CN103421161A - Polyurethane enveloped fertilizer and enveloping material thereof - Google Patents
Polyurethane enveloped fertilizer and enveloping material thereof Download PDFInfo
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- CN103421161A CN103421161A CN201310342033XA CN201310342033A CN103421161A CN 103421161 A CN103421161 A CN 103421161A CN 201310342033X A CN201310342033X A CN 201310342033XA CN 201310342033 A CN201310342033 A CN 201310342033A CN 103421161 A CN103421161 A CN 103421161A
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Abstract
The invention relates to a polyurethane enveloped material which comprises polyether polyatomic alcohol and isocyanate, wherein the hydroxyl value of the polyether polyatomic alcohol ranges from 100 to 415 mgKOH/g; the molecular weight of the polyether polyatomic alcohol ranges form 400 to 1700; the degree of functionality of the polyether polyatomic alcohol ranges from 2 to 4. Preferably, the polyurethane enveloped material further comprises foaming agent. Compared with the conventional enveloped reactants, the polyurethane enveloped material has the advantages that the molecular weight of reactants is low; the reaction speed is high; the degree of functionality of the polyether polyatomic alcohol is high; the intensity and ductility of the prepared polyurethane product are good; due to mixing of different types of polyatomic alcohol, the molecular chain of the polyurethane has different soft sections and hard sections, so as to improve the intensity and the ductility; the problem that as the adjustability of animal and vegetable oil based polyatomic alcohol is poor during polyurethane reaction process, requirements of production and use cannot be met is solved.
Description
Technical field
The present invention relates to the release and release control fertilizer field, particularly, the present invention relates to a kind of polyurethane coated fertilizer and coated fertilizer thereof.
Background technology
Boller and Graver utilize polyvalent alcohol and binary of fatty acids or epoxy resin can polymerization reaction take place to form the mechanism of high molecular polymer in 1961, using the fertiliser granulates surface as reaction interface, successfully synthesized polyurethane coated controlled-release fertilizer (US3218274, US3276857) on this interface.As the beginning, Hansen has also applied for similar two patents (US3223518, US3259482), nineteen sixty-five in 1961, has described technology how to utilize polyol and isocyanate polymerization reaction take place to prepare release and release control fertilizer.Polyurethane reaction thing selectable range is very wide, and product property and purposes be the difference great disparity also, so the selection of polyurethane coated material is the invention emphasis of this area always.
Moor in 1987 utilize water miscible containing amino fertilizer as core, utilize amino nucleation and the reaction of some compounds containing electrophilic group to give birth to and form the polymer capsule layer, invented " wear-resisting release and release control fertilizer " (US4804403), the Blank of Israel in 1988 is used some high viscosity unsaturated oil and low viscosity unsaturated oil (oleum lini, sunflower oil, synourin oil and soybean wet goods), under the effect of catalyzer 2-ethyl group-isocaproic acid metal-salt, at 160～180 ℃ of temperature, react handing-over film forming (US4880455) with rolling disc equipment.Describe Dicyclopentadiene (DCPD) in the people such as the Goertz patent of 1998 and produced the method (US6039781) of coated with resin fertilizer with some Synolac (such as oleum lini, soybean oil) polymerization film formation.Within 2000, the people such as Geiger utilize the amino of polyvalent alcohol in fertilizer to be combined, then use isocyanate and polyol reaction film forming, finally be surrounded by again machine wax, such method reduces the production cost of coated fertilizer, make the extensive application of coated fertilizer become possibility, this patent is all by Agrium, and the said firm develops
It is (US6663686) product that uses this technology to produce.Thereafter, application obtain the authorization various vegetalitas and animal raw fat as the patent of reaction raw materials (CN101323545A).These patents are included nearly all this biological grease utilized by human development, and all isocyanic ester that can synthesize, and the invention that the of animal or plant nature grease of so far usining prepares polyurethane coated fertilizer as reactant is terminated.At home, the patent that the Viscotrol C of take is made polyurethane coated fertilizer as the main body reactant is authorized (CN101006032A also, CN101648837A), using application that various polyurethane reaction materials prepare coated fertilizer as proprietary material also authorized (CN101323545A).
Polyvalent alcohol for polyurethane coated reaction is mainly vegetable and animals oils lipid polyvalent alcohol and part polyester polyol at present, for the isocyanic ester reacted, is mainly Toluene-2,4-diisocyanate, 4-vulcabond (TDI) and diphenylmethanediisocyanate (MDI).There are following shortcomings in these reactants:
(1) take animal-plant oil as basic material, it is a lot of that hydrogenation is prepared into the research of biopolyol, but be mainly Viscotrol C on market, soybean oil and palmitic hydrogenation product, and other equal difficult volume production, do not become stable bio-based polyhydric raw polyol.For this reason, in actually operating, be nearly all to adopt hydrogenated castor oil as the polyvalent alcohol raw material, actual available reaction raw materials is very limited.
(2) the most coating process is all to launch around the polyurethane based on castor oil reaction, and polyurethane product structure properties modification scope is very limited, can not improve the coated fertilizer controlled release properties by controlling reactant.
(3) the Viscotrol C hydroxyl value is certain, and its speed of response is also more fixing, and the structure properties of polymerisate is difficult to change, so adhesion problems is difficult to solve, and coating process also is restricted.
(4) isocyanic ester used in current patent is mainly TDI and MDI, and the former toxicity is larger, under latter's normal temperature, is that solid and chemical property easily change, use inconvenient, but the consideration speed of response, mainly used MDI, this makes the adding technology of MDI very complicated.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of polyurethane coated material.This coated fertilizer can be used for preparing polyurethane coated fertilizer, reaction fast, but serialization coating, its polyurethane chemistry response characteristic adapts to the continuous fluidized bed encapsulation tool, the reaction controllability is strong, the rete of prepared coated fertilizer has certain intensity and snappiness, release performance is good, solved the vegetable oil polyol speed of response slower, the problem that causes the easy adhesion of coating process, solve the problem that the vegetable oil-based polyols quality is difficult to regulate and control the coated fertilizer quality, improve and simplified the current operation processing method, strengthened the controllability of coating process, realized automatic continuous productive target.
The difference of have its source in used vulcabond, polyvalent alcohol, auxiliary agent and working method thereof that polyurethane reaction product property and purposes vary.Generally speaking vulcabond reveals the performance of intensity aspect as the hard segment table in polymer molecular chain, and polyether glycol goes out snappiness as soft section major embodiment in polymer molecular chain.Soft section-hard section over-all properties shows as the vitrifying conversion temp Tg of polymkeric substance, and when Tg ﹤ room temperature, aggregate performance goes out snappiness and elasticity, shows rigidity when Tg ﹥ room temperature.Because the diisocyanate molecules amount is relatively fixing, not strong as the modulability of hard section, and the molecular size range difference of polyester or polyether glycol can reach more than 10 times (200～8000), is therefore the emphasis of regulating the urethane performance.
Except biopolyol, also have a lot of monomers (as: polyvalent alcohol, polyvalent alcohol and polyether glycol), all can with isocyanic ester generation polyurethane reaction, polyvalent alcohol is (as polyoxyethylene glycol in theory, PEG) also can with isocyanic ester generation polyurethane reaction, for the preparation of coated fertilizer, but, because the viscosity ratio of polyvalent alcohol (as: polyoxyethylene glycol) is higher, not too be suitable for polyurethane coated.The present invention uses hard bubbles with polyether polyol for soft PU foam as reaction monomers.Polyether glycol is than polyester polyol water-tolerant, and reactive behavior is higher.At present product line is a lot, can meet produce variously hard bubble, the needs of soft bubble, range of choice is very wide.
When the polyether glycol functionality is 2, except two ends are hydroxyls, there is no side chain, the product of formation is linear molecule, shows as elasticity and snappiness; Along with the increase of functionality, side chain increases, and polymer molecule is T-shaped, shows rigidity.Therefore when selecting polyether glycol, according to the processing needs, select the polyether glycol of low functionality, high molecular, the urethane made is elastomerics, select high functionality, low-molecular-weight polyether glycol to make hard polyurethane material, as hard polyurethane foam; Polyether glycol between selection, prepare flexible PU foam.
In the reaction of particle surface generation polyurethane film-forming, it is generally acknowledged that fast reaction speed is beneficial to complete processing, therefore, polyurethane coated controlled-release fertilizer needs rigid-foam polyether polyol as reactant.In addition, after polyurethane film-forming, in order to ensure good controlled release properties, also wish that rete has certain snappiness.Can, by regulation and control segmented polyurethane-soft segment structure, arrive the regulation and control to the coated fertilizer release performance for this reason.
Described polyurethane coated material comprises polyether glycol and isocyanic ester, and the hydroxyl value of described polyether glycol is 100～415mgKOH/g, and molecular weight is 400～1700, and functionality is 2～4.
The hydroxyl value of described polyether glycol can be for such as 100 ± 10mgKOH/g, 107～117mgKOH/g, 115～130mgKOH/g, 120～140mgKOH/g, 163～173mgKOH/g, 230～250mgKOH/g, 265～295mgKOH/g, 280～340mgKOH/g, 300～360mgKOH/g, 350～370mgKOH/g, 365～395mgKOH/g or 380～420mgKOH/g etc.; Preferably, the hydroxyl value of described polyether glycol is 100～300mgKOH/g.
The functionality of polyether glycol can ensure that between 2～4 rete has certain toughness and intensity.
Preferably, described polyether glycol comprises the polyether polyol for soft PU foam that rigid-foam polyether polyol that hydroxyl value is 200～300mgKOH/g and hydroxyl value are 100～200mgKOH/g; Preferably, the mass ratio of described rigid-foam polyether polyol and polyether polyol for soft PU foam is 10:90～90:10, such as 11:89,12:88,15:85,20:80,25:75,30:70,40:60,50:50,60:40,70:30,80:20,85:15,87:13,88:12 or 89:11 etc.
Preferably, it is 500～800 that described polyether glycol comprises molecular weight, and the rigid-foam polyether polyol that hydroxyl value is 200～300mgKOH/g and molecular weight are 800～1700, the polyether polyol for soft PU foam that hydroxyl value is 100～200mgKOH/g; Preferably, the mass ratio of described rigid-foam polyether polyol and polyether polyol for soft PU foam is 10:90～90:10, such as 11:89,12:88,15:85,20:80,25:75,30:70,40:60,50:50,60:40,70:30,80:20,85:15,87:13,88:12 or 89:11 etc.
Preferably, described polyether glycol also comprises the block copolymerization ethoxylated polyhydric alcohol obtained by oxyethane and/or propylene oxide and polyvalent alcohol copolymerization; Preferably, the functionality of described block copolymerization ethoxylated polyhydric alcohol is 3～4; Preferably, the molecular weight of described block copolymerization ethoxylated polyhydric alcohol is 800～1200, more preferably 900～1100, be particularly preferably 1000; Preferably, the content of described block copolymerization ethoxylated polyhydric alcohol in polyether glycol is 5～50wt%, and more preferably 8～40wt%, be particularly preferably 10～30wt%; Described polyvalent alcohol such as propylene glycol, glycerine or Diethylene Glycol etc.
Preferably, the rigid-foam polyether polyol that described polyether glycol comprises that molecular weight is 500～800, functionality is 2～4, hydroxyl value is 200～300mgKOH/g, the polyether polyol for soft PU foam that molecular weight is 800～1700, functionality is 2～4, hydroxyl value is 100～200mgKOH/g, and the block copolymerization ethoxylated polyhydric alcohol that molecular weight is 800～1200, functionality is 3～4 is obtained by oxyethane and/or propylene oxide and polyvalent alcohol copolymerization; The mass ratio of described rigid-foam polyether polyol and polyether polyol for soft PU foam is 10:90～90:10; The content of described block copolymerization ethoxylated polyhydric alcohol in polyether glycol is 5～50wt%.
Preferably, described isocyanic ester is liquefied mdi and/or PAPI, is particularly preferably PAPI; The another name of described liquefied mdi is modification MDI, and English modified MDI by name or liquified MDI, by introducing consistency impurity, changed the crystallinity of product, eliminated at normal temperatures crystallization; MDI is diphenylmethanediisocyanate, and PAPI is poly methylene poly phenyl poly isocyanate.
Preferably, described polyurethane coated material also comprises catalyzer, to promote reaction, carries out; Preferably, described catalyzer is the organic amine catalyzer, is particularly preferably tetramethyl butane diamine and/or triethylenediamine.
Preferably, described polyurethane coated material also comprises whipping agent, and making the urethane of preparation is porous-film, and by controlling the amount of whipping agent, the quantity of control punch and size, reach the purpose of regulating nutrient release rate; Preferably, described whipping agent is water, HFC and/or pentamethylene, is particularly preferably pentamethylene; Described HFC is pentafluoropropane.
Described coated fertilizer is mainly used in particle surface and coats, and is particularly suitable for: the production film-coated controlled release fertilizer of serialization.
Two of purpose of the present invention is to provide a kind of polyurethane coated fertilizer, and it comprises granulated fertilizer and the adventitia generated by polyurethane coated material of the present invention.Described adventitia has certain intensity and snappiness, and release performance is good.
Three of purpose of the present invention is to provide a kind of preparation method of described polyurethane coated fertilizer, comprises the following steps:
(1) by the granulated fertilizer preheating, then with paraffin, mix, pre-treatment is carried out in the urea granules surface;
(2) polyether glycol, optional catalyzer and optional whipping agent are mixed, with atomization after the isocyanic ester short mix and be sprayed to the fertiliser granulates surface that step (1) obtains, obtain described polyurethane coated fertilizer.
Preferably, described method is carried out in fluidized-bed.
Preferably, described preheating temperature is 75～95 ℃, more preferably 80～90 ℃, is particularly preferably 85 ℃.
Preferably, be at least 1 minute described warm up time, is particularly preferably 2 minutes.
Preferably, described pretreatment time is 1～5 minute, more preferably 1.5～3 minutes, is particularly preferably 2 minutes.
Preferably, the mass ratio of described granulated fertilizer and paraffin is 100:1～200:1, and more preferably 130:1～180:1, be particularly preferably 150:1.
Preferably, described spray velocity is 0.5～6g/min, and more preferably 1～4g/min, be particularly preferably 3g/min.
Preferably, described spray time is 10～25 minutes, more preferably 12～20 minutes, is particularly preferably 15 minutes.
It is reaction mass that polyether glycol and isocyanic ester (particularly PAPI) are take in the present invention, requirement according to the controlled release rete to polyurethane product intensity and toughness, the design reactant ratio, select the rigid-foam polyether polyol with different molecular weight to be combined into proprietary coated fertilizer.With existing coating reaction mass, compare, advantage of the present invention is: the reaction mass molecular weight is little, speed of response is fast, the polyether glycol functionality is high, the polyurethane products strength high toughness of preparation is good, different polyvalent alcohols mixing make the polyurethane molecular chain have different soft section and hard section, can improve its intensity and toughness.Solve vegetable and animals oils polylol Modulatory character in the polyurethane reaction process occurs poor, can not meet the problem of producing and using.
The accompanying drawing explanation
Fig. 1 is the schema of a polyurethane coated fertilizer preparation technology's of the present invention embodiment;
Reference numeral is as follows:
1-Root's blower; 2-gas buffer tank; 3-well heater;
4-fluidized-bed; 5-air compressor; 6-nozzle;
7-coating liquid storage tank A; 8-peristaltic pump A; 9-coating liquid storage tank B;
10-peristaltic pump B.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1-2 adopts following methods to carry out the preparation of coated fertilizer:
(1) open Root's blower 1, air-flow is through after surge tank 2 cushioning balances, through electric heater 3 heating are laggard, enters fluidized-bed 4.Ensure that in fluidized-bed, temperature is 85 ℃, make fluidized-bed in running order.
(2) the 1.5kg granular urea is added to the fluidized-bed preheating 2 minutes, then the compressed gas that uses air compressor 5 to provide is by nozzle 6, the paraffin that 10g is positioned in storage tank 7 sprays into fluidized-bed, and pre-treatment is carried out in the urea granules surface, and the treatment time is 2 minutes.
(3) add polyether glycol, catalyzer and whipping agent according to metered proportions in storage tank A7, and mix, use peristaltic pump B8, be transported to nozzle 6.Meanwhile, in storage tank B9, add PAPI, by peristaltic pump B10, be transported to nozzle 6, with reaction mass atomization after short mix in nozzle of storage tank A.
(4) reaction mass, with the speed atomization of 3g/min, operates 15 minutes, after stop adding reaction mass, coating finishes, and takes out the coating sample.
Embodiment 1: the impact of different polyether glycols on coating operation and effect
It is different realizing adopting functionality, and several polyether glycols that hydroxyl value is different react with PAPI separately, prepare film-coated controlled release fertilizer, and processing scheme and result are as shown in table 1.Experimental procedure as mentioned above.
The release performance of table 1 different polyether glycol coating processing scheme and sample thereof
From table 1, polyether glycol hydroxyl value and functionality are of great impact to coated fertilizer nutrient release performance.Hard bubble or polyurethane coated fertilizer prepared at the polyether glycol in 100～200mgKOH/g scope by hydroxyl value has release performance preferably.Functionality is 2 o'clock, prepared coated fertilizer fertilizer releasing period is generally not long, in the water soaking experimentation, see as seen, the polyurethane coated fertilizer rete that functionality is 2, under the effect of water seepage water pressure, is spheroidal, that is to say rete is pliable and tough under whose seepage water pressure effect, deformation easily occurs, and causes nutrient to discharge fast; When functionality is 3, prepared film-coated controlled release fertilizer controlled release properties improves greatly, and the hydroxyl value processing optimum that is 110mgKOH/g, therefore ensures that rete has certain intensity and snappiness, extremely important for the mechanical property that improves its film layer structure.Hydroxyl value is 55, and functionality is 2 and 3 two, and to process release performances all very poor, illustrates that polyurethane coated controlled-release fertilizer should select rigid-foam polyether polyol.From the coating operating process, the processing that hydroxyl value is 55, speed of response is slower, adhesion phenomenon also easily occurs, so, no matter from improving speed of response, still, from the angle of controlled release properties, all require to adopt rigid-foam polyether polyol.
Embodiment 2: adjustment is hard bubbled, and the soft or hard section forms and ratio operates coating and the impact of effect
From embodiment 1, what hydroxyl value was 415 hard bubbles, although speed of response is the fastest, but controlled release properties is really not best, reason is that film strength is too large, and lacks certain elasticity, under the effect of water seepage water pressure, thereby easily occur breaking, cause seepage and release fast.For this reason, the present embodiment adjustment is hard bubbled, and the soft or hard section forms and ratio, adopts the polyvalent alcohol that functionality is 3 mixed and adopt the block copolymerization ethoxylated polyhydric alcohol to carry out coating processing (scheme is in Table 2).Testing polyether block copolymer used is the epoxy ethane-epoxy propane copolyether, specifically refers to that the EO/PO proportioning is 1/2.5, adopts the atmospheric synthesizing method preparation, the propylene oxide that central block is ethylene oxide unit(s)-epoxy ethane-epoxy propane triblock copolymer ether.
Table 2 adjustment is hard bubbled, and the soft or hard section forms and ratio operates coating and the impact of effect
Data by table 2 are visible, adopt the mode of blend and block copolymerization all can effectively improve the nutrient release performance of coated fertilizer, especially the polyether polyol for soft PU foam that is 110 when hydroxyl value accounts for 60%, when the hard section polyether glycol that hydroxyl value is 410 accounts for 40%, release period is the longest, approaches the release period of 3 months.
(1) open Root's blower 1, air-flow is through after surge tank 2 cushioning balances, through electric heater 3 heating are laggard, enters fluidized-bed 4.Ensure that in fluidized-bed, temperature is 75 ℃, make fluidized-bed in running order.
(2) the 2kg granular urea is added to the fluidized-bed preheating 10 minutes, the compressed gas that then uses air compressor 5 to provide is by nozzle 6, and the paraffin that 10g is positioned in storage tank 7 sprays into fluidized-bed, and pre-treatment is carried out in the urea granules surface, and the treatment time is 5 minutes.
(3) add polyether glycol, tetramethyl butane diamine and pentamethylene according to metered proportions in storage tank A7, and mix, use peristaltic pump B8, be transported to nozzle 6.Meanwhile, add PAPI in storage tank B9, by peristaltic pump B10, be transported to nozzle 6, with reaction mass atomization after short mix in nozzle of storage tank A, wherein, the hydroxyl value that described polyether glycol comprises 50wt% is the polyether glycol that 200mgKOH/g, molecular weight are 400～600, functionality is 3, and the block copolymerization ethoxylated polyhydric alcohol that obtains of the ethylene oxide/propylene oxide of 50wt% and propylene glycol copolymerization, the molecular weight of described block copolymerization ethoxylated polyhydric alcohol is 800, functionality is 3.
(4) reaction mass, with the speed atomization of 0.5g/min, operates 25 minutes, after stop adding reaction mass, coating finishes, and takes out the coating sample.
After tested, the initial stage solubility rate of the polyurethane coated fertilizer that the present embodiment obtains is 1.1%, and the differential solubility rate is 1.32%, and release period is 61 days.
Embodiment 4
(1) open Root's blower 1, air-flow is through after surge tank 2 cushioning balances, through electric heater 3 heating are laggard, enters fluidized-bed 4.Ensure that in fluidized-bed, temperature is 95 ℃, make fluidized-bed in running order.
(2) the 1kg granular urea is added to the fluidized-bed preheating 1 minute, the compressed gas that then uses air compressor 5 to provide is by nozzle 6, and the paraffin that 10g is positioned in storage tank 7 sprays into fluidized-bed, and pre-treatment is carried out in the urea granules surface, and the treatment time is 1 minute.
(3) add polyether glycol, trimethylene diamines and HFC according to metered proportions in storage tank A7, and mix, use peristaltic pump B8, be transported to nozzle 6.Meanwhile, add MDI in storage tank B9, by peristaltic pump B10, be transported to nozzle 6, with reaction mass atomization after short mix in nozzle of storage tank A, wherein, the hydroxyl value that described polyether glycol comprises 95wt% is the polyether glycol that 150mgKOH/g, molecular weight are 1600～1700, functionality is 3, and the block copolymerization ethoxylated polyhydric alcohol that obtains of the propylene oxide of 5wt% and propylene glycol copolymerization, the molecular weight of described block copolymerization ethoxylated polyhydric alcohol is 1200, functionality is 4.
(4) reaction mass, with the speed atomization of 6g/min, operates 10 minutes, after stop adding reaction mass, coating finishes, and takes out the coating sample.
After tested, the initial stage solubility rate of the polyurethane coated fertilizer that the present embodiment obtains is 0.2%, and the differential solubility rate is 0.93%, and release period is 87 days.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a polyurethane coated material, it comprises polyether glycol and isocyanic ester, and the hydroxyl value of described polyether glycol is 100～415mgKOH/g, and molecular weight is 400～1700, and functionality is 2～4.
2. polyurethane coated material as claimed in claim 1, is characterized in that, the hydroxyl value of described polyether glycol is 100～300mgKOH/g;
Preferably, the molecular weight of described polyether glycol is 800～1700;
Preferably, described polyether glycol comprises the polyether polyol for soft PU foam that rigid-foam polyether polyol that hydroxyl value is 200～300mgKOH/g and hydroxyl value are 100～200mgKOH/g; Preferably, the mass ratio of described rigid-foam polyether polyol and polyether polyol for soft PU foam is 10:90～90:10.
3. polyurethane coated material as claimed in claim 1 or 2, is characterized in that, described polyether glycol also comprises the block copolymerization ethoxylated polyhydric alcohol obtained by oxyethane and/or propylene oxide and polyvalent alcohol copolymerization; Preferably, the functionality of described block copolymerization ethoxylated polyhydric alcohol is 3～4; Preferably, the molecular weight of described block copolymerization ethoxylated polyhydric alcohol is 800～1200, more preferably 900～1100, be particularly preferably 1000; Preferably, the content of described block copolymerization ethoxylated polyhydric alcohol in polyether glycol is 5～50wt%, and more preferably 8～40wt%, be particularly preferably 10～30wt%.
4. polyurethane coated material as described as claim 1-3 any one, it is characterized in that, described polyether glycol comprises the rigid-foam polyether polyol that functionality is 2～4, hydroxyl value is 200～300mgKOH/g, the polyether polyol for soft PU foam that functionality is 2～4, hydroxyl value is 100～200mgKOH/g, and the block copolymerization ethoxylated polyhydric alcohol that molecular weight is 800～1200, functionality is 3～4 is obtained by oxyethane and/or propylene oxide and polyvalent alcohol copolymerization; The mass ratio of described rigid-foam polyether polyol and polyether polyol for soft PU foam is 10:90～90:10; The content of described block copolymerization ethoxylated polyhydric alcohol in polyether glycol is 5～50wt%.
5. polyurethane coated material as described as claim 1-4 any one, is characterized in that, described isocyanic ester is liquefied mdi and/or PAPI, is particularly preferably PAPI;
Preferably, described polyurethane coated material also comprises catalyzer; Preferably, described catalyzer is the organic amine catalyzer, is particularly preferably tetramethyl butane diamine and/or triethylenediamine;
Preferably, described polyurethane coated material also comprises whipping agent; Preferably, described whipping agent is water, HFC and/or pentamethylene, is particularly preferably pentamethylene.
6. a polyurethane coated fertilizer, it comprises granulated fertilizer and the adventitia generated by the described polyurethane coated material of claim 1-5 any one.
7. the preparation method of polyurethane coated fertilizer as claimed in claim 6 comprises the following steps:
(1) by the granulated fertilizer preheating, then with paraffin, mix, pre-treatment is carried out in the urea granules surface;
(2) polyether glycol, optional catalyzer and optional whipping agent are mixed, with atomization after the isocyanic ester short mix and be sprayed to the fertiliser granulates surface that step (1) obtains, obtain described polyurethane coated fertilizer.
8. method as claimed in claim 7, is characterized in that, described method is carried out in fluidized-bed;
Preferably, described preheating temperature is 75～95 ℃, more preferably 80～90 ℃, is particularly preferably 85 ℃;
Preferably, be at least 1 minute described warm up time, is particularly preferably 2 minutes.
9. method as claimed in claim 7 or 8, is characterized in that, described pretreatment time is 1～5 minute, more preferably 1.5～3 minutes, is particularly preferably 2 minutes;
Preferably, the mass ratio of described granulated fertilizer and paraffin is 100:1～200:1, and more preferably 130:1～180:1, be particularly preferably 150:1.
10. as the described method of claim 7-9 any one, it is characterized in that, described spray velocity is 0.5～6g/min, and more preferably 1～4g/min, be particularly preferably 3g/min;
Preferably, described spray time is 10～25 minutes, more preferably 12～20 minutes, is particularly preferably 15 minutes.
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| US14/453,362 US9416064B2 (en) | 2013-08-07 | 2014-08-06 | Method for producing controlled-release fertilizer coated with polyurethane |
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| CN107162789A (en) * | 2017-06-29 | 2017-09-15 | 宁夏农林科学院农业资源与环境研究所 | Paddy rice cleaner production full dose fertilising controlled release Blending Fertilizer and preparation and application process |
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| CN112125740A (en) * | 2020-09-23 | 2020-12-25 | 沈阳化工研究院有限公司 | Organic-inorganic hybrid coated slow-release fertilizer and preparation method thereof |
| CN116375531A (en) * | 2023-03-30 | 2023-07-04 | 中国农业科学院农业资源与农业区划研究所 | Temperature-sensitive polyurethane coated controlled-release fertilizer and preparation method thereof |
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