CN105753611A - Unsaturated polyester coated controlled-release fertilizer prepared from PET wastes and preparation method thereof - Google Patents
Unsaturated polyester coated controlled-release fertilizer prepared from PET wastes and preparation method thereof Download PDFInfo
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- CN105753611A CN105753611A CN201610013859.5A CN201610013859A CN105753611A CN 105753611 A CN105753611 A CN 105753611A CN 201610013859 A CN201610013859 A CN 201610013859A CN 105753611 A CN105753611 A CN 105753611A
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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
- 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
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Soil Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to unsaturated polyester coated controlled-release fertilizer prepared from PET wastes and a preparation method thereof and belongs to the technical field of controlled-release fertilizers.The unsaturated polyester coated controlled-release fertilizer comprises granulated fertilizer 1, unsaturated polyester coating inner layers 2 on the surface of the granulated fertilizer 1, unsaturated polyester coating middle layers 3 on the surfaces of the coating inner layers 2, and unsaturated polyester coating outer layers 4 on the surfaces of the coating middle layers 3, and the weights of the coating inner layers 2, the coating middle layers 3 and the coating outer layers 4 account for 1-5%, 1-5% and 1-3% of total weight of the fertilizer, respectively, wherein unsaturated polyester is made by subjecting PET wastes, diol, a catalyst and an active diluent as raw materials to reactions such as alcoholysis, esterification and co-condensation.The controlled-release fertilizer with different release periods of time can be prepared by adjusting a coating ratio, the PET wastes are resourcefully reused, waste is turned into wealth, environmental pollution is reduced, and the production cost of the coated controlled-release fertilizer is greatly reduced.
Description
Technical field
The invention belongs to sustained-controll-release fertiliser technical field, relate to a kind of unsaturated polyester (UP) film-coated controlled release fertilizer and preparation method thereof, it is more particularly related to the unsaturated polyester (UP) film-coated controlled release fertilizer prepared of a kind of PET of utilization waste material and method thereof.
Background technology
Chemical fertilizer is one of requisite Support Resource of modern agriculture, and utilization rate of fertilizer is low, and the substitute products of chemical fertilizer are relative with development of new fertilizers backward, directly result in the wasting of resources and environmental pollution.According to country's strategic plan about agricultural development " turn mode, adjust structure ", it is intended to base oneself upon the current fertilizer and pesticide of China and subtracts the Strategic Demand executing potentiation, to the year two thousand twenty, Project Areas utilization rate of nitrogen fertilizer is brought up to 43% by 33%, phosphate fertilizer utilization efficiency is brought up to 34% by 24%, fertilizer nitrogen phosphorus subtracts executes 20%, and crops on average increase production 3%, it is achieved crop production upgrading, abridged edition, potentiation.
Film-coated controlled release fertilizer is with granulated fertilizer for core, the inorganic substances of one layer of low aqueous solubility of surface-coated or microsolubility or organic polymer, change the stripping property of fertilizer nutrient, extend or control fertilizer nutrient release, make the supply of soil nutrient need fertilizer to require the new-type fertilizer coordinated with crop.Film-coated controlled release fertilizer type mainly has high polymer film-coated fertilizer and the big class of inorganic matter coated fertilizer two both at home and abroad at present.The coated fertilizer that inorganic matter coated fertilizer adopts is mainly sulfur, but there is hole, crack due on the peplos that sulfur makes, rate of release and the release time that can make the fertilizer nutrient in film accelerate, and sulfur is oxidizable in atmosphere, the peplos causing fertilizer surface comes off or broken, loses the controlled-release function of peplos.In the release and release control fertilizer of polymer capsule, there are again thermoplasticity and the two kinds of film-coated controlled release fertilizer of thermosetting resin.Such as, Authorization Notice No. a kind of production method reclaiming thermoplastic resin and thermosetting resin multi-layer composite coated controlled-release fertilizer that has been the patent disclosure of CN100567222C, this invention is first by the thermoplastic resin reclaimed and mineral powder, grain dust is miscible in the mixed solvent of acetic acid butyl ester and pentyl acetate, ebuillition of heated fluid bed spray on fertiliser granulates through two-fluid spray nozzle, form the thermoplastic resin film with nutrient control-release function, transfer it in heating drum fluid bed, the mixed liquor of gradation spraying thermosetting resin and firming agent and diluent, under rotating heating condition, outer layer generation fast setting at thermoplastic resin film reacts, form densification, the thermosetting resin film of light, the advantage that this product is integrated with two resin films, achieve toughness and elastic perfect adaptation.But the film-coated controlled release fertilizer cost that this patent system obtains is high, and still have employed low toxicity organic solvent in preparation process, the difficulty of marketing application is bigger.Additionally, prior art also discloses unsaturated polyester resin film-coated controlled release fertilizer, such as, the patent application that publication number is CN103044169A discloses a kind of release and release control fertilizer with unsaturated polyester resin peplos and production method thereof, epoxy resin integument liquid added or sprays on urea granules surface, after film-forming, forming priming coat.Again by the gradation gradually of unsaturated polyester resin coating liquid add or coat on the priming coat of granulated fertilizer, after film-forming unsaturated polyester resin film-coated controlled release fertilizer.Although the method is solvent-free, it is simple to prepare, nutrients release performance fine, but the epoxy resin of costliness makes its extensive use be subject to a definite limitation.Publication number is the preparation method that the patent application of CN103951503A discloses a kind of film-coated controlled release fertilizer, it is that polyisocyanates and polyhydric alcohol are mixed in proportion, with acetone for dissolving water generation reaction polyurethane, add Oleum Terebinthinae, polyvinyl alcohol reaction generates coating liquid, prepare coating controlled-release fertilizer, but the process employs low toxicity organic solvent, easily cause Soil Environmental Pollution.
The problems such as in sum, at present both at home and abroad film-coated controlled release fertilizer exists cost height, has solvent, complex process, most release and release control fertilizer to adopt homogenous materials and single mode to carry out peplos, and coated fertilizer is not degradable or controlled-release effect is not ideal enough.And owing to current organic polymer price is high, pure to carry out the filmcoated controlled release fertilizer price of peplos production by low molecule Material synthesis organic polymer higher, it is difficult to wide popularization and application.Therefore, need badly and develop a kind of low cost, solvent-free, technique simple, is suitable for film-coated controlled release fertilizer and the production technology thereof of large-scale production.Along with polyester industrial is fast-developing, according to statistics, in production of polyester with the course of processing, there are about 3%～5% will become waste material, pet waste output, is big simultaneously, light weight, takes up space big, such as irrational recycling, not only cause the huge wasting of resources, and serious environmental pollution will be produced.And PET waste material is carried out recycling, the research of the film-coated controlled release fertilizer producing excellent performance at home and abroad but rarely has report.
Summary of the invention
It is an object of the invention to provide unsaturated polyester (UP) film-coated controlled release fertilizer and method thereof prepared by a kind of PET of utilization waste material.
In order to realize first purpose of the present invention, the present invention adopts the following technical scheme that:
Unsaturated polyester (UP) film-coated controlled release fertilizer prepared by a kind of PET of utilization waste material, described release and release control fertilizer is made up of the unsaturated polyester (UP) peplos internal layer 2 on granulated fertilizer 1 and granulated fertilizer 1 surface, the unsaturated polyester (UP) peplos intermediate layer 3 on peplos internal layer 2 surface and the unsaturated polyester (UP) peplos outer layer 4 on surface, peplos intermediate layer 3, described peplos internal layer 2, peplos intermediate layer 3, peplos outer layer 4 weight account for the 1～5% of fertilizer gross weight, 1～5%, 1～3% respectively；Described peplos internal layer 2 by unsaturated polyester (UP), photosensitizer, assistant crosslinking agent A in mass ratio after ratio mix homogeneously for 100:2～5:0.5～1.5 coating liquid made formed through photocuring after being sprayed at granulated fertilizer 1 surface；Described peplos intermediate layer 3 by unsaturated polyester (UP), oxidant, reducing agent, assistant crosslinking agent B in mass ratio after ratio mix homogeneously for 100:1～5:1～3:0.1～0.15 coating liquid made formed through heat cure after being sprayed at peplos internal layer 2 surface；Described peplos outer layer 4 is solidify to form after the PUR made after the ratio mix homogeneously of 10～20:3～10:1～2:1～3:5～15 is sprayed at peplos intermediate layer 3 by unsaturated polyester resin, viscosifier, plasticizer, firming agent, diluent in mass ratio, wherein, described unsaturated polyester (UP) is to be Material synthesis by PET waste material, dihydroxylic alcohols, catalyst, reactive diluent.
Further, the unsaturated polyester (UP) described in technique scheme is adopted and is prepared from the following method, comprises the steps:
(1) by PET waste material, dihydroxylic alcohols, catalyst puts into equipped with thermometer, motor stirrer, in the reactor of nitrogen ingress pipe and fractionating device, it is heated to 190～210 DEG C and carries out alcoholysis, the alcoholysis time is 1～3.5 hour, treat that PET all dissolves, after particle, acid number in detection reaction system, reaction is terminated when acid number is down to 30mgKOH/g, obtain the monomer of PET alcoholysis product p-phthalic acid dihydroxylic alcohols, dimer and tetrameric mixture, wherein, the mass ratio of described PET waste material and dihydroxylic alcohols is 1～2:0.2～2.2, described catalyst amount accounts for the 0.1～2% of PET waste material quality；
(2) after PET alcoholysis reaction terminates, still temperature drop is low to moderate 140～160 DEG C, put into binary acid, then 155 DEG C progressively it are warming up to, it is incubated half an hour, then heating to 190～200 DEG C and carry out esterification 2～3 hours, wherein, the mass ratio of the addition of described binary acid and PET waste material is 0.2～3:l～2；
(3) still temperature drop is low to moderate 100 DEG C, reactive diluent is added in reactor, it is sufficiently stirred for the esterification products making step (2) prepare and carries out polycondensation reaction with reactive diluent is miscible, controlling setting-up point is 190～220 DEG C, response time is 1～2.5 hour, then cooling, filtration, prepares described unsaturated polyester (UP), wherein, described reactive diluent is 30～75:100 with the mass ratio of PET waste material.
Further, the dihydroxylic alcohols described in technique scheme is any one or several in ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and heptandiol.
Further, the catalyst described in technique scheme is any one or several in zinc acetate, butyl titanate, manganese acetate, manganese phosphate, calcium phosphate, aluminium isopropoxide, alkali metal and oxide thereof and hydroxide, sodium silicate and lead oxide.
Further, binary acid described in technique scheme is any one or several in p-phthalic acid, M-phthalic acid, phthalic anhydride, maleic acid, maleic anhydride, fumaric acid, glutaconate, glutaconic anhydride, 2,4-pentadienoic acids.
Further, reactive diluent described in technique scheme be acrylic acid methyl ester., propylene, butyl acrylate, styrene, methyl methacrylate, hydroxyethyl methylacrylate, 2-phenoxyethyl acrylate, phenoxyethyl acrylate, 1, any one or several in 6-hexanediyl ester, ethoxyquin 1,6-hexanediyl ester, propylene glycol diacrylate, tripropylene glycol diacrylate, polyethyleneglycol diacrylate, neopentylglycol diacrylate.
Further, photosensitizer described in technique scheme be Benzoinum, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin dimethylether, benzophenone, diphenylethan, 4-methyl benzophenone, 4-chlorobenzophenone, 4-phenyl benzophenone, 2, any one or several in 4-dihydroxy benaophenonel, 1-hydroxycyclohexyl phenyl ketone, 4,4'-double; two (dimethylamino) benzophenone.
Further, the assistant crosslinking agent A described in technique scheme is any one or two kinds of in stannous chloride or stannous octoate.
Further, the oxidant described in technique scheme is peroxidating Methanamide, methylethyl ketone peroxide, any one or several in methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, t-butyl perbenzoate.
Further, the reducing agent described in technique scheme is any one or several in cobalt naphthenate, isooctyl acid vanadium plumbous, sad, N, N-bis-(2-ethoxy) para-totuidine, N, N-dimethyl-p-toluidine, DMA.
Further, the assistant crosslinking agent B described in technique scheme is any one or several in stannous octoate, trientine, glutaraldehyde.
Further, the viscosifier described in technique scheme are any one in rosin resin, Petropols, phenolic resin, epoxy resin.
Further, the plasticizer described in technique scheme is dicyclohexyl phthalate (DCHP).
Further, the firming agent described in technique scheme is Isocyanate prepolymers body.
Further, the diluent described in technique scheme is any one or two kinds of in wax class, low molecular weight polycaprolactone alkene.
The a further object of the present invention is in that to provide the described above method utilizing PET waste material to prepare unsaturated polyester (UP) film-coated controlled release fertilizer, and described method comprises the steps:
(1) unsaturated polyester (UP) is utilized to carry out photocuring peplos: to add photosensitizer in unsaturated polyester resin, it is simultaneously introduced assistant crosslinking agent, coating liquid 1 is made after mix homogeneously, the granulated fertilizer 1 that particle diameter is 2～5mm is placed in disk and is preheated to 50～60 DEG C, described coating liquid 1 is pressed 1～5% showering of fertilizer gross weight to granulated fertilizer 1 surface rotated, be 20mW/cm in range of light intensity2～50mW/cm2When, irradiates 15 seconds～5 minutes, namely forms unsaturated polyester (UP) peplos internal layer 2 on granulated fertilizer 1 surface, unsaturated polyester (UP) in described coating liquid 1, photosensitizer, assistant crosslinking agent A mass ratio be 100:2～5:0.5～1.5；
(2) unsaturated polyester (UP) is utilized to carry out heat cure peplos: the fertilizer after photocuring peplos will be carried out, logical 50～60 DEG C of hot blasts in disk, it is sequentially added into oxidant in the unsaturated polyester resins of 15～35 DEG C, reducing agent, assistant crosslinking agent B, coating liquid 2 is made after mix homogeneously, described coating liquid 2 is pressed 1～5% showering surface to unsaturated polyester (UP) peplos internal layer 2 of fertilizer gross weight, solidify 1～10 minute, take out from disk, namely form unsaturated polyester (UP) peplos intermediate layer 3 on the surface of peplos internal layer 2 after cooling, unsaturated polyester (UP) in described coating liquid 2, oxidant, reducing agent, the mass ratio of assistant crosslinking agent B is 100:1～5:1～3:0.1～0.15；
(3) utilize unsaturated polyester resin to prepare PUR and carry out peplos: by unsaturated polyester resin, viscosifier, plasticizer, firming agent, diluent be in mass ratio 10～20:3～10:1～2:1～3:5～15 ratio mix homogeneously after make PUR, surface in step (2) is formed the fertilizer in unsaturated polyester (UP) peplos intermediate layer 3, logical 50～60 DEG C of hot blasts in disk, described PUR is pressed 1～3% showering of fertilizer gross weight to the surface in unsaturated polyester (UP) peplos intermediate layer 3 in disk, solidify 3～10 minutes, namely formed tough and tensile on the surface in peplos intermediate layer 3, the unsaturated polyester (UP) peplos outer layer 4 of smooth densification, the fertiliser granulates of film-forming is taken out from disk, cooling, namely described unsaturated polyester (UP) film-coated controlled release fertilizer is obtained.
The method of the described above unsaturated polyester (UP) film-coated controlled release fertilizer utilizing PET waste material to prepare, identical described in described unsaturated polyester (UP), photosensitizer, assistant crosslinking agent A, oxidant, reducing agent, assistant crosslinking agent B, viscosifier, plasticizer, firming agent, first purpose of diluent and the present invention.
Compared with prior art, the present invention has following beneficial effect:
1, the waste PET plastics of recovery are carried out resource recycling by the present invention, turn waste into wealth, decrease environmental pollution, make the production cost of the film-coated controlled release fertilizer of the application reduce simultaneously, cheap, wide market；
2, to prepare the whole process time of film-coated controlled release fertilizer short, simple to operation for the present invention；
3, the present invention can pass through to adjust different proportional spreading rates, and preparation possesses the sustained-controll-release fertiliser of different release time.
Detailed description of the invention
Present invention following example illustrate the technical characteristics of the present invention and the process advantage of the present invention, but the present invention is not limited in following embodiment, under the scope of objective belonging to front and back, the present invention also has various changes and modifications, and change is included in the technical scope of the present invention.Application claims needs scope of protection to be defined by appending claims and its equivalent.
Following each embodiment acid number (AV) in preparing unsaturated polyester resin process is adopted and is measured with the following method:
Accurately weighing appropriate amount of sample, pipette 15ml benzyl alcohol, 60 DEG C of water-bath backflows are dissolved, and cooling adds 3 bromothymol blues and 3 cresol red indicators, adds 10ml alcoholic solution, be titrated to terminal with potassium hydroxide/alcoholic solution, and do blank experiment.
In formula: V0、V1The respectively titration milliliter number of blank sample and sample；
The molar concentration that [M] is potassium hydroxide, W is sample weight.
Embodiment 1
The unsaturated polyester (UP) of the present embodiment is adopted and is prepared from the following method, comprises the steps:
(1) 1000gPET waste material, 200g ethylene glycol, 1g zinc acetate catalyst are put in the reactor equipped with thermometer, motor stirrer, nitrogen ingress pipe and fractionating device, it is heated to 200 DEG C and carries out alcoholysis, the alcoholysis time is 2 hours, all dissolve until PET, without after particle, acid number in detection reaction system, terminate reaction when acid number is down to 30mgKOH/g, obtain the monomer of PET alcoholysis product p-phthalic acid dihydroxylic alcohols, dimer and tetrameric mixture；
(2) after PET alcoholysis reaction terminates, still temperature drop is low to moderate 150 DEG C, puts into 550g M-phthalic acid, be then progressively warming up to 155 DEG C, be incubated half an hour, then heat to 200 DEG C and carry out esterification 2.5 hours.
(3) still temperature drop is low to moderate 100 DEG C, reactive diluent styrene 600g is added in reactor, it is sufficiently stirred for the esterification products making step (2) prepare and carries out polycondensation reaction with reactive diluent is miscible, controlling setting-up point is 200 DEG C, response time is 2 hours, then cooling, filtration, prepare described unsaturated polyester (UP).
The method of unsaturated polyester (UP) film-coated controlled release fertilizer prepared by a kind of PET of utilization waste material of the present embodiment, described method comprises the steps:
(1) unsaturated polyester (UP) is utilized to carry out photocuring peplos: to add 3g photosensitizer Benzoinum in above-mentioned prepared unsaturated polyester resin, it is simultaneously introduced 0.75g assistant crosslinking agent A stannous chloride, coating liquid 1 is made after mix homogeneously, the granulated fertilizer 1 that 3000g particle diameter is 2～5mm is placed in disk and is preheated to 50～60 DEG C, in the way of showering, described coating liquid 1 is applied in the ratio of fertilizer gross weight 2% granulated fertilizer 1 surface of rotation, is 20mW/cm in light intensity2～50mW/cm2When, irradiates 15 seconds～5 minutes, namely forms unsaturated polyester (UP) peplos internal layer 2 on granulated fertilizer 1 surface；
(2) unsaturated polyester (UP) is utilized to carry out heat cure peplos: the fertilizer after photocuring peplos will be carried out, logical 50～60 DEG C of hot blasts in disk, the oxidant peroxidating Methanamide of 1.5g it is sequentially added in the unsaturated polyester resins of 15～35 DEG C, the reducing agent dimethylaniline of 1.5g, 0.15g assistant crosslinking agent B stannous octoate, coating liquid 2 is made after mix homogeneously, by described coating liquid 2 in the 2% of fertilizer gross weight ratio showering to the surface of unsaturated polyester (UP) peplos internal layer 2, solidify 1～10 minute, take out from disk, namely form unsaturated polyester (UP) peplos intermediate layer 3 on the surface of peplos internal layer 2 after cooling；
null(3) utilize unsaturated polyester resin to prepare PUR and carry out peplos: by unsaturated polyester resin、Viscosifier rosin resin、Plasticizer phthalic acid dicyclohexyl maleate (DCHP)、Firming agent Isocyanate prepolymers body diluent microwax is in mass ratio for making PUR after the ratio mix homogeneously of 10:5:1:1.5:5，Surface in step (2) is formed the fertilizer in unsaturated polyester (UP) peplos intermediate layer 3，Logical 50～60 DEG C of hot blasts in disk，By described PUR in the 1% of fertilizer gross weight ratio showering to the surface in unsaturated polyester (UP) peplos intermediate layer 3 in disk，Solidify 3～10 minutes，Namely formed tough and tensile on the surface in peplos intermediate layer 3、The unsaturated polyester (UP) peplos outer layer 4 of smooth densification，The fertiliser granulates of film-forming is taken out from disk、Cooling，Namely described unsaturated polyester (UP) film-coated controlled release fertilizer is obtained.
Embodiment 2
The unsaturated polyester (UP) of the present embodiment and the preparation method of unsaturated polyester (UP) film-coated controlled release fertilizer are identical with embodiment 1, the total coating quantity differing only in the present embodiment is 7%, and namely coating liquid 1, coating liquid 2, PUR account for the ratio of fertilizer gross weight respectively 3%, 3%, 1%.
Embodiment 3
The unsaturated polyester (UP) of the present embodiment and the preparation method of unsaturated polyester (UP) film-coated controlled release fertilizer are identical with embodiment 1, the total coating quantity differing only in the present embodiment is 8%, and namely coating liquid 1, coating liquid 2, PUR account for the ratio of fertilizer gross weight respectively 3%, 3%, 2%.
Embodiment 4
The unsaturated polyester (UP) of the present embodiment and the preparation method of unsaturated polyester (UP) film-coated controlled release fertilizer are identical with embodiment 1, the total coating quantity differing only in the present embodiment is 9%, and namely coating liquid 1, coating liquid 2, PUR account for the ratio of fertilizer gross weight respectively 4%, 4%, 1%.
Embodiment 5
The unsaturated polyester (UP) of the present embodiment and the preparation method of unsaturated polyester (UP) film-coated controlled release fertilizer are identical with embodiment 1, the total coating quantity differing only in the present embodiment is 10%, and namely coating liquid 1, coating liquid 2, PUR account for the ratio of fertilizer gross weight respectively 4%, 4%, 2%.
Embodiment 6
The unsaturated polyester (UP) of the present embodiment is adopted and is prepared from the following method, comprises the steps:
(1) 1000gPET waste material, 200g propylene glycol, 1.2g manganese acetate catalyst are put in the reactor equipped with thermometer, motor stirrer, nitrogen ingress pipe and fractionating device, it is heated to 200 DEG C and carries out alcoholysis, the alcoholysis time is 2 hours 30 minutes, all dissolve until PET, without after particle, acid number in detection reaction system, terminate reaction when acid number drops to 30mgKOH/g, obtain the monomer of PET alcoholysis product p-phthalic acid dihydroxylic alcohols, dimer and tetrameric mixture；
(2) after PET alcoholysis reaction terminates, still temperature drop is low to moderate 150 DEG C, puts into 450g p-phthalic acid, be then progressively warming up to 155 DEG C, be incubated half an hour, then heat to 200 DEG C and carry out esterification 2 hours 30 minutes.
(3) still temperature drop is low to moderate 100 DEG C, reactive diluent acrylic acid methyl ester. 500g is added in reactor, it is sufficiently stirred for the esterification products making step (2) prepare and carries out polycondensation reaction with reactive diluent is miscible, controlling setting-up point is 200 DEG C, response time is 2 hours, then cooling, filtration, prepare described unsaturated polyester (UP).
The method of unsaturated polyester (UP) film-coated controlled release fertilizer prepared by a kind of PET of utilization waste material of the present embodiment, described method comprises the steps:
(1) unsaturated polyester (UP) is utilized to carry out photocuring peplos: to add 2g photosensitizer benzoin ethyl ether in above-mentioned prepared unsaturated polyester resin, it is simultaneously introduced 0.5g assistant crosslinking agent stannous octoate, coating liquid 1 is made after mix homogeneously, the granulated fertilizer 1 that 3000g particle diameter is 2～5mm is placed in disk and is preheated to 50～60 DEG C, by described coating liquid 1 in the ratio showering of fertilizer gross weight 4% to granulated fertilizer 1 surface rotated, it is 20mW/cm in range of light intensity2～50mW/cm2When, irradiates 15 seconds～5 minutes, namely forms unsaturated polyester (UP) peplos internal layer 2 on granulated fertilizer 1 surface；
(2) unsaturated polyester (UP) is utilized to carry out heat cure peplos: the fertilizer after photocuring peplos will be carried out, logical 50～60 DEG C of hot blasts in disk, 1.2g oxidant cyclohexanone peroxide it is sequentially added in the 100g unsaturated polyester resin of 15～35 DEG C, the reducing agent cobalt naphthenate of 1.2g, 0.1g assistant crosslinking agent B stannous octoate, coating liquid 2 is made after mix homogeneously, by described coating liquid 2 in the 4% of fertilizer gross weight ratio showering to the surface of unsaturated polyester (UP) peplos internal layer 2, solidify 1～10 minute, take out from disk, namely form unsaturated polyester (UP) peplos intermediate layer 3 on the surface of peplos internal layer 2 after cooling；
null(3) utilize unsaturated polyester resin to prepare PUR and carry out peplos: by unsaturated polyester (UP)、Viscosifier epoxy resin、Plasticizer phthalic acid dicyclohexyl maleate (DCHP)、Firming agent Isocyanate prepolymers body、Diluent polyethylene is in mass ratio for making PUR after the ratio mix homogeneously of 10:3:1:1:5，Surface in step (2) is formed the fertilizer in unsaturated polyester (UP) peplos intermediate layer 3，Logical 50～60 DEG C of hot blasts in disk，By described PUR in the 3% of fertilizer gross weight ratio showering to the surface in unsaturated polyester (UP) peplos intermediate layer 3 in disk，Solidify 3～10 minutes，Namely formed tough and tensile on the surface in peplos intermediate layer 3、The unsaturated polyester (UP) peplos outer layer 4 of smooth densification，The fertiliser granulates of film-forming is taken out from disk、Cooling，Namely described unsaturated polyester (UP) film-coated controlled release fertilizer is obtained.
Being filled in the soil of 20CM by 5% (2%-2%-1%) film-coated controlled release fertilizer 50g that embodiment 1 prepares, measure degradation rate, average every month degrades 2～3%.
Being immersed in 25 DEG C of water by the film-coated controlled release fertilizer that above-described embodiment 1～6 prepares, because different coating rate nutrients controls 2～7 months release time, concrete outcome is shown in table 1 below.
The film-coated controlled release fertilizer that table 1 embodiment 1～6 prepares performance parameter table in 25 DEG C of water
As it can be seen from table 1 along with the increase of coating quantity, the time of nutrients release is also more and more longer, the time of nutrients release is also had a significant effect by trilamellar membrane peplos ratio simultaneously.
Claims (10)
1. the unsaturated polyester (UP) film-coated controlled release fertilizer utilizing PET waste material to prepare, it is characterized in that: described release and release control fertilizer is made up of the unsaturated polyester (UP) peplos internal layer 2 on granulated fertilizer 1 and granulated fertilizer 1 surface, the unsaturated polyester (UP) peplos intermediate layer 3 on peplos internal layer 2 surface and the unsaturated polyester (UP) peplos outer layer 4 on surface, peplos intermediate layer 3, described peplos internal layer 2, peplos intermediate layer 3, peplos outer layer 4 weight account for the 1～5% of fertilizer gross weight, 1～5%, 1～3% respectively；Described peplos internal layer 2 by unsaturated polyester (UP), photosensitizer, assistant crosslinking agent A in mass ratio after ratio mix homogeneously for 100:2～5:0.5～1.5 coating liquid made formed through photocuring after being sprayed at granulated fertilizer 1 surface；Described peplos intermediate layer 3 by unsaturated polyester (UP), oxidant, reducing agent, assistant crosslinking agent B in mass ratio after ratio mix homogeneously for 100:1～5:1～3:0.1～0.15 coating liquid made formed through heat cure after being sprayed at peplos internal layer 2 surface；Described peplos outer layer 4 is solidify to form after the PUR made after the ratio mix homogeneously of 10～20:3～10:1～2:1～3:5～15 is sprayed at peplos intermediate layer 3 by unsaturated polyester resin, viscosifier, plasticizer, firming agent, diluent in mass ratio, wherein, described unsaturated polyester (UP) is to be Material synthesis by PET waste material, dihydroxylic alcohols, catalyst, reactive diluent.
2. the unsaturated polyester (UP) film-coated controlled release fertilizer that prepared by a kind of PET of utilization waste material according to claim 1, it is characterised in that: described unsaturated polyester (UP) is adopted and is prepared from the following method, comprises the steps:
(1) by PET waste material, dihydroxylic alcohols, catalyst puts into equipped with thermometer, motor stirrer, in the reactor of nitrogen ingress pipe and fractionating device, it is heated to 190～210 DEG C and carries out alcoholysis, the alcoholysis time is 1～3.5 hour, treat that PET all dissolves, after particle, acid number in detection reaction system, reaction is terminated when acid number is down to 30mgKOH/g, obtain the monomer of PET alcoholysis product p-phthalic acid dihydroxylic alcohols, dimer and tetrameric mixture, wherein, the mass ratio of described PET waste material and dihydroxylic alcohols is 1～2:0.2～2.2, described catalyst amount accounts for the 0.1～2% of PET waste material quality；
(2) after PET alcoholysis reaction terminates, still temperature drop is low to moderate 140～160 DEG C, put into binary acid, then 155 DEG C progressively it are warming up to, it is incubated half an hour, then heating to 190～200 DEG C and carry out esterification 2～3 hours, wherein, the mass ratio of the addition of described binary acid and PET waste material is 0.2～3:l～2；
(3) still temperature drop is low to moderate 100 DEG C, reactive diluent is added in reactor, it is sufficiently stirred for the esterification products making step (2) prepare and carries out polycondensation reaction with reactive diluent is miscible, controlling setting-up point is 190～220 DEG C, response time is 1～2.5 hour, then cooling, filtration, prepares described unsaturated polyester (UP), wherein, described reactive diluent is 30～75:100 with the mass ratio of PET waste material.
3. the unsaturated polyester (UP) film-coated controlled release fertilizer that prepared by a kind of PET of utilization waste material according to claim 2, it is characterised in that: dihydroxylic alcohols is any one or several in ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and heptandiol.
4. the unsaturated polyester (UP) film-coated controlled release fertilizer that prepared by a kind of PET of utilization waste material according to claim 2, it is characterised in that: described catalyst is any one or several in zinc acetate, butyl titanate, manganese acetate, manganese phosphate, calcium phosphate, aluminium isopropoxide, alkali metal and oxide thereof and hydroxide, sodium silicate and lead oxide.
5. the unsaturated polyester (UP) film-coated controlled release fertilizer that prepared by a kind of PET of utilization waste material according to claim 2, it is characterized in that: described binary acid is any one or several in p-phthalic acid, M-phthalic acid, phthalic anhydride, maleic acid, maleic anhydride, fumaric acid, glutaconate, glutaconic anhydride, 2,4-pentadienoic acids.
6. the unsaturated polyester (UP) film-coated controlled release fertilizer that prepared by a kind of PET of utilization waste material according to claim 2, it is characterized in that: described reactive diluent is acrylic acid methyl ester., propylene, butyl acrylate, styrene, methyl methacrylate, hydroxyethyl methylacrylate, 2-phenoxyethyl acrylate, phenoxyethyl acrylate, 1, 6-hexanediyl ester, ethoxyquin 1, 6-hexanediyl ester, propylene glycol diacrylate, tripropylene glycol diacrylate, polyethyleneglycol diacrylate, any one or several in neopentylglycol diacrylate.
7. the unsaturated polyester (UP) film-coated controlled release fertilizer that prepared by a kind of PET of utilization waste material according to claim 1, it is characterised in that: described assistant crosslinking agent A is any one or two kinds of in stannous chloride or stannous octoate.
8. the unsaturated polyester (UP) film-coated controlled release fertilizer that prepared by a kind of PET of utilization waste material according to claim 1, it is characterised in that: described assistant crosslinking agent B is any one or several in stannous octoate, trientine, glutaraldehyde.
9. one kind utilizes the method that PET waste material prepares unsaturated polyester (UP) film-coated controlled release fertilizer, it is characterised in that: described method comprises the steps:
(1) unsaturated polyester (UP) is utilized to carry out photocuring peplos: to add photosensitizer in unsaturated polyester resin, it is simultaneously introduced assistant crosslinking agent, coating liquid 1 is made after mix homogeneously, the granulated fertilizer 1 that particle diameter is 2～5mm is placed in disk and is preheated to 50～60 DEG C, described coating liquid 1 is pressed 1～5% showering of fertilizer gross weight to granulated fertilizer 1 surface rotated, be 20mW/cm in range of light intensity2～50mW/cm2When, irradiates 15 seconds～5 minutes, namely forms unsaturated polyester (UP) peplos internal layer 2 on granulated fertilizer 1 surface, unsaturated polyester (UP) in described coating liquid 1, photosensitizer, assistant crosslinking agent A mass ratio be 100:2～5:0.5～1.5；
(2) unsaturated polyester (UP) is utilized to carry out heat cure peplos: the fertilizer after photocuring peplos will be carried out, logical 50～60 DEG C of hot blasts in disk, it is sequentially added into oxidant in the unsaturated polyester resins of 15～35 DEG C, reducing agent, assistant crosslinking agent B, coating liquid 2 is made after mix homogeneously, described coating liquid 2 is pressed 1～5% showering surface to unsaturated polyester (UP) peplos internal layer 2 of fertilizer gross weight, solidify 1～10 minute, take out from disk, namely form unsaturated polyester (UP) peplos intermediate layer 3 on the surface of peplos internal layer 2 after cooling, unsaturated polyester (UP) in described coating liquid 2, oxidant, reducing agent, the mass ratio of assistant crosslinking agent B is 100:1～5:1～3:0.1～0.15；
(3) utilize unsaturated polyester resin to prepare PUR and carry out peplos: by unsaturated polyester resin, viscosifier, plasticizer, firming agent, diluent be in mass ratio 10～20:3～10:1～2:1～3:5～15 ratio mix homogeneously after make PUR, surface in step (2) is formed the fertilizer in unsaturated polyester (UP) peplos intermediate layer 3, logical 50～60 DEG C of hot blasts in disk, described PUR is pressed 1～3% showering of fertilizer gross weight to the surface in unsaturated polyester (UP) peplos intermediate layer 3 in disk, solidify 3～10 minutes, namely formed tough and tensile on the surface in peplos intermediate layer 3, the unsaturated polyester (UP) peplos outer layer 4 of smooth densification, the fertiliser granulates of film-forming is taken out from disk, cooling, namely described unsaturated polyester (UP) film-coated controlled release fertilizer is obtained.
10. the method that a kind of PET of utilization waste material according to claim 9 prepares unsaturated polyester (UP) film-coated controlled release fertilizer, it is characterised in that: described firming agent is Isocyanate prepolymers body.
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