonatoms of synthetic fatty acid and acid anhydrides thereof is 4-22, monoprotic acid or polyprotonic acid and the acid anhydrides thereof of preferred 4-12, for example toxilic acid, maleic anhydride, fumaric acid, caproic acid, capric acid, hexanodioic acid, sebacic acid, more preferably C
4-C
22Diprotic acid and acid anhydrides thereof, especially hexanodioic acid, sebacic acid and acid anhydrides thereof.Described aromatic acid and acid anhydrides thereof are preferably selected from aromatics monoprotic acid, aromatic diacid, aromatics triprotic acid and acid anhydrides thereof, specific examples comprises phenylformic acid, phthalic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, trimellitic acid, trimellitic acid 1,2-anhydride etc., preferred aromatic diacid, triprotic acid and acid anhydrides, especially Tetra hydro Phthalic anhydride, m-phthalic acid, trimellitic acid and trimellitic acid 1,2-anhydride.Described aromatic acid and acid anhydrides thereof can be unsubstituted, or by one or more C that are selected from
1-C
6Alkyl, C
1-C
6Alkoxyl group, C
1-C
6The substituting group of haloalkyl, halogen, nitro replaces.Described halogen or halogen are selected from fluorine, chlorine, bromine and iodine.Described C
1-C
6Alkyl and C
1-C
6Alkoxyl group and C
1-C
6The alkyl structure of haloalkyl partly refers to have 1-6 carbon atom, especially the saturated straight chain of 1-4 carbon atom or branched hydrocarbyl radical, methyl for example, ethyl, propyl group, the 1-methylethyl, butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, amyl group, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1,1,2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, 1-ethyl-1-methyl-propyl, 1-Ethyl-2-Methyl propyl group.Described C
1-C
6Haloalkyl refers to have straight chain or the branching saturated hydrocarbyl of 1-6 carbon atom, wherein the some or all of hydrogen atoms in these groups can be replaced by above-mentioned halogen atom, the example comprises chloromethyl, brooethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, the chlorine methyl fluoride, dichlorofluoromethyl, chlorodifluoramethyl-, the 1-chloroethyl, the 1-bromotrifluoromethane, the 1-fluoro ethyl, the 2-fluoro ethyl, 2,2-two fluoro ethyls, 2,2, the 2-trifluoroethyl, 2-chloro-2-fluoro ethyl, 2-chloro-2,2-two fluoro ethyls, 2,2-two chloro-2-fluoro ethyls, 2,2,2-, three chloroethyls, pentafluoroethyl group etc.Described C
1-C
6Alkoxyl group refers to that the example comprises methoxyl group, oxyethyl group, OCH via the straight chain with 1-6 carbon atom or the branching saturated hydrocarbyl of Sauerstoffatom connection
2-C
2H
5, OCH (CH
3)
2, n-butoxy, OCH (CH
3)-C
2H
5, OCH
2-CH (CH
3)
2, OC (CH
3)
3N-pentyloxy, 1-methyl butoxy, 2-methyl butoxy, 3-methyl butoxy, 1,1-dimethyl propoxy-, 1,2-dimethyl propoxy-, 2,2-dimethyl-propoxy-, 1-ethyl propoxy-, positive hexyloxy, 1-methyl pentyloxy, 2-methyl pentyloxy, 3-methyl pentyloxy, 4-methyl pentyloxy, 1,1-dimethyl butoxy, 1,2-dimethyl butoxy, 1,3-dimethyl butoxy, 2,2-dimethyl butoxy, 2,3-dimethyl butoxy, 3,3-dimethyl butoxy, 1-ethyl butoxy, 2-ethyl butoxy, 1,1,2-trimethylammonium propoxy-, 1,2,2-trimethylammonium propoxy-, 1-ethyl-1-methyl propoxy-, 1-Ethyl-2-Methyl propoxy-etc.
Copolycondensation among the present invention can carry out according to copolycondensation method well known by persons skilled in the art.The copolycondensation temperature is 100～280 ℃ for example, is preferably 140～250 ℃; Polymerization reaction time is 1～24 hour for example, is preferably 4～12 hours.The quality of polyreaction terminal point and gained Synolac is controlled by the acid number of resin.The milligram number (unit is the mgKOH/g resin) of the KOH that consumes with 1 gram resin during the acid number of resin refers to.The present invention is according to the GB/T2895-1982 standard, the acid number of measuring resin as mixed solvent take ethanol and the ether of equal-volume ratio.The inventor finds that after deliberation the acid number of gained Synolac performed polymer affects the performance that this polymkeric substance is used as the coating agent in the present invention.At polymerization formula one regularly, the acid number of general Synolac performed polymer is larger, and its wetting ability is better, easier formation polymer emulsion, but formed coating agent wetting ability is also higher simultaneously, thus cause the controlled release time of release and release control fertilizer to shorten.In the present invention, advantageously, the acid number of used Synolac performed polymer is 10～150mgKOH/g resin, preferred 20～120mgKOH/g resin, more preferably 30～80mgKOH/g resin, most preferably 40～70mgKOH/g resin.
In the present invention, the composition that is used for the feedstock composition of polyreaction can be regulated as required in the larger context, wherein vegetables oil and/or derive from the consumption of lipid acid of plant and the material combination objects system in the mol ratio of hydroxyl and carboxyl affect the acid number of performed polymer and the viscosity of system.The viscosity of Synolac performed polymer is larger, and used solubility promoter is more in following coating agent preparation process.Preferably, vegetables oil and/or the consumption that derives from the lipid acid of plant account for 30～70 % by weight of feedstock composition gross weight, more preferably 40～60 % by weight; The mol ratio of hydroxyl and carboxyl is preferably 0.8～1.4 in the material combination objects system, and more preferably 0.9～1.3.
In the present invention, the preparation method of described Synolac performed polymer can be alcoholysis method or fatty acid process, and the key distinction of the two is that the former is take vegetables oil as raw material, is raw material and the latter is the lipid acid that derives from vegetables oil.Preferred alcohols solution of the present invention.Copolycondensation can carry out in air or under protection of inert gas, and preferably in rare gas element, rare gas element is preferably nitrogen.Copolycondensation can carry out in solvent, also can carry out preferred molten copolycondensation technique under molten state.
(A) alcoholysis method
Alcoholysis method used among the present invention can carry out by alcoholysis method well-known to those skilled in the art.In preferred embodiments, with vegetables oil, polyvalent alcohol and at least a C that is selected from
4-C
22Synthetic fatty acid, C
4-C
22The component of the acid anhydrides of the acid anhydrides of synthetic fatty acid, aromatic acid, aromatic acid adds in the reactor, at 100～280 ℃, reacted under preferred 140～250 ℃ temperature 1～24 hour, preferred 4～12 hours, during with water eliminator in time except the water that generates in the dereaction.Obtain the Synolac performed polymer after the cooling.
In a further preferred embodiment; at first vegetables oil, polyvalent alcohol and diprotic acid (and/or its acid anhydrides) are added and agitator, reflux exchanger, thermometer are housed and have in the reactor of nitrogen protection; be warmed up to 160～260 ℃ of reactions 0.5～6 hour, preferred 200～240 ℃ of reactions 2～4 hours.Then cool to 120～200 ℃, add other polyprotonic acids (and/or its acid anhydrides), insulation reaction at least 0.5 hour, and with water eliminator in time except the water that generates in the dereaction.Randomly, when cooling to 130～160 ℃, add the rosin of 2～20 % by weight of total resin weight, preferred 3～10 % by weight, and under this temperature, reacted preferred 10 minutes to 0.5 hour 5 minutes to 2 hours.Obtain having the Synolac performed polymer of certain acid number after the cooling.
(B) fatty acid process
Fatty acid process used among the present invention can carry out by fatty acid process well-known to those skilled in the art.In preferred embodiments, at first will derive from the lipid acid of plant, polyvalent alcohol and at least a C that is selected from
4-C
22Synthetic fatty acid, C
4-C
22The component of the acid anhydrides of the acid anhydrides of synthetic fatty acid, aromatic acid, aromatic acid adds in the reactor, at 100～280 ℃, reacted under preferred 140～250 ℃ temperature 1～24 hour, preferred 4～12 hours, during with water eliminator in time except the water that generates in the dereaction.Obtain the Synolac performed polymer after the cooling.
In further preferred preparation method; lipid acid, polyvalent alcohol and the diprotic acid (and/or its acid anhydrides) that at first will derive from plant adds and agitator, reflux exchanger, thermometer to be housed and to have in the reactor of nitrogen protection; be warmed up to 160～260 ℃ of reactions 0.5～6 hour; preferred 200～240 ℃ of reactions 2～4 hours; and with water eliminator in time except the water that generates in the dereaction; then cool to 120～200 ℃; add other polyprotonic acids (and/or its acid anhydrides); insulation reaction at least 0.5 hour, and with water eliminator in time except the water that generates in the dereaction.Randomly, when cooling to 130～160 ℃, add the rosin of 2～20 % by weight of total resin weight, preferred 3～10 % by weight, and under this temperature, reacted preferred 10 minutes to 0.5 hour 5 minutes to 2 hours.Obtain having the Synolac performed polymer of certain acid number after the cooling.
(2) preparation polymer emulsion coating agent
The preparation of polymer emulsion coating of the present invention agent comprises the steps:
The Synolac performed polymer is neutralized with alkali,
Randomly add emulsifying agent,
Randomly add entry, and
Add siccative.
In preferred embodiments, with above-mentioned Synolac performed polymer heating and melting, and its temperature is controlled at 25～120 ℃, preferred 40～90 ℃, more preferably 50～80 ℃.Then under agitation in above-mentioned Synolac performed polymer, add alkali.The alkali that is used for neutralization is that any routine is used for one or more of the mineral alkali of neutralization and organic bases, the example comprises alkali metal hydroxide, alkaline earth metal hydroxides, amine etc., such as sodium hydroxide, potassium hydroxide, ammoniacal liquor, triethylamine, Trimethylamine 99, trolamine, morpholine, preferred ammoniacal liquor, triethylamine, Trimethylamine 99, sodium hydroxide and potassium hydroxide.Described alkali preferably uses with the form of the aqueous solution.It is 5～10 that the degree of neutralization preferably makes the pH value of the rear above-mentioned Synolac performed polymer system of neutralization, preferred 7～9.
Then randomly, in system, add emulsifying agent, the mixture of used emulsifying agent preferred anionic type emulsifying agent or anionic emulsifier and nonionic emulsifier.Described anionic emulsifier is one or more in all conventional anionic emulsifier, and for example R is C
8～C
18The sodium soap RCOONa of alkyl, sodium alkyl sulfate ROSO
3Na, alkyl sodium sulfonate RSO
3Na and sodium alkyl benzene sulfonate RC
6H
4SO
3Na, alkyl biphenyl ether sodium disulfonate, nilox resin and sodium alkyl naphthalene sulfonate.Described nonionic emulsifier is one or more in all conventional nonionic emulsifier, polyoxyethylene sorbitan fatty acid ester for example, alkylphenol polyoxyethylene class, alkyl polyoxyethylene ether class etc.With respect to the weight of Synolac, the anionic emulsifier consumption is preferably 0～3.0 % by weight, and the nonionic emulsifier consumption is preferably 0～5.0 % by weight.
If necessary, can further add entry in the Synolac performed polymer system after neutralization.For example, be 30～95 ℃ to temperature under agitation, add entry in preferred 45～85 ℃ Synolac performed polymer system, preferred deionized water and distilled water, cool to room temperature after the emulsification evenly.Can be mixed with the Synolac performed polymer emulsion with required solid content by adding entry as required.
At room temperature to the neutralization after Synolac performed polymer system in add siccative, obtain the agent of polymer emulsion coating after mixing.The siccative that described siccative is well known to those skilled in the art.Described siccative comprises main siccative and drier activator and/or urge dried promoting agent if necessary.Wherein main siccative can use separately, also can and/or urge in the dried promoting agent one or more to be used in combination with drier activator.Described main siccative for example is selected from one or more in cobalt salt and the manganese salt, preferred cobalt naphthenate, manganese naphthenate, and its consumption is 0.005～0.5 % by weight of Synolac performed polymer weight in the system, preferred 0.03～0.2 % by weight.Described drier activator for example is selected from one or more of lead, calcium, zinc, iron, barium, zirconates, preferred naphthenate, and its consumption is 0～0.5 % by weight of Synolac performed polymer weight in the system, preferred 0.01～0.5 % by weight.Describedly urge dried promoting agent to be called as in the present invention " promoting agent A ", it is that propyl carbinol by the o-phenanthroline of 38 % by weight, 22 % by weight ethyl hexanoates and 40 % by weight mixes, its consumption is 0～2.0 % by weight of Synolac performed polymer weight, preferred 0.05～1.0 % by weight, more preferably 0.1～0.8 % by weight.
It may be noted that in Synolac performed polymer system to add emulsifying agent and/or add in the situation of entry that the addition sequence of emulsifying agent, water and siccative is unimportant, can with the Synolac performed polymer with in the alkali and add with random order afterwards.
In the present invention, latex particle size is preferably 50 nanometers～5 micron in the polymer emulsion, more preferably 60 nanometers～1 micron, more preferably 70～300 nanometers.Wherein nano level and submicron order emulsion particle are preferred, and its advantage is good emulsion stability, and the polymeric film of formation is fine and close.
The solid content of polymer emulsion coating of the present invention agent is preferably 5～70 % by weight, more preferably 10～50 % by weight, further preferred 15～40 % by weight.Viscosity is preferably 10～5000mPa.S, more preferably 50～2000mPa.S, more preferably 80～500mPa.S.
(3) film-coated controlled release fertilizer and preparation method thereof
For the purpose of the present invention, the fertilizer slug particle can be any water soluble fertilizer, for example can be single fertilizer, for example nitrogenous fertilizer such as urea, phosphate fertilizer such as ammonium phosphate, potash fertilizer such as vitriolate of tartar, also can be compound manure, the composite fertilizer of any nitrogen phosphoris and potassium fertilizer ratio, and other water-soluble plant nutritive ingredients.
The method for preparing film-coated controlled release fertilizer of the present invention is included in the fluidized-bed, the agent of polymer emulsion coating is coated to fertiliser granulates surface and forms polymeric film, randomly on polymeric film coated inorganic powder to form the coating process of inorganic layer.Described coating process is preferably carried out in boiling type or rotary drum fluidized-bed.The preferred mode of spraying that adopts is coated to the fertiliser granulates surface with polymer emulsion coating of the present invention agent.
The coating process of polymer emulsion film-coated controlled release fertilizer of the present invention can this area conventional coating mode carry out.Temperature is preferably 30～95 ℃ in the fluidized-bed.
In a further preferred embodiment, fertiliser granulates is put into boiling type or rotary drum fluidized-bed, with its preheating, for example being preheating to preferred temperature is 70～95 ℃.Then with the polymer emulsion coating of the present invention agent under the room temperature, preferred preheating, for example be preheating at the most that 80 ℃ polymer emulsion coating of the present invention agent evenly sprays on the fertiliser granulates by double flowing nozzle, form the polymeric film of one deck continuous uniform.The consumption of polymer emulsion coating agent is regulated according to the size of fertiliser granulates with to the demand of fertilizer nutrient rate of release, presses dry matter weight and calculates, and the weight of polymeric film accounts for 5～30 % by weight of release and release control fertilizer gross weight, preferred 7～20 % by weight.
If necessary, then inorganic powder is sprayed and be preferably 30～95 ℃, more preferably in 70～95 ℃ the fluidized-bed, make it be coated on equably the fertiliser granulates surface of coated polymer, usually the inorganic powder consumption accounts for 0～10 % by weight of film-coated controlled release fertilizer gross weight, preferred 0.5～5 % by weight, more preferably 1～3 % by weight.
In a preferred embodiment of the invention, described inorganic powder is selected from one or more in talcum powder, diatomite, polynite, kaolin, calcium carbonate, wilkinite, attapulgite and the sepiolite powder, preferably talc powder, diatomite and calcium carbonate, more preferably micron order inorganic powder.The particle diameter of inorganic powder is more preferably less than 10 microns preferably less than 20 microns, most preferably less than 5 microns.Most preferably particle diameter is less than 5 microns talcum powder, diatomite or calcium carbonate.
Embodiment
By the following examples, the present invention is described in further detail, described embodiment only is the present invention is described and never limits the present invention.
In following all embodiment, used vegetables oil, lipid acid, polyvalent alcohol, polyprotonic acid, acid anhydrides, siccative, wax and inorganic powder are technical grade, and used alkali is chemically pure reagent, and institute's water is deionized water.
In following all embodiment, the fertilizer releasing period of release and release control fertilizer begins to represent to the required fate of accumulation nutrient release rate that reaches 80% with controlled release nutrients lixiviate in 25 ℃ of hydrostatic.Concrete measuring method is as follows: leave standstill the immersion release and release control fertilizer with 25 ℃ water, nutrient in the test portion passes through the film stripping in water, press the total nitrogen content of the rear titration measuring stripping of GB/T 8572 usefulness distillation, press the phosphorus content of GB/T 8573 usefulness Color Comparison Method of Ammonium Vanadate-molybdate strippings, press the potassium content that GB/T 8574 usefulness flare photometers are measured stripping.The stripping nutrient reach this nutrient total mass 80% the time the required time be the fertilizer releasing period of release and release control fertilizer.
Embodiment 1
(1) preparation Synolac performed polymer
480 gram oleum lini, 236 gram TriMethylolPropane(TMP)s and 166 gram m-phthalic acids are added agitator, reflux exchanger, thermometer are housed and have in the reactor of nitrogen protection; be warmed up to 235 ℃ of reactions 3.5 hours; then cool to 175 ℃; add 73 gram trimellitic acid 1,2-anhydrides; reaction is about 3 hours under this temperature, and in time removes the water that generates in the dereaction with water eliminator, when the acid number of system reaches the 62KOHmg/g resin; cool to 150 ℃, add 49 gram rosin reactions 20 minutes.
(2) preparation polymer emulsion coating agent
Synolac performed polymer in the step (1) is cooled to 65 ℃, under agitation add the ammoniacal liquor of 20 % by weight, making system pH is 7.Then add deionized water, the evenly rear cool to room temperature of stirring and emulsifying adds respectively 2 gram cobalt naphthenates, 1 gram zirconium naphthenate and 1.5 gram promoting agent A again, mixes, and obtains the agent of polymer emulsion coating.Coating agent emulsion grain particle diameter is 143 nanometers, and solid content is 35 % by weight, and viscosity is 124mPa.S.
(3) fertilizer coating process
Be that 3～4 millimeters urea (from Shandong Mingshui Chemical Co., Ltd, counting 46.4 with the N % by weight) is packed in the boiling type fluidized-bed and is heated to about 90 ℃ with 5 kilograms of particle diameters.Spray to the fertilizer surface with being preheating to 2.5 kilograms of about 80 ℃ above-mentioned coating agent from double flowing nozzle, spray rate is about per minute 35 grams.Be that evenly to spray temperature be that fertilizer about 80 ℃ is surperficial for 3 microns diatomite at last with 100 gram median sizes.
Calculate with dry matter weight, the gained film-coated controlled release fertilizer consists of urea and accounts for 83.7%, and polymkeric substance accounts for 14.6%, and diatomite accounts for 1.7%.The fertilizer releasing period of this release and release control fertilizer is 116 days.
Embodiment 2
With embodiment 1, difference is not spray diatomite.
Calculate with dry matter weight, the gained film-coated controlled release fertilizer consists of urea and accounts for 85.1%, and polymkeric substance accounts for 14.9%.The fertilizer releasing period of this release and release control fertilizer is 95 days.
Embodiment 3
With embodiment 1, it is that 2～4 millimeters composite fertilizer replaces that (composite fertilizer is from Shandong Kingenta Bio-engineering Stock Co., Ltd., with N-P that difference is the urea particle diameter among the embodiment 1
2O
5-K
2O % by weight meter: 16-16-16).
Calculate with dry matter weight, the composite fertilizer that consists of of gained film-coated controlled release fertilizer accounts for 83.7%, and polymkeric substance accounts for 14.6%, and diatomite accounts for 1.7%.The fertilizer releasing period of this release and release control fertilizer is 198 days.
Embodiment 4
(1) preparation Synolac performed polymer
190 gram oleum lini, 210 gram synourin oils, 223 gram TriMethylolPropane(TMP)s and 148 gram Tetra hydro Phthalic anhydrides are added agitator, reflux exchanger, thermometer are housed and have in the reactor of nitrogen protection, be warmed up to 225 ℃ of reactions 2.5 hours.Then cool to 170 ℃, add 64 gram trimellitic acids, reaction is about 3.5 hours under this temperature, and in time removes the water that generates in the dereaction with water eliminator, when the acid number of system reaches the 55mgKOH/g resin, cools to 160 ℃, adds 60 gram rosin reactions 15 minutes.
(2) preparation polymer emulsion coating agent
Synolac performed polymer in the step (1) is cooled to 75 ℃, under agitation add the ammoniacal liquor of 20 % by weight, making system pH is 7.5.Then add deionized water, the evenly rear cool to room temperature of stirring and emulsifying adds respectively 1.8 gram cobalt naphthenates, 1 gram zirconium naphthenate and 1.5 gram promoting agent A again, mixes, and obtains the agent of polymer emulsion coating.Coating agent emulsion grain particle diameter is 196 nanometers, and solid content is 35 % by weight, and viscosity is 296mPa.S.
(3) fertilizer coating process
Be in 3～4 millimeters urea (from Shandong Mingshui Chemical Co., Ltd, counting 46.4 with the N % by weight) the boiling type fluidized-bed of packing into, to be heated to about 90 ℃ with 5 kilograms of particle diameters.2 kilograms of above-mentioned coating agent that are preheating to 85 ℃ are sprayed to the fertilizer surface from double flowing nozzle, and spray rate is per minute 30 grams.Then the talcum powder that with 120 gram median sizes is 3 microns evenly sprays the fertilizer surface of temperature about 85 ℃.
Calculate with dry matter weight, the urea that consists of of gained film-coated controlled release fertilizer accounts for 85.9%, and polymkeric substance accounts for 12%, and talcum powder accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 92 days.
Embodiment 5
With embodiment 4, it is that 3～5 millimeters vitriolate of tartar replaces that (vitriolate of tartar produces from Shandong Kingenta Bio-engineering Stock Co., Ltd., with K that difference is the urea particle diameter among the embodiment 4
2The O % by weight counts 50).
Calculate with dry matter weight, the vitriolate of tartar that consists of of resulting polymers emulsion film-coated controlled release fertilizer accounts for 85.9%, and polymkeric substance accounts for 12%, and talcum powder accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 115 days.
Embodiment 6
(1) preparation Synolac performed polymer
175 gram oleum lini, 175 gram tung oil, 95 gram Oleum Gossypii semens, 215 gram TriMethylolPropane(TMP)s, 75 gram Tetra hydro Phthalic anhydrides and 83 gram m-phthalic acids are added agitator, reflux exchanger, thermometer are housed and have in the reactor of nitrogen protection, be warmed up to 240 ℃ of reactions 2.5 hours.Then cool to 180 ℃, add 48 gram trimellitic acids, reaction is about 3 hours under this temperature, and in time removes the water that generates in the dereaction with water eliminator, when the acid number of system reaches the 48KOHmg/g resin, cools to 160 ℃, adds 50 gram rosin reactions 20 minutes.
(2) preparation polymer emulsion coating agent
Synolac performed polymer in the step (1) is cooled to 70 ℃, under agitation add the ammoniacal liquor of 20 % by weight, making system pH is 7.Then add deionized water, the evenly rear cool to room temperature of stirring and emulsifying adds respectively 2 gram cobalt naphthenates and 2.5 gram promoting agent A again, mixes, and obtains the agent of polymer emulsion coating.Coating agent emulsion grain particle diameter is 154 nanometers, and solid content is 35 % by weight, and viscosity is 158mPa.S.
(3) fertilizer coating process
Be in 3～4 millimeters urea (from Shandong Mingshui Chemical Co., Ltd, counting 46.4 with the N % by weight) the boiling type fluidized-bed of packing into, to be heated to about 85 ℃ with 5 kilograms of particle diameters.1.7 kilograms of above-mentioned coating agent that are preheating to 80 ℃ are sprayed to the fertilizer surface from double flowing nozzle, and spray rate is per minute 30 grams.Then the calcium carbonate that with 120 gram median sizes is 3.5 microns evenly sprays the fertilizer surface of temperature about 85 ℃.
Calculate with dry matter weight, the urea that consists of of gained film-coated controlled release fertilizer accounts for 87.5%, and polymkeric substance accounts for 10.4%, and calcium carbonate accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 95 days.
Embodiment 7
With embodiment 6, it is that 2～4 millimeters composite fertilizer replaces that (composite fertilizer is from Shandong Kingenta Bio-engineering Stock Co., Ltd., with N-P that difference is the urea particle diameter among the embodiment 6
2O
5-K
2O % by weight meter: 16-16-16).
Calculate with dry matter weight, the composite fertilizer that consists of of gained film-coated controlled release fertilizer accounts for 87.5%, and polymkeric substance accounts for 10.4%, and calcium carbonate accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 185 days.
Embodiment 8
With embodiment 6, it is that 3～5 millimeters vitriolate of tartar replaces that (vitriolate of tartar produces from Shandong Kingenta Bio-engineering Stock Co., Ltd., with K that difference is the urea particle diameter among the embodiment 6
2The O % by weight counts 50).
Calculate with dry matter weight, the vitriolate of tartar that consists of of resulting polymers emulsion film-coated controlled release fertilizer accounts for 87.5%, and polymkeric substance accounts for 10.4%, and calcium carbonate accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 106 days.
Embodiment 9
(1) preparation Synolac performed polymer
300 gram tung oil, 125 gram soya-bean oil, 112 gram TriMethylolPropane(TMP)s, 70 gram tetramethylolmethanes and 162 gram m-phthalic acids are added agitator, reflux exchanger, thermometer are housed and have in the reactor of nitrogen protection, be warmed up to 235 ℃ of reactions 3 hours.Then cool to 180 ℃, add 50 gram trimellitic acid 1,2-anhydrides, reaction is about 3 hours under this temperature, and in time removes the water that generates in the dereaction with water eliminator, when the acid number of system reaches the 42KOHmg/g resin, cools to 155 ℃, adds 52 gram rosin reactions 20 minutes.
(2) preparation polymer emulsion coating agent
Synolac performed polymer in the step (1) is cooled to 70 ℃, under agitation add the ammoniacal liquor of 20 % by weight, making system pH is 7.Then add 1.5 gram Sodium dodecylbenzene sulfonatees and 2 gram polyoxyethylene octylphenol ethers, add again deionized water after mixing, the evenly rear cool to room temperature of stirring and emulsifying, add respectively again 1 gram cobalt naphthenate, 1 gram zirconium naphthenate and 1.5 gram promoting agent A, obtain the agent of polymer emulsion coating after mixing.Coating agent emulsion grain particle diameter is 72 nanometers, and solid content is 30 % by weight, and viscosity is 158mPa.S.
(3) fertilizer coating process
Be that 2～4 millimeters composite fertilizer is (from Shandong Kingenta Bio-engineering Stock Co., Ltd., with N-P with 5 kilograms of particle diameters
2O
5-K
2O % by weight meter: 16-16-16) pack in the boiling type fluidized-bed, be heated to about 85 ℃.2.2 kilograms of above-mentioned coating agent that are preheating to 80 ℃ are sprayed to the fertilizer surface from double flowing nozzle, and spray rate is per minute 35 grams.Then the diatomite that with 120 gram median sizes is 3 microns evenly sprays the fertilizer surface of temperature about 85 ℃.
Calculate with dry matter weight, the composite fertilizer that consists of of gained film-coated controlled release fertilizer accounts for 86.5%, and polymkeric substance accounts for 11.4%, and diatomite accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 175 days.
Embodiment 10
With embodiment 9, difference is coating agent consumption is reduced to 1.4 kilograms.
Calculate with dry matter weight, the composite fertilizer that consists of of gained film-coated controlled release fertilizer accounts for 90.3%, and polymkeric substance accounts for 7.6%, and diatomite accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 83 days.
Embodiment 11
With embodiment 9, difference is that be that 3～5 millimeters vitriolate of tartar replaces that (vitriolate of tartar produces from Shandong Kingenta Bio-engineering Stock Co., Ltd., with K with the composite fertilizer among the embodiment 9 with particle diameter
2The O % by weight counts 50).
Calculate with dry matter weight, the vitriolate of tartar that consists of of resulting polymers emulsion film-coated controlled release fertilizer accounts for 86.5%, and polymkeric substance accounts for 11.4%, and diatomite accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 92 days.
Embodiment 12
With embodiment 9, difference is that replacing the ammoniacal liquor of 20 % by weight to come regulation system pH value with 5 % by weight aqueous sodium hydroxide solutions is 7.
Calculate with dry matter weight, the composite fertilizer that consists of of gained film-coated controlled release fertilizer accounts for 86.5%, and polymkeric substance accounts for 11.4%, and diatomite accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 155 days.
Embodiment 13
(1) preparation Synolac performed polymer
163 gram linolic acid, 215 gram linolenic acid, 82 gram m-phthalic acids, 75 gram Tetra hydro Phthalic anhydrides and 275 gram TriMethylolPropane(TMP)s are added agitator, reflux exchanger, thermometer are housed and have in the reactor of nitrogen protection; be warmed up to 240 ℃ of reactions 3 hours; and with water eliminator in time except the water that generates in the dereaction; then cool to 180 ℃; add 68 gram trimellitic acid 1,2-anhydrides; insulation reaction and with water eliminator in time except the water that generates in the dereaction, the acid number of system reaches the 55KOHmg/g resin after about 4 hours.Add 60 gram rosin reactions 25 minutes when cooling to 150 ℃.
(2) preparation polymer emulsion coating agent
Synolac performed polymer in the step (1) is cooled to 65 ℃, under agitation add the ammoniacal liquor of 20 % by weight, making system pH is 7.Then add deionized water, the evenly rear cool to room temperature of stirring and emulsifying adds respectively 1.5 gram cobalt naphthenates, 1.5 gram zirconium naphthenates and 1.5 gram promoting agent A again, obtains the agent of polymer emulsion coating after mixing.Coating agent emulsion grain particle diameter is 98 nanometers, and solid content is 35 % by weight, and viscosity is 243mPa.S.
(3) fertilizer coating process
Be that 2～4 millimeters composite fertilizer is (from Shandong Kingenta Bio-engineering Stock Co., Ltd., with N-P with 5 kilograms of particle diameters
2O
5-K
2O % by weight meter: 16-16-16) pack in the boiling type fluidized-bed, be preheating to about 85 ℃.2 kilograms of above-mentioned coating agent that are preheating to 80 ℃ are sprayed to the fertilizer surface from double flowing nozzle, and spray rate is per minute 35 grams.Then the talcum powder that with 120 gram median sizes is 3 microns evenly sprays the fertilizer surface of temperature about 85 ℃.
Calculate with dry matter weight, the composite fertilizer that consists of of gained film-coated controlled release fertilizer accounts for 85.9%, and polymkeric substance accounts for 12%, and talcum powder accounts for 2.1%.The fertilizer releasing period of this release and release control fertilizer is 135 days.
Claims (53)
1. polymer emulsion coating agent is characterized in that this coating agent comprises the Synolac performed polymer with the form of neutralization,
Wherein said Synolac performed polymer is by comprising vegetables oil and/or deriving from the lipid acid of plant, polyvalent alcohol, at least a C that is selected from
4-C
22Synthetic fatty acid, C
4-C
22The feedstock composition of the component of the acid anhydrides of the acid anhydrides of synthetic fatty acid, aromatic acid, aromatic acid obtains by copolycondensation,
Wherein said vegetables oil and/or the consumption that derives from the lipid acid of plant account for 30～70 % by weight of feedstock composition gross weight; The mol ratio of hydroxyl and carboxyl is 0.8～1.4 in the feedstock composition.
2. according to claim 1 polymer emulsion coating agent, wherein said vegetables oil and/or the consumption that derives from the lipid acid of plant account for 40～60 % by weight of feedstock composition gross weight.
3. according to claim 1 polymer emulsion coating agent, wherein the mol ratio of hydroxyl and carboxyl is 0.9～1.3 in the feedstock composition.
4. according to claim 1 polymer emulsion coating agent, the acid number of wherein said Synolac performed polymer is 10～150mgKOH/g resin.
5. according to claim 4 polymer emulsion coating agent, the acid number of wherein said Synolac performed polymer is 20～120mgKOH/g resin.
6. according to claim 4 polymer emulsion coating agent, the acid number of wherein said Synolac performed polymer is 30～80mgKOH/g resin.
7. according to claim 4 polymer emulsion coating agent, the acid number of wherein said Synolac performed polymer is 40～70mgKOH/g resin.
8. according to claim 1 polymer emulsion coating agent, the solid content that it is characterized in that this coating agent is 5～70 % by weight.
9. according to claim 8 polymer emulsion coating agent, the solid content that it is characterized in that this coating agent is 10～50 % by weight.
10. according to claim 8 polymer emulsion coating agent, the solid content that it is characterized in that this coating agent is 15～40 % by weight.
11. polymer emulsion coating agent according to claim 1, the viscosity that it is characterized in that this coating agent is 10～5000mPa.S.
12. polymer emulsion coating agent according to claim 11, the viscosity that it is characterized in that this coating agent is 50～2000mPa.S.
13. polymer emulsion coating agent according to claim 11, the viscosity that it is characterized in that this coating agent is 80～500mPa.S.
14. polymer emulsion coating agent according to claim 1 is characterized in that in the described coating agent that latex particle size is 50 nanometers～5 micron.
15. polymer emulsion coating agent according to claim 14 is characterized in that in the described coating agent that latex particle size is 60 nanometers～1 micron.
16. polymer emulsion coating agent according to claim 14 is characterized in that latex particle size is 70～300 nanometers in the described coating agent.
17. each polymer emulsion coating agent according to claim 1-16, wherein said vegetables oil is selected from one or more in siccative oil and the semi-drying oil; The described lipid acid that derives from plant is selected from one or more in oleic acid, linolic acid, linolenic acid, Yatall MA and the rosin; Described polyvalent alcohol is selected from one or more in glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol and the glycol ether; Described C
4-C
22Synthetic fatty acid and acid anhydrides thereof are selected from C
4-C
22Monoprotic acid, polyprotonic acid and acid anhydrides thereof; Described aromatic acid and acid anhydrides thereof are selected from aromatics monoprotic acid, aromatic diacid, aromatics triprotic acid and acid anhydrides thereof.
18. polymer emulsion coating agent according to claim 17, wherein said vegetables oil are selected from oleum lini, tung oil, synourin oil, soya-bean oil, Oleum Gossypii semen and Na Sikeer oil.
19. polymer emulsion coating agent according to claim 17, wherein said C
4-C
22Synthetic fatty acid and acid anhydrides thereof are selected from C
4-C
22Diprotic acid and acid anhydrides thereof.
20. polymer emulsion coating agent according to claim 19, wherein said C
4-C
22Diprotic acid and acid anhydrides thereof select oneself diacid, sebacic acid and acid anhydrides thereof.
21. polymer emulsion coating agent according to claim 17, wherein said aromatic acid and acid anhydrides thereof are selected from Tetra hydro Phthalic anhydride, m-phthalic acid, trimellitic acid and trimellitic acid 1,2-anhydride.
22. each polymer emulsion coating agent according to claim 1-16, the preparation method who it is characterized in that described performed polymer is alcoholysis method or fatty acid process.
23. each polymer emulsion coating agent according to claim 1-16, wherein said copolycondensation is copolycondensation or melt co-polycondensation.
24. each polymer emulsion coating agent according to claim 1-16, wherein said copolycondensation temperature is 100～280 ℃; Polymerization reaction time is 1～24 hour.
25. polymer emulsion coating agent according to claim 24, wherein said copolycondensation temperature is 140～250 ℃.
26. polymer emulsion coating agent according to claim 24, wherein said polymerization reaction time is 4～12 hours.
27. one kind prepares each the method for polymer emulsion coating agent of claim 1-26, it comprises the steps:
The Synolac performed polymer is neutralized with alkali,
Randomly add emulsifying agent,
Randomly add entry, and
Add siccative.
28. the method for preparing the agent of polymer emulsion coating according to claim 27, wherein said alkali are one or more in mineral alkali and the organic bases.
29. the method for preparing the agent of polymer emulsion coating according to claim 28, wherein said alkali is selected from alkali metal hydroxide, alkaline earth metal hydroxides and amine.
30. the method for preparing the agent of polymer emulsion coating according to claim 28, wherein said alkali is selected from ammoniacal liquor, triethylamine, Trimethylamine 99, sodium hydroxide and potassium hydroxide.
31. the method for preparing the agent of polymer emulsion coating according to claim 28, wherein system pH is 5～10 after the neutralization.
32. the method for preparing the agent of polymer emulsion coating according to claim 31, wherein system pH is 7～9 after the neutralization.
33. each the method for preparing the agent of polymer emulsion coating according to claim 27-32, wherein said emulsifying agent is selected from the mixture of anionic emulsifier or anionic emulsifier and nonionic emulsifier.
34. the method for preparing the agent of polymer emulsion coating according to claim 33, wherein with respect to Synolac weight, the anionic emulsifier consumption is 0～3.0 % by weight.
35. the method for preparing the agent of polymer emulsion coating according to claim 33, wherein with respect to Synolac weight, the nonionic emulsifier consumption is 0～5.0 % by weight.
36. each the method for preparing the agent of polymer emulsion coating according to claim 27-32, wherein said siccative comprise main siccative and non-essential drier activator and/or urge dried promoting agent.
37. the method for preparing the agent of polymer emulsion coating according to claim 36, wherein said main siccative is selected from one or more in cobalt salt and the manganese salt, and its consumption is 0.005～0.5 % by weight of Synolac performed polymer weight; Described drier activator is selected from one or more in lead, calcium, zinc, iron, barium, the zirconates, and its consumption is 0～0.5 % by weight of Synolac performed polymer weight; Described to urge dried promoting agent be that propyl carbinol by o-phenanthroline, 22 % by weight ethyl hexanoates and 40 % by weight of 38 % by weight mixes, and its consumption is 0～2.0 % by weight of Synolac performed polymer weight.
38. the method for preparing the agent of polymer emulsion coating according to claim 37, wherein said main siccative is selected from cobalt naphthenate and manganese naphthenate.
39. the method for preparing the agent of polymer emulsion coating according to claim 37, the consumption of wherein said drier activator are 0.01～0.5 % by weight of Synolac performed polymer weight.
40. the method for preparing the agent of polymer emulsion coating according to claim 37, wherein said to urge the consumption of dried promoting agent be 0.05～1.0 % by weight of Synolac performed polymer weight.
41. film-coated controlled release fertilizer, its coating by fertilizer core and fertilizer core outside forms, it is characterized in that described coating comprises contains right and requires 1～26 each the agent of polymer emulsion coating or the polymeric film of the polymer emulsion coating agent that obtains of each method according to claim 27-40, and choose the inorganic layer that outside polymeric film, contains inorganic powder wantonly, wherein said inorganic powder is selected from one or more in talcum powder, diatomite, polynite, kaolin, calcium carbonate, wilkinite, attapulgite and the sepiolite powder.
42. film-coated controlled release fertilizer according to claim 41 wherein calculates with dry matter weight, the weight of described polymeric film is 5～30% of release and release control fertilizer gross weight.
43. film-coated controlled release fertilizer according to claim 41 wherein calculates with dry matter weight, the weight of described polymeric film is 7～20% of release and release control fertilizer gross weight.
44. film-coated controlled release fertilizer according to claim 41 is characterized in that inorganic powder accounts for 0～10 % by weight of release and release control fertilizer gross weight.
45. film-coated controlled release fertilizer according to claim 44 is characterized in that inorganic powder accounts for 0.5～5 % by weight of release and release control fertilizer gross weight.
46. film-coated controlled release fertilizer according to claim 44 is characterized in that inorganic powder accounts for 1～3 % by weight of release and release control fertilizer gross weight.
47. film-coated controlled release fertilizer according to claim 41, wherein said inorganic powder is selected from talcum powder, diatomite and calcium carbonate.
48. film-coated controlled release fertilizer according to claim 41, wherein said inorganic powder are micron-sized.
49. film-coated controlled release fertilizer according to claim 41, wherein said inorganic powder are the inorganic powder less than 5 microns.
50. film-coated controlled release fertilizer according to claim 41, wherein said inorganic powder are selected from particle diameter less than 5 microns talcum powder, diatomite and calcium carbonate.
51. method for preparing each film-coated controlled release fertilizer among the claim 41-50, it is included in the fluidized-bed, with in the claim 1～26 each the agent of polymer emulsion coating or according to claim 27-40 the polymer emulsion coating agent that obtains of each method be coated to and form polymeric film on the fertiliser granulates, and randomly on polymeric film coated inorganic powder to form the coating process of inorganic layer.
52. the method according to 51, wherein said fluidized-bed are boiling type or rotary drum fluidized-bed.
53. the method according to 51 or 52 wherein is coated to the agent of polymer emulsion coating on the fertiliser granulates and forms polymeric film and form polymeric film for the agent of described polymer emulsion coating is sprayed on the fertiliser granulates surface by double flowing nozzle.
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| Title |
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| 姚俊杰等.用聚合物乳液为包膜剂制备缓释尿素.《化工进展》.2005,第24卷(第6期),666-670. * |
| 陈德明等.缓释和控释尿素的研究与开发综述.《化工进展》.2002,第21卷(第7期),455-461. * |
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