CN102942415B - Physical and chemical dual-control-type polymer-coated controlled-release fertilizer and preparation method thereof - Google Patents
Physical and chemical dual-control-type polymer-coated controlled-release fertilizer and preparation method thereof Download PDFInfo
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- CN102942415B CN102942415B CN201210460521.6A CN201210460521A CN102942415B CN 102942415 B CN102942415 B CN 102942415B CN 201210460521 A CN201210460521 A CN 201210460521A CN 102942415 B CN102942415 B CN 102942415B
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Abstract
The invention discloses a physical and chemical dual-control-type polymer-coated controlled-release fertilizer and a preparation method thereof. The fertilizer consists of a particle fertilizer and a polymer film which covers the surface of the particle fertilizer, wherein the weight of the polymer film accounts for 3-15 percent of the total weight of the polymer-coated controlled-release fertilizer. The substance for forming the polymer film is a polymer with a constitutional repeating unit being shown as a formula I and an end group being methyl, wherein R is at least one of H, C1-C8 alkyl and naphthyl ethyl, and R' is at least one of H and C1-C8 alkyl. The coating material has good film forming performance, has good physical controlled-release performance for nitrogen, phosphorus, potassium and the like in the core particle of the fertilizer, and simultaneously can realize the function releasing of chemically reactive substances such as alpha-naphthylacetic acid in the soil environment. The coating process of the controlled-release fertilizer is mature; and by adopting a fluidized bed coating method, the investment cost is low and the feasibility is high.
Description
Technical field
The invention belongs to fertilizer control release technical field, particularly a kind of " physics, chemical double-controlling type " polymer coating controlled release fertilizer and preparation method thereof.
Background technology
Chemical fertilizer has Yi Rong, quick-acting advantage, also has very large defect simultaneously, and the excessive use of chemical fertilizer, has brought a large amount of nutrient loss, and causes a series of Environmental and resource issue, so development Controlled Release Fertilizer becomes an inexorable trend of fertilizer development.The research direction of release and release control fertilizer comprises environmentally friendly coated fertilizer, reduces the multifunction research of release and release control fertilizer cost and fertilizer etc. at present.
Release and release control fertilizer, keeping it to control on the slow basis discharging of nutrient,, constantly to multifunction development, improves the summation effect of fertilizer.Current multi-functional controlled release fertilizer mainly contain following several form: (1) multiple fertilizer mixing manufacture Fei Xinhuoyi composite fertilizer is core core, carries out coating (200410021079.2,200710080227.1,200810015602.9).The object of this kind of fertilizer is single fertilization, meets crop multiple element demand, meets the crop demand in whole vegetative period simultaneously, has reduced a large amount of fertilising work and the injury to crop.Another example is that to take weathered coal humic acid etc. be that coating agent coated compound fertilizer is made double-control composite release and release control fertilizer in China Agriculture Academe Fertilizer Institute, the multiple nutrient of core core has sustained release performance, and integument also has nutrient slowly-released performance (200510051250.9).(2) by adding chemical inhibitor, obtain several functions, this kind of fertilizer reaches the function of soil organisms adjusting or fertilizer release regulation by the effect of inhibitor.Calendar year 2001, Shenyang Inst. of Applied Ecology, Chinese Academy of Sciences applied for a patent (01133415.0), added urease inhibitor and/or nitrification inhibitor in fertile core, both can meet soil organisms is suppressed, and can play again the effect of nitrogenous fertilizer controlled release.(3) take the materials such as water-holding agent as coating agent wraps up fertile core, can prepare the water holding controlled release fertilizer with water holding controlled release dual-use function, and water-holding agent also has the effect (200410050219.9 of improvement soil, 200710052235.5,200910081289.3,201110275712.0,201110275715.4).A kind of sustained release dosage has been prepared with vinylformic acid, acrylamide, Semen Maydis powder, wilkinite etc. by Shijiazhuang Jianyuan Starch Derivative Co., Ltd., add and prepare slow-release fertilizer or slow releasing medicinal, do not affect fertilizer, medicine quality and performance, can play and inhale fertile fertilizer conservation, suction medicine guarantor's medicine and water-absorbing-retaining effect, be a kind of multi-functional sustained release dosage (200610012360.9).(4) sterilant, bio-active substance etc. is combined with slow-release fertilizer, the multi-functional controlled release that preparation has nutrient controlled release and other effects is fertile.These functional substance also can be prepared and be had multi-functional release and release control fertilizer (200310109321.7,200910037633.9) by modes such as granulation or compressing tablets together with fertilizer.
In the research of above-mentioned fertilizer multifunction, concentrate on the diversification of fertilizer core granulation composition and the method that has adopted multi-coated, realize the final diversification of fertilizer function.But the fertilizer of above preparation dissolves comparatively fast in water, its fertilizer releasing period is generally shorter, is difficult to reach the effect of slow/controlled release, and being difficult to provides nutrient for crop late growing stage.And also rarely has report as the naphthylacetic acid of crop growth regulator, dormin, Whitfield's ointment etc. with the combination of release and release control fertilizer.And this class material and the combination of release and release control fertilizer only rest at present the means such as mixes, carrier is held back, and there is no the relevant report of this class material of chemical bonding mode controlled release.The means such as carrier combination or mixing are poor to the controlled-release effect of target compound, and the control of rate of release is difficult to realize, and can not reach for a long time slowly release, effective when long.The crop growth regulator rate of release of chemical bonding is controlled, long action time.So research and development have good release performance concurrently and multi-functional fertilizer is the important directions of release and release control fertilizer development.
Summary of the invention
The object of this invention is to provide a kind of " physics, chemical double-controlling type " polymer coating controlled release fertilizer and preparation method thereof.
Polymer coating controlled release fertilizer provided by the invention, is comprised of granulated fertilizer and the polymeric film that is wrapped in granulated fertilizer surface; Wherein, described polymeric film accounts for 3%～15% of described polymer coating controlled release fertilizer gross weight;
Described polymeric film accounts for 3～15% of described polymer coating controlled release fertilizer gross weight;
The material that forms described polymeric film is that repeated structural unit is
, the end group polymkeric substance that is methyl, wherein, R is selected from H, C
1-C
8alkyl and naphthalene ethyl
in at least one, R ' is selected from hydrogen and C
1-C
8alkyl at least one.
Described C
1-C
8alkyl be methyl or ethyl or n-propyl or sec.-propyl or normal-butyl; The number-average molecular weight of described polymkeric substance is 10
4～10
7, preferably 10
5～10
7; The second-order transition temperature of described polymeric film is-25～80 ℃, preferably 40～60 ℃;
The particle diameter of described granulated fertilizer is 2～4mm.
More specifically, described polymkeric substance is according to the method preparation comprising the steps and obtain: acrylic monomer and/or acrylic ester monomer and solvent and initiator are mixed and carry out polyreaction, react complete obtaining after polyacrylic ester, add again plant-growth regulator, dewatering agent and catalyzer to carry out catalytic dehydration condensation reaction, react the complete described polymkeric substance that obtains.
Wherein, described acrylic monomer is selected from least one in vinylformic acid, methacrylic acid, ethylacrylic acid and hydroxyethyl vinylformic acid; Described acrylic ester monomer is selected from least one in Hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, ethyl propenoate and butyl acrylate;
The ethyl acetate that described solvent is 0-80:0-80:0-80 by weight ratio, butylacetate and hexanaphthene form, and the weight of described ethyl acetate, butylacetate and hexanaphthene is not all 0;
Described initiator is selected from least one in benzoyl peroxide and Diisopropyl azodicarboxylate;
Described dewatering agent is dicyclohexylcarbodiimide;
Described catalyzer is DMAP;
Described plant-growth regulator is selected from α-naphthaleneacetic acid;
The ratio of weight and number of described acrylic monomer or acrylic ester monomer, solvent and initiator is 20～70:20～80:0.005～0.2, preferably 40～60:40～60:0.005～0.1;
In described polymerization procedure, temperature is 70～90 ℃, and preferably 80～90 ℃, the time is 2～7 hours, preferably 4～7 hours; Described polyreaction is carried out in inert atmosphere; Described inert atmosphere is nitrogen atmosphere;
The ratio of weight and number of described polyacrylic ester, plant-growth regulator, dewatering agent and catalyzer is 40～80:0～20:0～10:0～2, preferably 50～70:5～10:2～7:0.5～1; In described catalytic dehydration step of condensation, temperature is normal temperature, and the time is 5～10 hours.
Polymkeric substance shown in above-mentioned formula I is obtained to described polymeric film according to conventional film.
The method of the described polymer coating controlled release fertilizer of preparation provided by the invention, comprises the steps:
1) acrylic monomer and/or acrylic ester monomer and solvent and initiator are mixed and carry out polyreaction, react complete obtaining after polyacrylic ester, add again plant-growth regulator, dewatering agent and catalyzer to carry out catalytic dehydration condensation reaction, react the complete described polymkeric substance that obtains;
2) by described step 1) resulting polymers and described step 1) solvent for use, filler and auxiliary agent mix and obtain after polymer capsule liquid, in coating tower, blasting hot blast makes granulated fertilizer in flow state, described polymer capsule liquid is evenly sprayed to described granulated fertilizer surface, be dried and obtain described polymer coating controlled release fertilizer.
In this step, the first step polyreaction gained is physics controlled release polymer film material, and second step catalytic dehydration condensation reaction gained is " physics, chemical double-controlling type " polymeric film;
Step 1 described in aforesaid method), in, described acrylic monomer is selected from least one in vinylformic acid, methacrylic acid, ethylacrylic acid and hydroxyethyl vinylformic acid; Described acrylic ester monomer is selected from least one in Hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, ethyl propenoate and butyl acrylate;
The ethyl acetate that described solvent is 0-80:0-80:0-80 by weight ratio, butylacetate and hexanaphthene form, and the weight of described ethyl acetate, butylacetate and hexanaphthene is not all 0;
Described initiator is selected from least one in benzoyl peroxide and Diisopropyl azodicarboxylate;
Described dewatering agent is dicyclohexylcarbodiimide;
Described catalyzer is DMAP;
Described plant-growth regulator is selected from α-naphthaleneacetic acid.
The ratio of weight and number of described acrylic monomer or acrylic ester monomer, solvent and initiator is 20～70:20～80:0.005～0.2, preferably 40～60:40～60:0.005～0.1;
In described polymerization procedure, temperature is 70～90 ℃, and preferably 80～90 ℃, the time is 2～7 hours, preferably 4～7 hours; Described polyreaction is carried out in inert atmosphere; Described inert atmosphere is nitrogen atmosphere;
The ratio of weight and number of described polyacrylic ester, plant-growth regulator, dewatering agent and catalyzer is 40～80:0～20:0～10:0～2, preferably 50～70:5～10:2～7:0.5～1; In described catalytic dehydration step of condensation, temperature is normal temperature, and the time is 5～10 hours.
Described step 2) in, described filler is selected from least one in paraffin, talcum powder, zeolite powder and wilkinite, wherein to account for the weight ratio of polymeric film material be 0～0.03 to paraffin, the weight ratio that talcum powder accounts for polymeric film material is 0～0.02, the weight ratio that zeolite powder accounts for polymeric film material is 0～0.01, and the weight ratio that wilkinite accounts for polymeric film material is 0～0.02;
Described auxiliary agent is selected from least one in methyl iso-butyl ketone (MIBK), trimethylcyclohexanone and diethylene glycol monobutyl ether, wherein to account for the weight ratio of polymeric film material be 0～0.03 to methyl iso-butyl ketone (MIBK), the weight ratio that trimethylcyclohexanone accounts for polymeric film material is 0～0.02, and the weight ratio that diethylene glycol monobutyl ether accounts for polymeric film material is 0～0.02;
The consumption of described filler and auxiliary agent is not all 0;
Described granulated fertilizer is selected from least one in urea, volatile salt, ammonium nitrate, ammonium sulfate, Repone K, saltpetre, Secondary ammonium phosphate, primary ammonium phosphate or composite fertilizer.
The consumption of described polymeric film is 3～15% of described polymer coating controlled release fertilizer gross weight; The consumption of described filler is 0～8% of described polymeric film weight; The consumption of described auxiliary agent is the 0-8% of described polymeric film weight; The consumption of described filler and auxiliary agent is not all 0;
In described spraying step, atomizing pressure is 3～5kPa, and temperature is 50～70 ℃; In described drying step, temperature is 70～90 ℃, and preferably 70～80 ℃, the time is 5～30 minutes, preferably 10～20 minutes.
The invention provides a kind of preparation method of polymer coating controlled release fertilizer of " physics, the chemical double-controlling type " that realizes fertilizer multifunction target, the polymkeric substance that is wrapped in fertilizer surface is played and is controlled the effect that nutrient discharges by " physical isolation " effect, simultaneously that the biologically active substances such as plant-growth regulator is surperficial at mould material by chemical bonding, biologically active substance is hydrolyzed and is slowly released by chemical bond, thereby reaches the effect of " chemical controlled release ".This polymer coating controlled release fertilizer, compares with coated fertilizer in the past, has realized the physics controlled release of nutrient and " dual " controlled release of active substance chemistry controlled release.There is following obvious advantage:
1) coated fertilizer has carried out special formulating of recipe, and for the coating purposes of fertilizer, the specific aim of material application improves greatly specially.This serial coated fertilizer has good film forming properties, has good physics controlled release properties, and can complete voluntarily chemical activation substance release function at occurring in nature, belongs to dual controlled release material.
2) different from conventional heating for dissolving polymer process, dissolve polymer film material, reduces the volatilization of the solvent of energy consumption and dissolution process at normal temperatures.
3) coating process is simple, adopts common fluidized-bed coating method, and cost of investment is low, simple and feasible.
4) by changing composition and the ratio of monomer in mould material, molecular size range and the second-order transition temperature of regulation and control mould material, controlled release properties, snappiness, hardness and the shock resistance of optimization film material.
5) by composition and the ratio of close and distant aqueous monomer and functional group in change mould material, chemical activation substances content, hydrophilic and hydrophobic, water tolerance and the permeability of regulation and control mould material, thus can realize the effect of good " physics, chemical double-controlling are released ".
6) by optimizing structure and the thickness of film material, film material price is 65% of conventional film material price, thereby greatly reduces the production cost of fertilizer, and release and release control fertilizer is applied on field crop becomes possibility.
7) the present invention is when realizing the nitrogen phosphorus potassium controlled release in fertilizer nutrient particle, also in mould material bonding α-naphthaleneacetic acid, realized the regulating effect to plant-growth.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of polymeric film;
Fig. 2 is the coated fertilizer nutrient release profiles of embodiment 1;
Fig. 3 is the polymeric film material α-naphthaleneacetic acid release profiles of embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
The selection of solvent: for the solvent toxicity problem in similar patent in the past, the present invention is according to the principle of " similar mixing ", selection mechanism is close, the solvent of low toxicity, superior performance is tested, screening solubility property is good, evaporation rate is moderate, the solvent of low toxicity, searching can be dissolved this polymkeric substance well, can meet again the solvent of spraying precipitated phase conversion method film-forming process requirement.The selection step of solvent is as follows: with 100mL graduated cylinder, measure by ethyl acetate: butylacetate: the mixed solvent of the ratio of weight and number preparation that hexanaphthene is 0～80:0～80:0～80 joins in 500mL reaction flask, be placed on iron stand, add this polymkeric substance of 4g, put into respectively churned mechanically stirring rake, thermometer, reflux.Open stirring power supply, under 20～28 ℃ or room temperature, stir 5 minutes, observe and find, this polymer dissolution, becomes true solution.This true solution is transparent low viscosity, with glass stick, dips after solution, and in air, solvent evaporates is rapid, forms the film of intact on glass stick.Polymkeric substance true solution is placed into room temperature, and solution keeps vitreous state.
The coating method of polymer coating controlled release fertilizer specifically carries out according to following steps: in reactor, by 100 parts of synthetic polymeric film materials, add 100～4000 parts of mixed solvents, add according to the above ratio various fillers, auxiliary agent simultaneously, after heat temperature raising, stirring, make polymer capsule liquid, cooling transfer is standby; Take 3kg coating liquid (wherein polymeric film material account for granulated fertilizer gross weight 12%), 5kg grade is at the round granulated fertilizer (as urea) of 2～4mm, granulated fertilizer is placed in boiling type coating tower, at 55～75 ℃, carry out preheating in 10～15 minutes, fluidisation pressure is adjusted to the fertiliser granulates shape that fully seethes with excitement is as the criterion, and atomizing pressure is 3kPa; Hot blast temperature is under 50～70 ℃ of conditions, and coating liquid is evenly coated in to granulated fertilizer surface, continues to dry 5～50 minutes after one time coating completes in coating tower, at particle surface, forms one deck plastic film, and solvent is by condenser recycling; The fertilizer of wrapping is emitted in shutdown, the cooling finished product controlled release coat urea fertilizer that is.
For the coating liquid auxiliary agent problem in above-mentioned patent, the present invention is according to reducing coating liquid viscosity, improve unit plane coating rate, effectively regulate controlled release properties, reducing membrane wrapping thickness principle, the coating liquid that screenability is good.Add filler paraffin, talcum powder, zeolite powder or wilkinite; Auxiliary agent methyl iso-butyl ketone (MIBK), trimethylcyclohexanone or diethylene glycol monobutyl ether are to regulate fertilizer surface properties.
The applicable fertilizer of the present invention can be various water miscible granulated fertilizers, comprises urea, volatile salt, ammonium nitrate, ammonium sulfate, Repone K, saltpetre, Secondary ammonium phosphate, primary ammonium phosphate etc., can be straight fertilizer, also composite fertilizer; Require the particle diameter of granulated fertilizer to be: optimum particle diameter is at 2～4mm.In the present invention, employing be granular urea and composite fertilizer, granular urea first sieves, and controls particle diameter within the scope of 2～4mm.
Plant-growth regulator discharges to be evaluated: by different polymeric film materials, after accurately weighing, be immersed in buffered soln, every sampling in 7 days, by UV spectrum (281nm wavelength), measure chemical activation substances content in solution, calculational chemistry activating substance releasability.
Nutrient physics release characteristics check: the fertilizer sample of getting preparation, put into nylon net bag, then immerse in 200mL distilled water, sealing, is placed in 25 ℃ of constant incubators, while reaching 80% respectively at accumulative total rate of release, taking out 25mL soak solution analyzes, residue soak solution is outwelled, rejoined 200mL distilled water, keep cumulative volume constant.Meanwhile, separately get identical coated fertilizer, through levigate, to 100 orders, measure contained each nutrient content in sample.Mensuration project and method: in urea, N adopts the method that GB GB/T23348-2009 recommends to measure; In composite fertilizer, N adopts GB GB/T8572-2001 recommend method to measure, and P adopts the method that GB GB/T8573-1999 recommends to measure, and K adopts the method that GB GB/T8574-2002 recommends to measure.
This polymer is different from other materials part and is, film material can be controlled chemical activation substances content and be uniformly distributed on film material, and can carry out controlled release release according to plant physiology is required, meets the regulating and controlling effect of chemical activation material to plant; And can control the molecular size range of macromolecular material and distribution and then reach controlling diaphragm material and discharge.Film material strength decreased as too low in molecular weight, if the too high plasticizing forming difficulty of molecular weight, the second-order transition temperature of this polymkeric substance is-25～80 ℃, the scope of polymericular weight is 10
4～10
7.
Embodiment 1
1) by butyl methacrylate, methyl methacrylate, Hydroxyethyl acrylate is that the ratio of 65:25:10 is mixed by ratio of weight and the number of copies, the ethyl acetate that adds above-mentioned monomer total amount ratio of weight and number 40, stirs, passes into nitrogen, is heated to 75 ℃, adding monomer weight portion rate is the benzoyl peroxide of 0.03 part, initiated polymerization, reacted after 6 hours, obtained physics controlled release polymer polyacrylic ester film material solution; Adding polymer weight portion rate is 10 α-naphthaleneacetic acid again, and the dicyclohexylcarbodiimide that ratio of weight and number is 10, stirs, adding ratio of weight and number is 1 DMAP, catalytic dehydration, normal-temperature reaction, after 10 hours, obtains the polymeric film material of " physics, chemical double-controlling are released ".
Fig. 1 is the infared spectrum of this polymeric film material; As seen from the figure, this polymer architecture is correct, for repeated structural unit is
, the end group polymkeric substance that is methyl, R is methyl and naphthalene ethyl
, R ' is methyl and normal-butyl.GPC determining molecular weight is 10
5.
2) by step 1) resulting polymers film material 100g is dissolved in 2500g ethyl acetate and hexanaphthene massfraction than in the mixed solvent for 2:3, the mixture that adds the methyl iso-butyl ketone (MIBK) that accounts for respectively wilkinite that polymeric film material weight ratio is 0.005,0.005 talcum powder, 0.02 paraffin and 0.001, is uniformly mixed and makes coating mixture.The granular urea that is 2～4mm by 1500g diameter packs in boiling type fluidized-bed, is heated to 70 ℃.At hot blast temperature, being at 70 ℃, is under 3kPa with two-fluid spray nozzle at air atomizing pressure, and the speed spraying with per minute 2g, all sprays to solution on granular urea.The control release urea of gained, polymeric membrane accounts for 6% of fertilizer gross weight, and this fertilizer is in the water of 25 ℃, and nutrient physical control time of releasing is 6 months, and it is 3 months that α-naphthaleneacetic acid is controlled time of releasing.
Fig. 2 is this embodiment gained coated fertilizer nutrient release profiles; Fig. 3 is this embodiment resulting polymers mould material α-naphthaleneacetic acid release profiles.As seen from the figure, naphthylacetic acid discharges slower in the early stage, after 7 days, with constant speed, discharges, and in one month, discharges 40%, according to naphthylacetic acid rate of release, calculates, and this material naphthylacetic acid release period reaches 2 months.
Embodiment 2
1) by butyl methacrylate: methyl methacrylate: Hydroxyethyl acrylate: the vinylformic acid by ratio of weight and the number of copies ratio of 50:30:10:10 mixes, add ethyl acetate by ratio of weight and the number of copies 40, stir, pass into nitrogen, be heated to 85 ℃, add polymer weight portion rate to be 0.05 part and obtain benzoyl peroxide, initiated polymerization, reacted after 4 hours, obtained physics controlled release polymer polyacrylic ester film material solution; Adding polymer weight portion rate is 15 α-naphthaleneacetic acid again, ratio of weight and number is that 15 dicyclohexylcarbodiimide stirs, and adding ratio of weight and number is 2 DMAP, catalytic dehydration, after normal-temperature reaction 7 hours, obtain the polymeric film material of " physics, chemical double-controlling are released ".
The infrared spectrogram of this polymeric film material and Fig. 1 are without substantive difference, and known this polymer architecture is correct, for repeated structural unit is
, the end group polymkeric substance that is methyl, wherein, R is H, methyl and naphthalene ethyl
, R ' is methyl and normal-butyl, GPC determining molecular weight is 10
7.
2) by step 1) resulting polymers film material 60g is dissolved in 2000g ethyl acetate by ratio of weight and the number of copies: in the mixed solvent that hexanaphthene is 4:1, the mixture that adds the methyl iso-butyl ketone (MIBK) that accounts for respectively wilkinite that polymeric film material weight ratio is 0.01,0.03 talcum powder, 0.02 paraffin and 0.001, stirring and dissolving makes coating liquid.The granular urea that is 2～4mm by 1500g diameter packs in boiling type fluidized-bed, is heated to 80 ℃.At hot blast temperature, being at 80 ℃, is 5kPa with two-fluid spray nozzle at air atomizing pressure, and the progress spraying with per minute 2g, all sprays to solution on granular urea.The control release urea of gained, polymeric membrane accounts for 4% of fertilizer gross weight, and this fertilizer is in the water of 25 ℃, and nutrient physical control time of releasing is 5 months, and be 4 months control time of releasing of α-naphthaleneacetic acid.
Claims (11)
1. a polymer coating controlled release fertilizer, is comprised of granulated fertilizer and the polymeric film that is wrapped in granulated fertilizer surface; It is characterized in that: described polymeric film accounts for 3～15% of described polymer coating controlled release fertilizer gross weight;
The material that forms described polymeric film is that repeated structural unit is
, the end group polymkeric substance that is methyl, wherein, R is selected from H, C
1-C
8alkyl and naphthalene ethyl
in at least one, R ' is selected from hydrogen and C
1-C
8alkyl at least one;
Described polymkeric substance is according to the method preparation comprising the steps and obtain: acrylic monomer and/or acrylic ester monomer and solvent and initiator are mixed and carry out polyreaction, react complete obtaining after polyacrylic ester, add again plant-growth regulator, dewatering agent and catalyzer to carry out catalytic dehydration condensation reaction, react the complete described polymkeric substance that obtains; Described plant-growth regulator is α-naphthaleneacetic acid;
The ethyl acetate that described solvent is 0-80:0-80:0-80 by weight ratio, butylacetate and hexanaphthene form, and the weight of described ethyl acetate, butylacetate and hexanaphthene is not all 0;
Described initiator is selected from least one in benzoyl peroxide and Diisopropyl azodicarboxylate;
Described dewatering agent is dicyclohexylcarbodiimide;
Described catalyzer is DMAP;
The ratio of weight and number of described acrylic monomer or acrylic ester monomer, solvent and initiator is 20～70:20～80:0.005～0.2;
In described polymerization procedure, temperature is 70～90 ℃, and the time is 2～7 hours; Described polyreaction is carried out in inert atmosphere;
The ratio of weight and number of described polyacrylic ester, plant-growth regulator, dewatering agent and catalyzer is 40～80:0～20:0～10:0～2; In described catalytic dehydration step of condensation, temperature is normal temperature, and the time is 5～10 hours.
2. fertilizer according to claim 1, is characterized in that: described C
1-C
8alkyl be methyl or ethyl or n-propyl or sec.-propyl or normal-butyl; The number-average molecular weight of described polymkeric substance is 10
4～10
7; The second-order transition temperature of described polymeric film is-25～80 ℃;
The particle diameter of described granulated fertilizer is 2～4mm.
3. fertilizer according to claim 2, is characterized in that: the number-average molecular weight of described polymkeric substance is 10
5～10
7; The second-order transition temperature of described polymeric film is 40～60 ℃.
4. fertilizer according to claim 1, is characterized in that: described acrylic monomer is selected from least one in vinylformic acid, methacrylic acid, ethylacrylic acid and hydroxyethyl vinylformic acid; Described acrylic ester monomer is selected from least one in Hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, ethyl propenoate and butyl acrylate; Described inert atmosphere is nitrogen atmosphere.
5. fertilizer according to claim 1, is characterized in that:
The ratio of weight and number of described acrylic monomer or acrylic ester monomer, solvent and initiator is 40～60:40～60:0.005～0.1;
In described polymerization procedure, temperature is 80～90 ℃, and the time is 4～7 hours;
The ratio of weight and number of described polyacrylic ester, plant-growth regulator, dewatering agent and catalyzer is 50～70:5～10:2～7:0.5～1.
6. a method of preparing the arbitrary described polymer coating controlled release fertilizer of claim 1-5, comprises the steps:
1) acrylic monomer and/or acrylic ester monomer and solvent and initiator are mixed and carry out polyreaction, react complete obtaining after polyacrylic ester, add again plant-growth regulator, dewatering agent and catalyzer to carry out catalytic dehydration condensation reaction, react the complete polymkeric substance described in claim 1 or 2 that obtains; Described plant-growth regulator is α-naphthaleneacetic acid;
2) by described step 1) resulting polymers and described step 1) solvent for use, filler and auxiliary agent mix and obtain after polymer capsule liquid, in coating tower, blasting hot blast makes granulated fertilizer in flow state, described polymer capsule liquid is evenly sprayed to described granulated fertilizer surface, be dried and obtain described polymer coating controlled release fertilizer;
Wherein, step 1) ethyl acetate, butylacetate and hexanaphthene that described in, solvent is 0-80:0-80:0-80 by weight ratio form, and the weight of described ethyl acetate, butylacetate and hexanaphthene is not all 0;
Described initiator is selected from least one in benzoyl peroxide and Diisopropyl azodicarboxylate;
Described dewatering agent is dicyclohexylcarbodiimide;
Described catalyzer is DMAP;
Described step 1), in, the ratio of weight and number of described acrylic monomer or acrylic ester monomer, solvent and initiator is 20～70:20～80:0.005～0.2;
In described polymerization procedure, temperature is 70～90 ℃, and the time is 2～7 hours; Described polyreaction is carried out in inert atmosphere;
The ratio of weight and number of described polyacrylic ester, plant-growth regulator, dewatering agent and catalyzer is 40～80:0～20:0～10:0～2; In described catalytic dehydration step of condensation, temperature is normal temperature, and the time is 5～10 hours;
Described step 2) in, described filler is selected from least one in paraffin, talcum powder, zeolite powder and wilkinite, wherein to account for the weight ratio of polymeric film material be 0～0.03 to paraffin, the weight ratio that talcum powder accounts for polymeric film material is 0～0.02, the weight ratio that zeolite powder accounts for polymeric film material is 0～0.01, and the weight ratio that wilkinite accounts for polymeric film material is 0～0.02;
Described auxiliary agent is selected from least one in methyl iso-butyl ketone (MIBK), trimethylcyclohexanone and diethylene glycol monobutyl ether, wherein to account for the weight ratio of polymeric film material be 0～0.03 to methyl iso-butyl ketone (MIBK), the weight ratio that trimethylcyclohexanone accounts for polymeric film material is 0～0.02, and the weight ratio that diethylene glycol monobutyl ether accounts for polymeric film material is 0～0.02;
The consumption of described filler and auxiliary agent is not all 0.
7. method according to claim 6, is characterized in that: described step 1), described acrylic monomer is selected from least one in vinylformic acid, methacrylic acid, ethylacrylic acid and hydroxyethyl vinylformic acid; Described acrylic ester monomer is selected from least one in Hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, ethyl propenoate and butyl acrylate.
8. method according to claim 6, is characterized in that: described inert atmosphere is nitrogen atmosphere.
9. method according to claim 6, is characterized in that: described step 1), the ratio of weight and number of described acrylic monomer or acrylic ester monomer, solvent and initiator is 40～60:40～60:0.005～0.1;
In described polymerization procedure, temperature is 80～90 ℃, and the time is 4～7 hours;
The ratio of weight and number of described polyacrylic ester, plant-growth regulator, dewatering agent and catalyzer is 50～70:5～10:2～7:0.5～1.
10. method according to claim 6, is characterized in that:
Described granulated fertilizer is selected from least one in urea, volatile salt, ammonium nitrate, ammonium sulfate, Repone K, saltpetre, Secondary ammonium phosphate or primary ammonium phosphate.
11. methods according to claim 6, is characterized in that: described step 2), the consumption of described polymeric film is 3～15% of described polymer coating controlled release fertilizer gross weight; The consumption of described filler is 0～8% of described polymeric film weight; The consumption of described auxiliary agent is the 0-8% of described polymeric film weight; The consumption of described filler and auxiliary agent is not all 0;
In described spraying step, atomizing pressure is 3～5kPa, and temperature is 50～70 ℃; In described drying step, temperature is 70～90 ℃, and the time is 5～30 minutes.
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| CA3088448A1 (en) * | 2018-02-09 | 2019-08-15 | Rynan Technologies Pte Ltd | Smart release potash fertilizer granules |
| CN112745458A (en) * | 2020-12-30 | 2021-05-04 | 四川省新兰月生物科技有限公司 | Water-retaining agent for enhancing stress resistance and preparation method thereof |
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| CN101508616B (en) * | 2009-03-31 | 2012-05-02 | 中国农业大学 | Moisture-retention sustained and controlled release fertilizer and method of preparing the same |
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