CN101932537A - Aqueous polymer coating agent, film-coated controlled release fertilizer and preparation method thereof - Google Patents
Aqueous polymer coating agent, film-coated controlled release fertilizer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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Abstract
The present invention relates to a kind of aqueous polymer coating agent and comprise film-coated controlled release fertilizer of this coating agent and preparation method thereof.This coating agent is carried out letex polymerization by hard monomer, soft monomer and the function monomer that is selected from the unsaturated acid of free redical polymerization and is obtained in the presence of initiator, emulsifying agent and optional assistant for emulsifying agent, the weight ratio of wherein said hard monomer and soft monomer is 2: 1～1: 2, and described function monomer accounts for 0.2～15 weight % of total monomer weight.
Description
Aqueous polymer coating agent, film-coated controlled release fertilizer and preparation method thereof technical field
Film-coated controlled release fertilizer the present invention relates to a kind of aqueous polymer coating agent and comprising the coating agent and preparation method thereof, belongs to material and technical field of fertilizers.Background technology
Improve utilization rate of fertilizer, reduction dose be agriculture, woods, herd, gardening, flowers, the field such as lawn reduce the important method of production cost; be also the important means preserved the ecological environment, thus control Slow release fertilizers be increasingly taken seriously in fertilizer industry.The controlled release ^^ of current commercialization has polytype, and wherein film-coated controlled release fertilizer is main flow and main development direction.
Release and release control fertilizer can be divided into two major classes by the type of coated fertilizer：One class is the release and release control fertilizer using inorganic matter as coating agent, for example US 3,342,577, US 3,877,415, US 5,219, described in 465, wherein fused solution sulphur to be coated in the sulfur-coated urea being made on urea（SCU) it is its Typical Representative.The advantage of this control Dry fertilizer is that raw material and production cost are low, has the disadvantage that film material is too crisp, and film layer is easily broken in production, storage and transportation；Other film surface easily forms larger hole, therefore has influence on its control Slow and release performance；Painting sulfur fertilizer material is used for a long time and also results in soil acidification.Another kind of is the release and release control fertilizer using organic polymer material as coating agent, such as US 3,223,518, US 3,475,154th, US 4,019,890, described in CN 1603288, the main preparation methods of such release and release control fertilizer are that high polymer material dissolving is first made into Dilute Polymer Solutions in organic solvent, fertiliser granulates surface are then coated onto, as the volatilization high polymer material of solvent in fertiliser granulates surface forms one layer of polymeric film.What it is due to this kind of surface parcel is one layer of polymeric membrane for hooking densification with toughness, so its intensity and wear and shock-resistant performance are greatly improved.The foster ^ rules of organic polymer film-coated controlled release fertilizer are mainly controlled by nutrient by the spreading factor of polymer film layer material, thus the rate of release of nutrient can effectively be controlled by the composition and the approach of structure design to coating high polymer material, the release of release and release control fertilizer nutrient is matched with plant to the demand of nutrient.But the shortcoming of this kind of release and release control fertilizer is that coated fertilizer price and production cost are high, and the use of especially a large amount of organic solvents not only causes a large amount of consumption of the energy and resource, and very big harm is caused to health of human body and environment.Although plus solvent recovery system can partly reduce above-mentioned consumption and harm in process of production,
But equipment disposably puts into height, complex process.
The drawbacks of organic solvent type polymer coating agent then can be eliminated using aqueous polymer coating agent.
US 4,549,897 discloses polymer emulsion as the feasibility of fertilizer envelope agent, then also has and utilizes the research for gathering inclined two chloroethenes Xishui suspension as coating agent（See the Fertilizer such as Shavia A Research, 1993,35: 1;The Powder such as Tzika M Technology, 2003,132: 16).There are problems that viscosity is larger, solid content is relatively low yet with aqueous polymer coating agent, the need for moisture evaporation is slow during coating and dissolving, therefore this kind of coating agent far can not also meet actual production.CN 1388169 and CN 1546543 disclose the method that waterborne polymeric fertilizer envelope agent is prepared by primary raw material of polymeric materials such as waste plastics, although this method partly overcomes the shortcoming of organic molten type polymer fertilizer envelope agent, but the polymeric materials such as waste plastic are dissolved first by part organic solvent because this method is inevitable, then aqueous polymer coating agent could be prepared with high speed shearing emulsification technology, therefore the harm of organic solvent is not completely eliminated；Further, since main film forming substance has been high polymer material, its composition has been difficult to change with structure, thus substantially reduces by adjusting polymer composition and structure to adjust the possibility that release and release control fertilizer nutrient Dry is put.The content of the invention
The purpose of the present invention is for current polymer coating agent problem present in release and release control fertilizer production, in the case of without using any organic solvent, a kind of environment-friendly low viscosity, the aqueous polymer coating agent of high solids content, and the film-coated controlled release fertilizer comprising the coating agent are provided.
The purpose of the present invention is realized by a kind of aqueous polymer coating agent, the coating agent is carried out emulsion polymerization in the presence of initiator, emulsifying agent and optional assistant for emulsifying agent by the function monomer of hard monomer, soft monomer and the unsaturated acids selected from free redical polymerization and obtained, wherein the weight ratio of the hard monomer and soft monomer is 2:1~1:2, the function monomer accounts for 0.2 ~ 15 weight of total monomer weight. /..
The present invention also provides a kind of film-coated controlled release fertilizer, its coating outside fertilizer core and fertilizer core is constituted, the polymer film of aqueous polymer coating agent formation of the wherein described coating comprising the present invention, and the inorganic layer containing inorganic particle optionally outside polymer film.
The present invention also provides a kind of method for making the film-coated controlled release fertilizer, it, which is included in fluid bed, is coated to aqueous polymer coating agent of the present invention on fertiliser granulates, adhere to inorganic particle to form the coating process of inorganic layer in fertiliser granulates surface formation polymer film, and optionally on polymer film.
Because coating agent of the present invention is using water as medium, completely eliminate the shortcoming of organic solvent type coating agent, simultaneously because preparation process is from monomer, the Nomenclature Composition and Structure of Complexes of film forming polymer can be adjusted by adjusting polymerization formula and technique, so as to reach the purpose of regulation and control release and release control fertilizer nutrients release.And the viscosity of aqueous polymer coating agent of the present invention is low, solid content is high, and glass transition temperature can be adjusted by the ratio of hard soft monomer in formula.Additionally, due to, containing the functional group of Parties cooperations can occur with hydrone, such material also has certain water retention property concurrently in polymer capsule material.
In further preferred embodiment of the present invention, the coating of coating control Dry fertilizer of the present invention includes the polymer film formed by aqueous polymer coating agent of the present invention and the inorganic layer containing inorganic particle outside polymer film.In the preferred embodiment, the inorganic layer containing inorganic particle not only also can partly be played a part of regulation nutrient Dry and put as outermost layer with anti-sticking and wear-resistant.
The advantage of the film-coated controlled release fertilizer of the present invention is environmentally friendly, and controlled release period can be adjusted by the composition of coating agent, structure and consumption, to meet release request of the Different Crop different application occasion to fertilizer.Embodiment
In a preferred embodiment of the invention, prepare one or more of the hard monomer in styrene monomer and methyl methacrylate used in aqueous polymer coating agent of the present invention, the styrene monomer for example including：Styrene and 0-methyl styrene.The soft monomer is selected from chemical general formula
CH2One or more in=CH-C (0) OR propylene ^ esters, wherein R is d-C18Straight or branched alkyl, preferably Yue bases, ethyl, butyl, 2- ethylhexyls or octadecyl.The function monomer is the unsaturated acids of free redical polymerization, is preferably selected from the one or more in acrylic acid, methacrylic acid and butene dioic acid.To adjust, glass transition temperature is 5 ~ 65*C, more preferably preferably 15 50,25 ~ 45 " C.The weight ratio of hard soft monomer is 2:1~1:2, preferably 1.8:1〜1:1.5, more preferably 1.5:1~1:1.2.The consumption of function monomer is 0.2 ~ 15 weight %, preferably 0.5 ~ 5 weight % of total monomer weight.
Preferably, the emulsifying agent that the present invention is used is the mixture of anionic emulsifier or anionic emulsifier and nonionic emulsifier.Anionic emulsifier used in the present invention is all conventional anion type emulsifying agents well known to those skilled in the art, for example including：Sodium soap RCOONa, wherein
R is C12~C18Alkyl；Alkane《^ Ι Ι acid sodium ROS03Na, wherein R are C12〜C18Alkyl；Sodium alkyl sulfonate RS03Na, wherein R are C12~C18Alkyl；Alkyl ^ t acid sodium RC6H4S03Na, wherein R are C12~C18Alkyl;Alkyl biphenyl ether sodium disulfonate；Disproportionated rosin and Negel (pull open powder).For the purpose of the present invention, anionic emulsifier preferably is the one or more in above-mentioned anionic emulsifier.Nonionic emulsifier used in the present invention is all conventional nonionic type emulsifying agents well known to those skilled in the art, for example including：Polyoxyethylene sorbitan fatty acid ester class, APES class, alkyl polyoxyethylene ether class etc..For the purpose of the present invention, nonionic emulsifier preferably is the one or more in above-mentioned nonionic emulsifier.Assistant for emulsifying agent used in the present invention be preferably carbon number be more than or equal to 8 long-chain fatty alcohol, for example including：N-octyl alcohol, isooctanol, dodecanol etc..
Anionic emulsifier can be used alone, and can also be used in combination with nonionic emulsifier.Relative to total monomer weight, anionic emulsifier consumption is preferably 0.3 5.0 weight %, more preferably 1.0 3.0 weight %；Nonionic emulsifier consumption is preferably 0 5.0 weight %, more preferably 0 ~ 3.0 weight %；Assistant for emulsifying agent consumption is preferably 0-1.0 weight %, more preferably 0 ~ 0.3 weight %.
In the present invention, the initiator for emulsion polymerization is all conventional heat bows well known to those skilled in the art for emulsion polymerization！Send out agent and redox f I hair agent, preferably persulfate S I hair agent, such as ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.The consumption of initiator is the 0.2 2.0 weight %, preferably 0.5 ~ 1 weight % of total monomer weight.
In a further preferred embodiment, emulsion polymerization is carried out in the presence of Slow electuaries, and Slow electuaries used are any conventional Slow electuaries, such as ammonium hydrogen carbonate or sodium acid carbonate.The consumption of Slow electuaries is preferably 0.3 2.0 weight % of total monomer weight.
The reaction temperature of emulsion polymerization of the present invention is preferably 60 ~ 95 " C.Emulsion polymerisation time is preferably 3 12 hours.Gained aqueous polymer coating agent solid content is 20 ~ 70 weight %, more preferably 35 ~ 50 weight %.Viscosity is preferably 10 ~ 2000mPa.S, more preferably 30 500 mPa.S.
In the present invention, emulsion polymerization can be carried out in any conventional manner, and emulsion polymerization technique preferably includes：Semi-continuous process, the seed law and pre-emulsifying method.
(A) semi-continuous emulsion polymerizing technique
In the emulsion polymerization technique, by the way of initiator and monomer are each added portionwise.In preferred embodiments, part is added into the reaction vessel equipped with water, emulsifying agent and Slow electuaries,
It is preferred that 5 30 weight % mix monomer（Hard monomer, soft monomer and function monomer can be mixed in advance）.Certain temperature is risen to, the initiator of part, preferably 50 70 weight % is added when such as 60, and adds remaining mix monomer simultaneously, controls the addition speed of monomer reaction system is controlled to the reaction temperature in setting.Monomer adds remaining initiator after adding, at the reaction temperatures reaction a period of time.The residual monomer addition time is preferably 1.5 5 hours, and total reaction time is preferably 3 ~ 10 hours.
(B) seeded emulsion polymerization technique
In the emulsion polymerization technique, all function monomers, 10-30 weight % hard monomer and 10 ~ 30 weight % soft monomers are added in the reaction vessel equipped with water, emulsifying agent and Slow electuaries first, it is warming up to certain temperature, 30 ~ 50 weight % initiator is added during such as 60*C, react 0.5 2.0 hours, preferably 1 1.5 hours at the reaction temperatures；Then remaining mix monomer is at the uniform velocity added, remaining initiator is then added, at the reaction temperatures reaction a period of time.The residual monomer addition time is preferably 1 ~ 3 hour, and total reaction time is preferably 5 ~ 12 hours.
(C) pre-emulsification emulsion polymerization technique
In the emulsion polymerization technique, by the way of monomer pre-emulsion is added dropwise and initiator is added portionwise.In preferred embodiments, the mix monomer of 40 70 weight % water, 50 ~ 70 weight % emulsifying agent and 60 90 weight % is added in container, 0 ~ 60, preferred stirring and emulsifying 0.5 1.5 hours at room temperature, it is preferred that 0.6 1.0 hours, monomer pre-emulsion is made.Remaining water, emulsifying agent, assistant for emulsifying agent and mix monomer are added in reaction vessel, stirring is warming up to certain temperature, initiator as added 30 ~ 70 weight % when 60, and monomer pre-emulsion is at the uniform velocity instilled simultaneously, remaining initiator is added after completion of dropping.A period of time is reacted at the reaction temperatures.The monomer pre-emulsion addition time is preferably 1 ~ 3 hour, and total reaction time is preferably 5 12 hours.
In the present invention, the size of emulsion polymerization resulting polymers emulsion particle is mainly adjusted by the species and consumption of emulsifying agent and the consumption of function monomer, the dry state particle diameter of polymer is 30 2000 nanometers, more preferably preferably 40 ~ 600 nanometers, 50 100 nanometers.Wherein nano grade polymer emulsion particle is preferred, and its advantage is good emulsion stability, and the polymer film of formation is fine and close.
Aqueous polymer coating agent of the present invention is applicable to any water soluble fertilizer, it for example can be single fertilizer, such as nitrogenous fertilizer such as urea, phosphate fertilizer such as ammonium phosphate, potash fertilizer such as potassium sulfate, can also be compound fertilizer, the complex fertilizer of any nitrogen phosphoris and potassium fertilizer ratio, and other water-soluble plant nutritional ingredients.
Aqueous polymer coating agent of the present invention can in the form of exclusive use, or with can biology drop
Solution natural polymer or the form that is applied in combination of other coating agents and be used for any water soluble fertilizer.In the case where being applied in combination, for example, can form composite coated dose with biodegradable natural polymer or other coating agents and be applied in combination, can also each independent coating and be applied in combination.
The coating process of Inventive polymers film-coated controlled release fertilizer can be carried out in the conventional coating mode of this area, preferably in fluid bed.The coating process, which is included in fluid bed, is coated to aqueous polymer coating agent of the present invention on fertiliser granulates, adheres to inorganic particle to form the coating process of inorganic layer in fertiliser granulates surface formation polymer film, and optionally on polymer film.Aqueous polymer coating agent of the present invention is coated to fertiliser granulates surface, it is preferred to use the mode of spraying is carried out.The coating process is carried out more preferably in boiling type or rotary drum fluid bed.Temperature is preferably 30 ~ 80 in fluid bed ", coating agent spraying temperature is preferably 30 ~ 60 " C;The temperature of plate of inorganic particle is preferably 30 ~ 80.In a preferred embodiment, fertiliser granulates are put into boiling type or rotary drum fluid bed, it is preheating to 30-801C, " the C; be preferred to use double flowing nozzle by the aqueous polymer coating agent even application for preparing of the present invention on fertiliser granulates so that in the polymer film of fertiliser granulates surface one layer of continuous uniform of formation it is preferred that 40 ~ 60.Polymer film thickness can be adjusted between 20 ~ 150 microns as needed.Calculated with dry matter weight, the weight of polymer film preferably accounts for 4 ~ 20 weight % of release and release control fertilizer gross weight, more preferably 6 15 weight %.
If desired, inorganic particle is sprayed into fluid bed, it is uniformly adhered the fertiliser granulates surface in coated polymer, the amount of usual inorganic particle accounts for 0.3 ~ 10 weight % of film-coated controlled release fertilizer gross weight, preferably 0.5 ~ 5 weight./ o, more preferably 1 ~ 3 weight %.In a preferred embodiment of the invention, one or more of the inorganic particle in talcum powder, diatomite, montmorillonite, kaolin, carbonic acid erbium, bentonite, attapulgite and sepiolite powder, preferably talc powder, diatomite and calcium carbonate, more preferably micro inorganic powder.The particle diameter of inorganic particle is preferably smaller than 20 microns, more preferably less than more preferably less than 10 microns, 5 microns.Most preferably particle diameter is less than 5 microns of talcum powder, diatomite or carbonic acid 5.Embodiment
Below by embodiment, the present invention is furture elucidated, and these embodiments are only that the explanation present invention and are never limited in the present invention.
Monomer purity used is polymer grade in embodiment, and emulsifying agent and Slow electuaries are industrial products, are triggered
Agent is AR, and reaction medium is distilled water, and inorganic particle is technical grade.Viscosity rotary viscosity design determining under the monomer conversion gravimetric detemination of polymerisation, product 25, polyalcohol emulsion particle particle diameter determination of transmission electron microscopy, glass transition temperature of polymer is determined with DSC methods.
The foster of release and release control fertilizer puts the phase and is extracted with controlled release nutrients in 25 hydrostatic and start to represent to the number of days needed for 80% accumulation nutrient release rate is reached.Specific assay method is as follows：Release and release control fertilizer is standing and soak for 25* water, nutrient in sample is by film dissolution into water, by total nitrogen contents of the GB/T 8572 with titration measuring dissolution after distillation, by the vanadium part copper colorimetric method for determining dissolution Brick contents of GB/T 8573, the potassium content of dissolution is determined with flare photometer by GB/T 8574.Dissolution nutrient reaches that the time required during the 80% of the nutrient gross mass is the fertilizer releasing period of release and release control fertilizer.
Embodiment 1
(1) preparation of aqueous polymer coating agent
Using polymerization technique（A), 900 grams of water, 13 grams of Shi bis- Wan base Liu Suan Satisfied, 6 grams of n-octyl alcohols and 8 grams of ammonium hydrogen carbonate are sequentially added in 3 liters of round-bottomed flasks equipped with glassed agitator, reflux condenser, thermometer and constant pressure funnel, stirring dissolves it.8 grams of ammonium persulfates are dissolved in stand-by in 100 grams of water.510 grams of styrene, 470 gram of third Xi acid butyl ester and 20 grams of acrylic acid are put into dropping funel and are well mixed, then the 20 % mix monomer is added in reaction bulb, start and stir and be warming up to the ammonium persulfate aqueous solution that 60 milliliters are added after about 60, and remaining mix monomer is at the uniform velocity added dropwise from dropping funel simultaneously.Control monomer dropping speed and " C, the monomer dropping time is 2 hours about 85 by reaction temperature control.Remaining 40 milliliters of ammonium persulfate aqueous solutions are added after dripping off, and are reacted 4 hours at the reaction temperatures.Room temperature is cooled to, with 10 % ammoniacal liquor regulation system pH value to neutrality, then stops stirring, discharging and obtains target product.Polymerization reaction monomer conversion ratio is 98.4 %, and product viscosity is 34mPa.S, and particle diameter is 70 nanometers, and glass transition temperature of polymer is 38.2 * C.
(2) fertilizer coating process
10kg particle diameters (are come from into Shandong Kingenta Bio-engineering Stock Co., Ltd., with N-P for the composite fertilizer of 2 ~ 4 millimeters205-K20 weight % is counted：15-15-15) in ^ ^ boiling types fluidized bed, 55 ~ 65 Γ are preheating to, 45* 2.1k then will be preheated togAbove-mentioned coating agent sprays to fertilizer surface from double flowing nozzle, and spray rate is 120 grams per minute.Calculated with dry matter weight, the composition of resulting polymers film-coated controlled release fertilizer accounts for about 90.6 weight % for composite fertilizer, and polymer film accounts for about 9.4 weight %.The fertilizer releasing period of the release and release control fertilizer is about 185 days.
Embodiment 2
(1) preparation of aqueous polymer coating agent
Polymerization unit and polymerization technique step be the same as Example 1, difference is to use 300 grams of styrene, 150 grams of Yue base acrylic acid Yue esters, 490 grams of butyl acrylate, 60 grams of acrylic acid, 10 grams of lauryl sodium sulfate, 12 grams of Octylphenol polyoxyethylene ether, 5 grams of n-octyl alcohol, 12 grams of ammonium persulfate, 12 grams of ammonium hydrogen carbonate, 1000 grams of water.Polymerization reaction monomer conversion ratio is 98.9 %, and product viscosity is 58mPa.S, and particle diameter is 62 nanometers, and glass transition temperature of polymer is 25.l t：.
(2) fertilizer coating process
By 10kgParticle diameter (comes from Shandong Kingenta Bio-engineering Stock Co., Ltd., with N-P for the composite fertilizer of 2 ~ 4 millimeters205-K20 weight % is counted：16-16-16) loading in boiling type fluid bed, be preheating to 50 60, " then the above-mentioned coating agents of the 1.8kg for being preheated to 40 are sprayed to fertilizer surface, spray rate is 100 grams per minute by C from double flowing nozzle.Calculated with dry matter weight, the composition of resulting polymers film-coated controlled release fertilizer accounts for about 91.8 weight % for composite fertilizer, and polymer film accounts for about 8.2 weight %.The fertilizer releasing period of the release and release control fertilizer is about 120 days.
Embodiment 3
(1) preparation of aqueous polymer coating agent
Using polymerization technique（B), 900 grams of water, 15 grams of neopelexes, 12 grams of Octylphenol polyoxyethylene ethers, 5 grams of n-octyl alcohols and 15 grams of ammonium hydrogen carbonate are sequentially added in the 3 Sheng Round bottoms flasks equipped with glassed agitator, reflux condenser, thermometer and constant pressure funnel, stirring dissolves it.10 grams of ammonium persulfates are dissolved in stand-by in 100 grams of water.50 milliliters of ammonium persulfate aqueous solution will be added when in 80 grams of methyl methacrylates, 100 grams of butyl acrylates and 30 grams of methacrylic acid reaction bulbs, being warming up to 60, reacted 1.5 hours in about 80 times.Then the mixed liquor being made up of 340 grams of styrene and 450 grams of butyl acrylates is at the uniform velocity added dropwise from dropping funel, time for adding is 1.5 hours.Then remaining 50 milliliter ammonium persulfate aqueous solution is added, about 85 continuation is warming up to and reacts 3,5 hours.Discharged after cooling, neutralization, obtain target product.Polymerization reaction monomer conversion ratio is 99.0 %;Product viscosity is 35mPa.S, and particle diameter is 97 nanometers, and glass transition temperature of polymer is 15.6 X：.
(2) fertilizer coating process
10kg particle diameters (are come from into Shandong Kingenta Bio-engineering Stock Co., Ltd., with N-P for 2 ~ 4 millimeters of composite fertilizer205-K20 weight % is counted：
, it is preheating to
50 ~ 60 ", then will be preheated to 40 " the above-mentioned coating agents of 1.5kg spray to fertilizer surface from double flowing nozzle, spray rate be it is per minute, 80 grams.Calculated with dry matter weight, the composition of resulting polymers film-coated controlled release fertilizer accounts for about 93 weight % for composite fertilizer, and polymer film accounts for about 7.0 weight %.The fertilizer releasing period of the release and release control fertilizer is about 100 days.
Embodiment 4
(1) preparation of aqueous polymer coating agent
Using polymerization technique（C), by 500 grams of water, 2 grams of lauryl sodium sulfate, Yi Jia Ru Round bottoms flask of 3 grams of dodecyl Lian Ben Mi sodium disulfonates and 5 grams of octyl group benzene distiller's yeast APEOs, stirring dissolves it.450 grams of styrene, 470 grams of butyl acrylates, 12 grams of octadecyl acrylates and 60 grams of methacrylic acids are well mixed, and 80% mix monomer is once added in above-mentioned round-bottomed flask, emulsified 45 minutes, obtained monomer pre-emulsion is transferred to stand-by in constant pressure funnel with 700 revs/min of speed under normal temperature.14 grams of ammonium persulfates are dissolved in stand-by in 100 grams of distilled water.
400 grams of water, the sour sodium of 2 grams of dodecane ^ t, 3 grams of dodecyl phenylether sodium disulfonates, 5 grams of octyl phenol Ju Yang Yi Xi Mi, 5 grams of dodecanols and 16 grams of ammonium hydrogen carbonate are sequentially added in 3 liters of round-bottomed flasks equipped with glassed agitator, reflux condenser, thermometer and constant pressure funnel, it is dissolved under stirring, remaining 20 % mix monomer is then added.Stir and be warming up to 60 " 60 milliliters of ammonium persulfate aqueous solutions are added during C, and monomer pre-emulsion is at the uniform velocity added dropwise from dropping funel simultaneously, reaction temperature is controlled about 80 ", time for adding is about 2 hours.Remaining 40 milliliters of ammonium persulfate aqueous solutions are added after dripping, about 85 are then warming up to, continue to react 3.5 hours.Room temperature is cooled to, with 10 % ammoniacal liquor regulation system ρ Η values to neutrality, then stops stirring, discharging obtains target product.Polymerization reaction monomer conversion ratio is 99.5 %, and product viscosity is 24mPa.S, and particle diameter is 64 nanometers, and glass transition temperature of polymer is 22.5.
(2) fertilizer coating process
By 10kgParticle diameter is the sulfuric acid clock of 3 ~ 5 millimeters（From Shandong Kingenta Bio-engineering Stock Co., Ltd., with K20 weight % is calculated as in 50) boiling type fluid bed and is heated to 55 ~ 65, the above-mentioned coating agents of the 1.3kg for being preheated to about 45 then is sprayed into fertilizer surface by double flowing nozzle, spray rate is 80 grams per minute.Calculated with dry matter weight, the composition of resulting polymers film-coated controlled release fertilizer accounts for about 93.9 weight % for potassium sulfate, and polymer film accounts for about 6.1 weight %.The nutrient Dry phases of putting of the release and release control fertilizer are about 55 days.
Embodiment 5
(1) preparation of aqueous polymer coating agent
Using polymerization technique（C), 500 grams of water, 2.5 grams of neopelexes, 2.5 grams of lauryl sodium sulfate and 4 grams of polyoxyethylene 20 sorbitan monooleates are sequentially added in round-bottomed flask, stirring dissolves it.390 grams of styrene, 570 grams of ethyl acrylates and 40 grams of acrylic acid are well mixed, and 80% mix monomer is once added in above-mentioned round-bottomed flask, emulsified 45 minutes, the monomer pre-emulsion is moved into stand-by in constant pressure funnel with 700 revs/min of speed under normal temperature.10 grams of persulfuric acid clocks are dissolved in stand-by in 100 grams of water.
400 grams of water, 2.5 grams of neopelexes, 2.5 grams of lauryl sodium sulfate, 4 grams of polyoxyethylene 20 sorbitan monooleates, 4 grams of n-octyl alcohols and 15 grams of sodium acid carbonates are sequentially added in 3 liters of round-bottomed flasks equipped with glassed agitator, reflux condenser, thermometer and constant pressure funnel, remaining 20 % mix monomer is added after being uniformly dissolved under stirring.Stir and be warming up to the persulfuric acid clock aqueous solution of about 60 60 milliliters of additions, and monomer pre-emulsion is at the uniform velocity added dropwise from dropping funel simultaneously, it is 2 hours that reaction temperature, which is controlled in about time for adding, after completion of dropping, remaining 40 milliliter persulfate aqueous solution is added, about:Continue to react 4 hours under 80TC.Room temperature is cooled to, with 10 % ammoniacal liquor regulation system pH value to neutrality, then stops stirring, discharging obtains target product.Polymerization reaction monomer conversion ratio is 97.8 %, and product viscosity is 47mPa.S, and particle diameter is 78 nanometers, and glass transition temperature of polymer is 19.4.
(2) fertilizer coating process
By 10kgParticle diameter is the granular urea of 3 ~ 5 millimeters（From Shandong Mingshui Chemical Co., Ltd, with N weight. /.It is calculated as 46.4) loading in boiling type fluid bed and being heated to the 1.7k of about 60 " then C will be preheated to about 45 by a double flowing nozzle "gAbove-mentioned coating agent sprays to fertilizer surface, and spray rate is 80 grams per minute.Calculated with dry matter weight, the composition of resulting polymers film-coated controlled release fertilizer accounts for about 92.3 weight % for urea, and polymer film accounts for about 7.7 weight %.The foster ^ phases of putting of the release and release control fertilizer are about 65 days.
Embodiment 6
(1) preparation of aqueous polymer coating agent
Be the same as Example 5.
(2) fertilizer coating process
By 10kgParticle diameter is 35 millimeters of granular urea（From Shandong Mingshui Chemical Co., Ltd, with N weight. /.Be calculated as 46.4) loading in boiling type fluid bed and be heated to about 60, then by a double flowing nozzle by be preheated to about 45 1.7kgAbove-mentioned coating agent sprays to fertilizer surface, and spray rate is 80 grams per minute.Then the diatomite that 250 grams of average grain diameters are 3 microns is uniformly sprayed to the fertilizer surface that temperature is 60 C or so.Calculated with dry matter weight, the composition of resulting polymers coating control Dry fertilizer accounts for about 90.2 weight % for urea, and polymer film accounts for about 7.5 weight %, and diatomite accounts for 2.3 weight %.The fertilizer releasing period of the release and release control fertilizer is about 80 days.
Claims (18)
- Claim1. a kind of aqueous polymer coating agent, the coating agent is by hard monomer, soft monomer and selected from can be free ' 'The weight ratio of wherein described hard monomer and soft monomer is 2:1〜1:2, preferably 1.8:1〜1:1.5；The function monomer accounts for 0.2 15 weight % of total monomer weight, preferably 0.5 ~ 5 weight %.2. aqueous polymer coating agent according to claim 1, wherein one or more of the hard monomer in styrene monomer and methyl methacrylate；The soft monomer is selected from chemical formulaCH2One or more in=CH-C (0) OR acrylate, wherein R is d ds straight or branched alkyl, preferably methyl, ethyl, butyl, 2- ethylhexyls or octadecyl；One or more of the function monomer in acrylic acid, Yue bases acrylic acid and butene dioic acid.3. aqueous polymer coating agent according to claim 1, wherein the emulsifying agent is anionic emulsifier and optional nonionic emulsifier.4. aqueous polymer coating agent according to claim 3, wherein the anionic emulsifier is selected from sodium soap RCOONa, wherein R is C12〜(：18Alkyl；Sodium alkyl sulfate ROS03Na, wherein R are C12〜C18Alkyl；Sodium alkyl sulfonate RS03Na, wherein R are C12~C18Alkyl；Alkyl ^ ^ acid sodium RC6H4S03Na, wherein R are C12~C18Alkyl；Alkyl biphenyl ether sodium disulfonate；One or more in disproportionated rosin and Negel；One or more of the nonionic emulsifier in polyoxyethylene sorbitan fatty acid ester class, APES class and alkyl polyoxyethylene ether class；The assistant for emulsifying agent is the long-chain fatty alcohol that carbon number is more than or equal to 8.5. according to the aqueous polymer coating agent of claim 3 or 4, wherein relative to total monomer weight, anionic emulsifier consumption is 0.3 ~ 5.0 weight %, nonionic emulsifier consumption is 0 5.0 weight %, and assistant for emulsifying agent consumption is 0 ~ 1.0 weight %.6. aqueous polymer coating agent as claimed in one of claims 1-5, wherein the emulsion polymerization is semi-continuous process, the seed law or pre-emulsifying method emulsion polymerization.7. aqueous polymer coating agent as claimed in one of claims 1-5, wherein initiator are using the form being added portionwise.8. aqueous polymer coating agent as claimed in one of claims 1-5, wherein emulsion polymerization temperature are 60 ~ 95 °C, emulsion polymerisation time is 3 ~ 12 hours.9. aqueous polymer coating agent as claimed in one of claims 1-5, its solid content is 20 ~ 70 weight %.10. according to any one of claim 1-5 aqueous polymer coating agent, its viscosity is 10 2000mPa.S, preferably 30 500 mPa.S.11. aqueous polymer coating agent as claimed in one of claims 1-5, its particle dry state particle diameter is 30 ~ 2000 nanometers, preferably 40 ~ 600 nanometers, more preferably 50：100 nanometers.12. aqueous polymer coating agent as claimed in one of claims 1-5, its glass transition temperature is 5 65'C, preferably 15 50 ", more preferably 25 ~ 45 " C.13. a kind of film-coated controlled release fertilizer, its coating outside fertilizer core and fertilizer core is constituted, it is characterised in that the polymer film of aqueous polymer coating agent formation of the coating comprising any one of claim 1-12.14. film-coated controlled release fertilizer according to claim 13, wherein being calculated with dry matter weight, the weight of the polymer film is 4 ~ 20 weight %, preferably 6 ~ 15 weight % of release and release control fertilizer gross weight.15. coated release-controlled ^ ^ according to claim 13, wherein the coating is also included in the outer inorganic layer containing inorganic particle of polymer film.16. coated release-controlled ^ ^ according to claim 15, wherein the amount without body accounts for 0.3 10 weight % of film-coated controlled release fertilizer gross weight, more preferably preferably 0.5 5 weight %, 1 ~ 3 weight %.17. a kind of method of the coating control Dry fertilizer prepared described in claim any one of 13-16, it is included in fluid bed, it is preferred that in boiling type or rotary drum fluid bed, the aqueous polymer coating agent is sprayed on fertiliser granulates, preferably the aqueous polymer coating agent is sprayed in fertiliser granulates surface by double flowing nozzle, adhere to inorganic particle to form the coating process of inorganic layer in fertiliser granulates surface formation polymer film, and optionally on polymer film.18. the method according to claim 17 for preparing film-coated controlled release fertilizer, it is characterised in that temperature is 30 ~ 80 in fluid bed, and " C, coating agent spraying temperature is 30 ~ 60, and " C, inorganic particle temperature of plate is 30 ~ 80 X：.
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| CN2007101418861A CN101348394B (en) | 2007-08-15 | 2007-08-15 | Aqueous polymer coating agent and coated controlled release fertilizer |
| CN200710141886.1 | 2007-08-15 | ||
| PCT/CN2008/000712 WO2009021388A1 (en) | 2007-08-15 | 2008-04-08 | Aqueous polymer coating agent,coated release-controlled fertilizer and preparation thereof |
| CN2008801024843A CN101932537A (en) | 2007-08-15 | 2008-04-08 | Aqueous polymer coating agent, film-coated controlled release fertilizer and preparation method thereof |
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| CN103755468A (en) * | 2013-12-26 | 2014-04-30 | 合肥工业大学 | Novel controlled-release fertilizer coating agent and preparation method thereof |
| CN105085778B (en) * | 2014-04-22 | 2018-11-16 | 广东华润涂料有限公司 | Coating composition water-based latex, preparation method and application for slow-release function ingredient |
| CN106083351A (en) * | 2016-06-17 | 2016-11-09 | 安庆市富江水产养殖有限公司 | A kind of environmental protection water-fast aquaculture pasture and water special fertilizer |
| CN106083363A (en) * | 2016-06-17 | 2016-11-09 | 安庆市富江水产养殖有限公司 | A kind of aquaculture pasture and water environmental protection high usage fertilizer |
| CN106589218B (en) * | 2016-12-12 | 2019-02-19 | 湖南农业大学 | A kind of film forming agent, preparation method and application for seed pelleting |
| CN111072791A (en) * | 2019-12-27 | 2020-04-28 | 河南新孚望新材料科技有限公司 | Preparation method of high amylose starch for coating agent |
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| JPH04293914A (en) * | 1991-03-25 | 1992-10-19 | Japan Synthetic Rubber Co Ltd | Polymer powder |
| CN1082573A (en) * | 1993-08-24 | 1994-02-23 | 四川省建筑科学研究院 | Water soluble imitation glaze coating compound |
| JP4293914B2 (en) * | 2004-01-07 | 2009-07-08 | クォンツ・リサーチ株式会社 | Stock price chart providing apparatus, stock price chart providing method, and stock price chart providing program |
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