CN100475750C - Composite envelope type slow release fertilizer - Google Patents
Composite envelope type slow release fertilizer Download PDFInfo
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- CN100475750C CN100475750C CNB200510094262XA CN200510094262A CN100475750C CN 100475750 C CN100475750 C CN 100475750C CN B200510094262X A CNB200510094262X A CN B200510094262XA CN 200510094262 A CN200510094262 A CN 200510094262A CN 100475750 C CN100475750 C CN 100475750C
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Abstract
The present invention provides one kind of composite coated slow released fertilizer. The composite coated slow released fertilizer consists of one fertilizer core and one coating film, and the coating film includes one organic film layer with high barrier property, one thermosetting polymer film layer and/or sulfur-containing thermosetting polymer composite film layer. The organic film layer with high barrier property as the inside layer or intermediate layer is preferably made of non-polar organic material of low or high molecular weight. The thermosetting polymer may be one or several of polyurethane, epoxy resin, unsaturated polyester, etc. The organic film layer with high barrier property may contain slow releasing regulator and/or extender. The composite coated slow released fertilizer has long releasing period and excellent regulation performance.
Description
One, technical field
The present invention relates to a kind of concentrated fertilizer, particularly a kind of composite envelope type slow release fertilizer belongs to the fertilizer industry field.
Two, background technology
Slow release fertilizer is the future thrust of countries in the world fertilizer industry.Slow release fertilizer has organic synthesis type slow release fertilizer and enveloped slow release fertilizer two classes.Wherein, enveloped slow release fertilizer is at fertiliser granulates surface-coated organic polymer or inorganics coating, speed that fertilizer dissolves in Tian Tuzhong is slowed down and becomes slow release fertilizer.Particularly, the organic polymer enveloped slow release fertilizer can have excellent controllable sustained-release performance, therefore is the emphasis of slow release fertilizer research and development always.
Wherein, with the enveloped slow release fertilizer of thermosetting polymer as coated fertilizer, owing to be to adopt low viscous prepolymer or reactive component to carry out coating, can be not with an organic solvent in the coating process, therefore in the coating process, to use the thermoplastic polymer enveloped slow release fertilizer of a large amount of organic solvents with respect to adopting the solution coating, thermosetting polymer enveloped slow release fertilizer production process is polluted little, and product cost is low, is the main direction of enveloped slow release fertilizer.
But the normally high polar polymkeric substance of thermosetting polymer such as urethane, Resins, epoxy, unsaturated polyester etc., therefore only adopts thermosetting polymer not high as the release period of the enveloped slow release fertilizer of coated fertilizer preparation, such as 20～40 days.Therefore, all the time, obtaining long release period is the direction that the thermosetting polymer enveloped slow release fertilizer is made great efforts.
Three, summary of the invention
The object of the present invention is to provide the long thermosetting polymer enveloped slow release fertilizer of a kind of release period.
The technical solution that realizes the object of the invention is: a kind of composite envelope type slow release fertilizer, coating by fertilizer core and fertilizer core outside is formed, wherein, coating comprises: (a) high gas barrier organic film, (b) thermosetting polymer rete and/or sulfur-bearing thermosetting polymer mixture film.
The high gas barrier organic film of composite envelope type slow release fertilizer of the present invention, the preferably nexine of whole coating or middle layer.
The high gas barrier organic film of composite envelope type slow release fertilizer of the present invention, preferably nonpolar organic film.Nonpolar organic film material can be lower molecular weight nonpolar organic matter and/or high molecular non-polar polymer.The lower molecular weight nonpolar organic matter can be to be in solid wax, low-molecular-weight polyolefin and the petroleum resin etc. one or more under the room temperature.The high molecular non-polar polymer can be one or more in polyolefine, cis-1,4-polybutadiene rubber, natural rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) and terpolymer EP rubber, styrene-butadiene-styrene block copolymer and the styrene isoprene styrene block copolymer (SIS) etc.
Thermosetting polymer in the composite envelope type slow release fertilizer coating of the present invention can be in urethane, Resins, epoxy, unsaturated polyester, resol, furane resin, unsaturated oil resin and the aminoresin etc. one or more.
In the sulfur-bearing thermosetting polymer mixture film of composite envelope type slow release fertilizer of the present invention, the average quality mark of sulphur can be 0%～95%.
Can contain slowly-releasing conditioning agent and/or extender in the high gas barrier organic film in the composite envelope type slow release fertilizer coating of the present invention.The slowly-releasing conditioning agent can be one or more in softening agent, water-soluble cpds, plant powder, longer chain fatty acid and ester, long chain aliphatic alcohol, rosin and ester thereof, pitch, clay, talcum powder, molecular sieve powder and the bone meal etc.Extender can be one or more in sulphur, lime carbonate, carbon black, process white and the silicon-dioxide etc.
The coating overall average thickness of composite envelope type slow release fertilizer of the present invention can be 20～180 μ m.Wherein, the mean thickness of high gas barrier organic film can be 2～30 μ m, and the overall average thickness of thermosetting polymer rete and sulfur-bearing thermosetting polymer mixture film can be 20～180 μ m; The overall average thickness of thermosetting polymer rete can be 0～180 μ m, and the overall average thickness of sulfur-bearing thermosetting polymer mixture film can be 0～180 μ m.
Compared with prior art, the present invention has following remarkable advantage: (1) composite envelope type slow release fertilizer of the present invention adopts water and fertilizer is seen through the very low high gas barrier organic film (particularly nonpolar organic film) of ability, carry out composite coatedly with thermosetting polymer rete and/or sulfur-bearing thermosetting polymer mixture film, so the release period of composite envelope type slow release fertilizer of the present invention is more much longer than adopting separately the enveloped slow release fertilizer of thermosetting polymer rete and/or sulfur-bearing thermosetting polymer mixture film.(2) particularly, when composite envelope type slow release fertilizer of the present invention adopts sulfur-bearing thermosetting polymer mixture film in coating, can also further improve the gas barrier ability of whole coating, the release period of composite envelope type slow release fertilizer of the present invention is further prolonged water and fertilizer; And,, in coating, adopt sulfur-bearing thermosetting polymer mixture film to reduce the consumption of the high thermosetting polymer of price, so the cost of composite envelope type slow release fertilizer of the present invention can be lower because the price of sulphur is very low.(3) composite envelope type slow release fertilizer of the present invention can pass through to add the slowly-releasing conditioning agent at high gas barrier organic film, prepare the slow release fertilizer of different release periods, and with the application requiring of suitable different occasions and different plants, and method is flexible, economical and effective.
Four, description of drawings
Fig. 1 is the high gas barrier organic film of spherical fertilizer core 1-thermosetting polymer rete 3-2-thermosetting polymer rete 3 structure iron of composite envelope type slow release fertilizer of the present invention.
Fig. 2 is the high gas barrier organic film of spherical fertilizer core 1-2-thermosetting polymer rete 3 structure iron of composite envelope type slow release fertilizer of the present invention.
Fig. 3 is high gas barrier organic film 2 structure iron of spherical fertilizer core 1-thermosetting polymer rete 3-of composite envelope type slow release fertilizer of the present invention.
Fig. 4 is the high gas barrier organic film of spherical fertilizer core 1-sulfur-bearing thermosetting polymer mixture film 4-2-sulfur-bearing thermosetting polymer mixture film 4 structure iron of composite envelope type slow release fertilizer of the present invention.
Fig. 5 is the high gas barrier organic film of spherical fertilizer core 1-2-sulfur-bearing thermosetting polymer mixture film 4 structure iron of composite envelope type slow release fertilizer of the present invention.
Fig. 6 is high gas barrier organic film 2 structure iron of spherical fertilizer core 1-sulfur-bearing thermosetting polymer mixture film 4-of composite envelope type slow release fertilizer of the present invention.
Fig. 7 is the high gas barrier organic film of spherical fertilizer core 1-sulfur-bearing thermosetting polymer mixture film 4-2-thermosetting polymer rete 3 structure iron of composite envelope type slow release fertilizer of the present invention.
Fig. 8 is the high gas barrier organic film of spherical fertilizer core 1-thermosetting polymer rete 3-2-sulfur-bearing thermosetting polymer mixture film 4 structure iron of composite envelope type slow release fertilizer of the present invention.
Fig. 9 is the high gas barrier organic film of spherical fertilizer core 1-sulfur-bearing thermosetting polymer mixture film 4-2-sulfur-bearing thermosetting polymer mixture film 4-thermosetting polymer rete 3 structure iron of composite envelope type slow release fertilizer of the present invention.
Figure 10 is the high gas barrier organic film of spherical fertilizer core 1-thermosetting polymer rete 3-2-sulfur-bearing thermosetting polymer mixture film 4-thermosetting polymer rete 3 structure iron of composite envelope type slow release fertilizer of the present invention.
Figure 11 is the high gas barrier organic film of spherical fertilizer core 1-thermosetting polymer rete 3-sulfur-bearing thermosetting polymer mixture film 4-2-sulfur-bearing thermosetting polymer mixture film 4-thermosetting polymer rete 3 structure iron of composite envelope type slow release fertilizer of the present invention.
Figure 12 is the high gas barrier organic film of spherical fertilizer core 1-2-sulfur-bearing thermosetting polymer mixture film 4-thermosetting polymer rete 3 structure iron of composite envelope type slow release fertilizer of the present invention.
Figure 13 is high gas barrier organic film 2 structure iron of spherical fertilizer core 1-sulfur-bearing thermosetting polymer mixture film 4-thermosetting polymer rete 3-of composite envelope type slow release fertilizer of the present invention.
Figure 14 is high gas barrier organic film 2 structure iron of spherical fertilizer core 1-thermosetting polymer rete 3-sulfur-bearing thermosetting polymer mixture film 4-of composite envelope type slow release fertilizer of the present invention.
Five, embodiment
Composite envelope type slow release fertilizer of the present invention is made up of the coating of fertilizer core 1 and fertilizer core outside, and wherein coating comprises: (a) high gas barrier organic film 2, (b) thermosetting polymer rete 3 and/or sulfur-bearing thermosetting polymer mixture film 4.
Composite envelope type slow release fertilizer of the present invention, nexine, middle layer or skin that high gas barrier organic film can be a whole coating, but the preferably nexine or the middle layer of whole coating.Like this, high gas barrier organic film can be subjected to the thermosetting polymer rete of its outside and/or the protection of sulfur-bearing thermosetting polymer mixture film, cracky not, and release period is reliable and stable.Certainly, high gas barrier organic film can be the skin of whole coating, the preferably high gas barrier polymkeric substance of high gas barrier organic film material this moment.
The fertilizer core of composite envelope type slow release fertilizer of the present invention can be nitrogenous fertilizer, phosphate fertilizer, potash fertilizer or compound fertilizer etc.The shape of fertilizer core can be granular, sheet etc., but with granular be good, preferably spherical.
The coating of composite envelope type slow release fertilizer of the present invention can be the composite film of thermosetting polymer rete and high gas barrier organic film.At this moment, the structure of slow release fertilizer can at first be a thermosetting polymer rete 3 from fertilizer core 1 promptly as shown in Figure 1 outward, is high gas barrier organic film 2 then, is thermosetting polymer rete 3 more outward.Structure can at first be high gas barrier organic film 2 from fertilizer core 1 promptly as shown in Figure 2 outward also, is thermosetting polymer rete 3 then.Accompanying drawing 1 texture ratio accompanying drawing 2 structures are excellent.Can also at first be thermosetting polymer rete 3 outward from fertilizer core 1 promptly as shown in Figure 3, be high gas barrier organic film 2 then.Accompanying drawing 1 and accompanying drawing 2 texture ratio accompanying drawings 3 structures are excellent.
The coating of composite envelope type slow release fertilizer of the present invention also can be the composite film of sulfur-bearing thermosetting polymer mixture film and high gas barrier organic film, and this composite film is more excellent with the composite film of high gas barrier organic film than thermoset polymer film.At this moment, the structure of slow release fertilizer can at first be a sulfur-bearing thermosetting polymer mixture film 4 from fertilizer core 1 promptly as shown in Figure 4 outward, is high gas barrier organic film 2 then, is sulfur-bearing thermosetting polymer mixture film 4 more outward.Structure can at first be high gas barrier organic film 2 from fertilizer core 1 promptly as shown in Figure 5 outward also, is sulfur-bearing thermosetting polymer mixture film 4 then.Accompanying drawing 4 texture ratio accompanying drawings 5 structures are excellent.Structure can also at first be a sulfur-bearing thermosetting polymer mixture film 4 from fertilizer core 1 promptly as shown in Figure 6 outward, is high gas barrier organic film 2 then.Accompanying drawing 4 and accompanying drawing 5 texture ratio accompanying drawings 6 structures are excellent.
The coating of composite envelope type slow release fertilizer of the present invention can also be thermosetting polymer rete, sulfur-bearing thermosetting polymer mixture film and high gas barrier organic film three's a composite film.Wherein, the structure that sulfur-bearing thermosetting polymer mixture film is close to high gas barrier organic film is preferred, and the sulfur-bearing thermosetting polymer mixture film texture ratio sulfur-bearing thermosetting polymer mixture film of being close to surface in the high gas barrier organic film to be close to the structure of high gas barrier organic film outside surface excellent.At this moment, the structure of slow release fertilizer can at first be a sulfur-bearing thermosetting polymer mixture film 4 from fertilizer core 1 promptly as shown in Figure 7 outward, is high gas barrier organic film 2 then, is thermosetting polymer rete 3 more outward.Structure can at first be a thermosetting polymer rete 3 from fertilizer core 1 promptly as shown in Figure 8 outward also, is high gas barrier organic film 2 then, is sulfur-bearing thermosetting polymer mixture film 4 more outward.Accompanying drawing 7 texture ratio accompanying drawings 8 structures are excellent.Structure can at first be a sulfur-bearing thermosetting polymer mixture film 4 from fertilizer core 1 promptly as shown in Figure 9 outward also, secondly is high gas barrier organic film 2, is sulfur-bearing thermosetting polymer mixture film 4 then, is thermosetting polymer rete 3 more outward.Structure can at first be a thermosetting polymer rete 3 from fertilizer core 1 promptly as shown in Figure 10 outward also, secondly is high gas barrier organic film 2, is sulfur-bearing thermosetting polymer mixture film 4 then, is thermosetting polymer rete 3 more outward.Structure can also be as shown in Figure 11, at first be thermosetting polymer rete 3 outward promptly from fertilizer core 1, next is a sulfur-bearing thermosetting polymer mixture film 4, it then is high gas barrier organic film 2, being sulfur-bearing thermosetting polymer mixture film 4 then, is thermosetting polymer rete 3 more outward.Structure can also at first be high gas barrier organic film 2 from fertilizer core 1 promptly as shown in Figure 12 outward, is sulfur-bearing thermosetting polymer mixture film 4 then, is thermosetting polymer rete 3 more outward.Wherein, accompanying drawing 7, accompanying drawing 9 and accompanying drawing 11 structures that sulfur-bearing thermosetting polymer mixture film 4 is in 2 li surfaces of high gas barrier organic film are preferred in above-mentioned six kinds of structures, and accompanying drawing 9 and accompanying drawing 11 texture ratio accompanying drawings 7 structures are excellent.Structure can also at first be a sulfur-bearing thermosetting polymer mixture film 4 from fertilizer core 1 promptly as shown in Figure 13 outward, is thermosetting polymer rete 3 then, is high gas barrier organic film 2 more outward.Structure can also at first be a thermosetting polymer rete 3 from fertilizer core 1 promptly as shown in Figure 14 outward, is sulfur-bearing thermosetting polymer mixture film 4 then, is high gas barrier organic film 2 more outward.Accompanying drawing 14 texture ratio accompanying drawings 13 structures are excellent.Certainly, can also be the structure of other array mode.
In addition, can also be variation structure on the architecture basics of accompanying drawing 1～accompanying drawing 14.Such as, can be the MULTIPLE COMPOSITE structure of coating structure shown in accompanying drawing 1～accompanying drawing 14, can also be the MULTIPLE COMPOSITE structure that makes up mutually between the coating structure shown in accompanying drawing 1～accompanying drawing 14.But consider that from technological angle these MULTIPLE COMPOSITE structures are not preferred structures.
In the sulfur-bearing thermosetting polymer mixture film of composite envelope type slow release fertilizer of the present invention, when sulphur content is too low, the existence of sulphur is to reducing cost and reducing the DeGrain of rete gas barrier, but the toughness of rete is low when too high, be fragility, therefore the average quality mark of sulphur can be good between 20%～95%, be preferably between 30%～90% between 0%～95%.In case of necessity, the softening agent that can add certain content in sulfur-bearing thermosetting polymer mixture film improves the toughness of rete; Certainly, also can in sulfur-bearing thermosetting polymer mixture film, sneak into the toughness that toughness polymer improves rete.
Sulphur content in the sulfur-bearing thermosetting polymer mixture film can change in gradient in the thicknesses of layers direction.Such as, high both sides are low, from high to low or sulphur content Gradient distribution from low to high in the middle of being, wherein high can be up to 100%, lowly can be low to moderate 0%.And the direction of graded is preferably, be in high gas barrier organic film inward the sulfur-bearing thermosetting polymer mixture film of the direction of fertilizer core (promptly toward) reduce gradually in sulphur content on the direction of fertilizer core; And be in high gas barrier organic film outward the sulfur-bearing thermosetting polymer mixture film of (promptly with opposite) toward the direction of fertilizer core reduce gradually in sulphur content on the direction on fertilizer surface, be that outer sulphur content in the sulfur-bearing thermosetting polymer mixture film is low, skin can have high toughness like this.Sulphur content height in high gas barrier organic film sulfur-bearing thermosetting polymer mixture film outward; as 80% when above; the outer thermosetting polymer rete that one deck thin (as 3～10 μ m) can be arranged of sulfur-bearing thermosetting polymer mixture film is to protect inner rete better.
The high gas barrier organic film of composite envelope type slow release fertilizer of the present invention, be meant the transmitance of water and fertilizer rete far below simple thermosetting polymer rete, promptly high gas barrier organic film material to the transmitance of water and fertilizer far below the thermosetting polymer that is adopted in the coating.High gas barrier organic film material, can be molecular structure Semi-polarity group organic materials or non-hydrogen, the high electronegative element of non-carbon organic materials seldom such as oxygen, nitrogen, chlorine seldom, be lower than 8% acrylonitrile-butadiene-styrene copolymer (ABS resin) and paracril, contain high electronegative element coumarone indene resin seldom etc. such as acrylonitrile content.But, the preferably nonpolar organic film of high gas barrier organic film in the composite envelope type slow release fertilizer coating of the present invention.Nonpolar organic film material can be the lower molecular weight nonpolar organic matter, also can be the high molecular non-polar polymer, can also the high molecular non-polar polymer be arranged existing lower molecular weight nonpolar organic matter again.
The lower molecular weight nonpolar organic matter can be to be in solid wax, low-molecular-weight polyolefin and the petroleum resin etc. one or more under the room temperature.Wherein, wax can be petroleum wax, synthetic wax, natural wax, mineral wax etc.; Low-molecular-weight polyolefin can be a polyethylene wax, also can be other low-molecular-weight polyolefins such as low-molecular-weight polypropylene, low-molecular-weight polystyrene, low-molecular-weight polyisobutylene.Certainly, the fusing point of lower molecular weight nonpolar organic matter or softening temperature are higher for well, and the thermosetting polymer rete can adopt higher solidification value like this.
The high molecular non-polar polymer can be one or more in polyolefine, cis-1,4-polybutadiene rubber, natural rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) and terpolymer EP rubber, styrene-butadiene-styrene block copolymer and the styrene isoprene styrene block copolymer (SIS) etc.Wherein, polyolefine comprises polyethylene, polypropylene, polyisobutene and polystyrene etc.When nonpolar organic film is the rubber rete, during as retes such as cis-1,4-polybutadiene rubber, natural rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) and terpolymer EP rubbers, the rubber rete can vulcanize, and also can not vulcanize.
Nonpolar organic film material in the composite envelope type slow release fertilizer of the present invention, can be the mixture of lower molecular weight nonpolar organic matter and high molecular non-polar polymer, the fusing point or the softening temperature of the lower molecular weight nonpolar organic matter that adopt this moment can be lower than room temperature.
Nonpolar organic film in the composite envelope type slow release fertilizer of the present invention, it can be lower molecular weight nonpolar organic matter rete, also can be high molecular non-polar polymer rete, can also be the composite film of lower molecular weight nonpolar organic matter rete and high molecular non-polar polymer rete.
Composite envelope type slow release fertilizer of the present invention, the thermosetting polymer of employing can be one or more in urethane, Resins, epoxy, unsaturated polyester, resol, furane resin, unsaturated oil resin and the aminoresin.It certainly is the thermosetting polymer that other maybe can be arranged.
Can contain slowly-releasing conditioning agent and/or extender in the high gas barrier organic film of composite envelope type slow release fertilizer of the present invention.The slowly-releasing conditioning agent can be one or more in softening agent, water-soluble cpds, plant powder, longer chain fatty acid and ester, long chain aliphatic alcohol, rosin and ester thereof, pitch, clay, talcum powder, molecular sieve powder and the bone meal etc.Such as, in high molecular non-polar polymer rete, add softening agent (softening agent all is the low molecular weight polar organism basically), water-soluble cpds (comprising fertilizer itself), starch, wood powder, plant debris, pitch, clay, talcum powder, molecular sieve powder and bone meal etc., all can improve the permeability of high molecular non-polar polymer rete, to regulate the release period of composite envelope type slow release fertilizer of the present invention to water and fertilizer.Also such as, in lower molecular weight nonpolar organic matter rete, add additive such as clorafin, rosin and ester thereof, pitch, longer chain fatty acid and ester, the long chain aliphatic alcohol etc. of band polar group, also can add water-soluble cpds (comprising fertilizer itself), starch, wood powder, plant debris, clay, talcum powder, molecular sieve powder and bone meal etc.Certainly, also can be other slowly-releasing conditioning agent.
Extender can be one or more in sulphur, lime carbonate, carbon black, process white and the silicon-dioxide etc.Wherein, sulphur is preferred, and the consumption of sulphur can be between 0%～98%, best≤90%.Lime carbonate, carbon black, process white and silicon-dioxide etc. are Nano filling preferably.Certainly, also can be other extender.
The coating overall average thickness of composite envelope type slow release fertilizer of the present invention can be between 20～180 μ m.Wherein, the mean thickness of high gas barrier organic film can be between 2～30 μ m, and the overall average thickness of thermosetting polymer rete and sulfur-bearing thermosetting polymer mixture film can be between 20～180 μ m; The overall average thickness of thermosetting polymer rete can be between 0～180 μ m, and the overall average thickness of sulfur-bearing thermosetting polymer mixture film can be between 0～180 μ m.
Certainly, the overall average thickness of the coating overall average thickness of composite envelope type slow release fertilizer of the present invention, high gas barrier organic film overall average thickness, thermosetting polymer rete and sulfur-bearing thermosetting polymer mixture film, the overall average thickness of thermosetting polymer rete and the overall average thickness of sulfur-bearing thermosetting polymer mixture film etc. can be bigger than the ceiling value separately of above-mentioned proposition.These thickness are bigger, and then the release period of composite envelope type slow release fertilizer of the present invention can be longer.
Because the surface properties difference between fertilizer, sulphur, thermosetting polymer and the high gas barrier organic film material, in order to regulate mutual wetting and spreading film-forming properties and/or keying action between them, can in the coating liquid of thermosetting polymer, sulfur-bearing thermosetting polymer and high gas barrier organic film material, add tensio-active agent.Particularly, in sulfur-bearing thermosetting polymer mixture, add tensio-active agent or coupling agent, can improve the keying action between sulphur and thermosetting polymer in the sulfur-bearing thermosetting polymer mixture film, the mechanical property of sulfur-bearing thermosetting polymer mixture film is improved, make its gas barrier enhancing to water and fertilizer, and can improve the ultimate value of sulphur content in the sulfur-bearing thermosetting polymer mixture film, reduce the coating consumption of sulfur-bearing thermosetting polymer mixture film.
In addition, can add other additive in thermosetting polymer rete in the composite envelope type slow release fertilizer coating of the present invention, sulfur-bearing thermosetting polymer mixture film and the high gas barrier organic film, to reach such as certain performance of further adjusting rete or the purpose that reduces cost etc.Such as, in sulfur-bearing thermosetting polymer mixture film and thermosetting polymer rete, add the gas barrier filler (preferably Nano filling) of increment such as lime carbonate, can reach the purpose that reduces cost, can improve the purpose of rete gas barrier simultaneously.
Composite envelope type slow release urea of the present invention with urea as fertilizer sources core is example below, and the specific implementation method and the invention effect of composite envelope type slow release fertilizer of the present invention is described.Adopt stripping method evaluation sustained release performance in the water, stripping method is to measure the dissolution rate of urea in water in the composite envelope type slow release urea of the present invention in the water, specific practice is: 10 grams composite envelope type slow release urea of the present invention is soaked in 200 milliliters the water, 25 ℃ of constant temperature soak, and measure initial stage solubility rate and average differential solubility rate.The initial stage solubility rate is meant that the urea quality that begins stripping in the 24h that soaks at first accounts for the percentage ratio that urea total mass in the 10 grams composite envelope type slow release urea of the present invention is got by institute, and average differential solubility rate then is to account for 10 percentage ratios that restrain urea total mass the composite envelope type slow release urea of the present invention of getting from soaking the 2nd day urea quality to average stripping every day in the 7th day.According to initial stage solubility rate ψ
1With average differential solubility rate ψ
m, can calculate the release period t of composite envelope type slow release urea of the present invention in water (my god):
With particle diameter is in the granular industrial urea adding fluidized-bed encapsulation tool of 2.0～4.0mm, and makes Granular Urea be in boiling state, and the Granular Urea temperature remains on 65 ℃ in the fluidized-bed.With 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 for the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) melt spray is on the Granular Urea surface, and spraying reaches 3% of final finished composite envelope type slow release urea total mass up to this layer urethane film quality that forms.Then, at polyurethane film laminar surface spraying paraffin (paraffin melting point is 75 ℃) melt, reach 4% of final finished composite envelope type slow release urea total mass up to the paraffin film quality that forms.At last, (trolamine: the mol ratio of glycol ether is 0.3: 1 at the mixture of Parafilm laminar surface spraying 4,4-diphenylmethanediisocyanate MDI, trolamine and glycol ether again, the mol ratio of-NCO :-OH is 1.1: 1) melt, spraying reaches 15% of final finished composite envelope type slow release urea total mass up to this layer urethane film quality that forms.Make the urethane cures in the rete abundant, promptly get composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 132 days.
With particle diameter is in the granular industrial urea adding fluidized-bed encapsulation tool of 2.0～4.0mm, and makes Granular Urea be in boiling state, and the Granular Urea temperature remains on 70 ℃ in the fluidized-bed.Petroleum resin (softening temperature is 100 ℃) benzole soln is sprayed at urea surface, and spraying reaches 3% of final finished composite envelope type slow release urea total mass up to the petroleum resin film quality that forms.Then, at the F98-1 type synvaren of petroleum resin film surface spraying plasticizer-containing butyl phthalate benzyl ester 10%, spraying reaches 19% of final finished composite envelope type slow release urea total mass up to the resol rete quality that forms.Make the phenolic resin curing in the rete abundant, promptly get composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 119 days.
With particle diameter is in the granular industrial urea adding fluidized-bed encapsulation tool of 2.0～4.0mm, and makes Granular Urea be in boiling state, and the Granular Urea temperature remains on 70 ℃ in the fluidized-bed.S-583 type unsaturated polyester prepolymer (containing benzoyl peroxide 1.5% and little amount of catalyst) is sprayed on the Granular Urea surface, and spraying reaches 19% of final finished composite envelope type slow release urea total mass up to the unsaturated polyester resin film quality that forms.Then, the cyclohexane solution of styrene-butadiene-styrene block copolymer is sprayed at the unsaturated polyester resin film surface, and spraying reaches 3% of final finished composite envelope type slow release urea total mass up to the styrene-butadiene-styrene block copolymer film quality that forms.Thorough drying is removed hexanaphthene in the rete, and the unsaturated polyester resin in the rete is solidified fully, promptly gets composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 142 days.
With particle diameter is in the granular industrial urea adding fluidized-bed encapsulation tool of 2.0～4.0mm, and makes Granular Urea be in boiling state, and the Granular Urea temperature remains on 75 ℃ in the fluidized-bed.With 4,4-diphenylmethanediisocyanate MDI, (trolamine: the mol ratio of glycol ether is 0.2: 1 to the mixture of trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) melt slowly sprays toward the Granular Urea surfaces from two groups of different nozzles respectively simultaneously with about 150 ℃ fusion sulphur, by controlling their spraying throughput ratio, making the average quality mark of sulphur in the sulfur-containing polyurethane mixture film of formation is 70%, and spraying reaches 6% of final finished composite envelope type slow release urea total mass up to the sulfur-containing polyurethane mixture film quality that forms.Then, the benzole soln of polyethylene wax (molecular weight is 1800) is sprayed at sulfur-containing polyurethane blend films laminar surface, reaches 3% of final finished composite envelope type slow release urea total mass up to the polyethylene wax film quality that forms, thorough drying is removed benzene in the rete.At last, spray 4 respectively from two groups of different nozzles, (trolamine: the mol ratio of glycol ether is 0.2: 1 for 4-diphenylmethanediisocyanate MDI sulfur-containing mixture (massfraction of sulphur is 25%) and trolamine-glycol ether sulfur-containing mixture, the massfraction of sulphur is 25%) at the polyethylene wax film surface, the spraying throughput ratio of control MDI sulfur-containing mixture and trolamine-glycol ether sulfur-containing mixture, make by in the sulfur-containing polyurethane mixture film that MDI sulfur-containing mixture and trolamine-reaction of glycol ether sulfur-containing mixture forms-mol ratio of NCO :-OH is 1.1: 1, spraying reaches 14% of final finished composite envelope type slow release urea total mass up to this layer sulfur-containing polyurethane mixture film quality of formation.Make the urethane cures in the rete abundant, promptly get composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 156 days.
Embodiment 5
With particle diameter is in the granular industrial urea adding fluidized-bed encapsulation tool of 2.0～4.0mm, and makes Granular Urea be in boiling state, and the Granular Urea temperature remains on 75 ℃ in the fluidized-bed.Benzole soln at Granular Urea surface spraying cis-1,4-polybutadiene rubber rubber reaches 2% of final finished composite envelope type slow release urea total mass up to the cis-1,4-polybutadiene rubber rubber film quality that forms, and thorough drying is removed benzene in the rete.Then, the furan resin adhesive of the plasticizer-containing diisobutyl phthalate 10% fusion sulphur with about 150 ℃ is slowly sprayed toward cis-1,4-polybutadiene rubber rubber film surfaces simultaneously from two groups of different nozzles respectively; The spraying flow of fusion sulphur is maximum when beginning, reduce to gradually when finishing is zero, and the spraying flow certain value from the outset of furan resin adhesive increases to maximum when finishing gradually, so that the massfraction of sulphur is reduced to 0% gradually from 80% in the sulfur-bearing furane resin mixture film that forms, the average quality mark of sulphur is 50% in the whole sulfur-bearing furane resin mixture film, and whole sulfur-bearing furane resin mixture film quality accounts for 22% of final finished composite envelope type slow release urea total mass.Furane resin in the rete are solidified fully, promptly get composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 151 days.
Embodiment 6
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 75 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum, and the rotary drum internal pressure is 0.15MPa.The S-583 type unsaturated polyester pre-polymer mixture (containing benzoyl peroxide 1.5% and little amount of catalyst) of the plasticizer-containing butyl phthalate benzyl ester 10% fusion sulphur with about 150 ℃ is slowly sprayed toward the Granular Urea surfaces simultaneously from two groups of different nozzles respectively, by controlling their spraying throughput ratio, making the average quality mark of sulphur in the sulfur-bearing unsaturated polyester resin mixtures rete of formation is 60%, and spraying reaches 23% of final finished composite envelope type slow release urea total mass up to the sulfur-bearing unsaturated polyester resin mixtures film quality that forms.Then, again at sulfur-bearing unsaturated polyester resin mixtures film surface spraying high-impact polystyrene benzole soln, reach 3% of final finished composite envelope type slow release urea total mass up to the high-impact polystyrene film quality that forms, thorough drying is removed benzene in the rete.Unsaturated polyester resin in the rete is solidified fully, promptly get composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 153 days.
Embodiment 7
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 70 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.CYD-115 type epoxy prepolymer is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with the mixture melt of mixed amine solidifying agent and about 150 ℃ fusion sulphur, by controlling their spraying throughput ratio, making the average quality mark of sulphur in the sulfur-bearing epoxy resin composition rete of formation is 70%, and spraying reaches 12% of final finished composite envelope type slow release urea total mass up to the sulfur-bearing epoxy resin composition film quality that forms.Then, benzole soln at sulfur-bearing epoxy resin composition film surface spraying ethylene-propylene rubber(EPR) (containing the benzoyl peroxide vulcanizing agent), reach 1% of final finished composite envelope type slow release urea total mass up to the ethylene-propylene rubber(EPR) film quality that forms, thorough drying is removed benzene in the rete.At last, at the mixture melt of ethylene-propylene rubber(EPR) film surface spraying CYD-115 type epoxy prepolymer and mixed amine solidifying agent, reach 10% of final finished composite envelope type slow release urea total mass again up to the Resins, epoxy rete quality that forms.Make in the rete ethylene-propylene rubber(EPR) sulfuration fully and the Resins, epoxy resin solidification abundant, promptly get composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 110 days.
Embodiment 8
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 70 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.With 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 for the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) melt spray is in the Granular Urea surface, reaches 4% of final finished composite envelope type slow release urea total mass up to the urethane rete quality that forms.Then, the industrial naptha solution at polyurethane film laminar surface spraying styrene-butadiene rubber(SBR) rubber reaches 2% of final finished composite envelope type slow release urea total mass up to the styrene-butadiene rubber(SBR) rubber film quality that forms, and thorough drying is removed industrial naptha in the rete.At last, with 4,4-diphenylmethanediisocyanate MDI, (trolamine: the mol ratio of glycol ether is 0.3: 1 to the mixture of trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.15: 1) melt slowly sprays toward styrene-butadiene rubber(SBR) rubber retes from two groups of different nozzles respectively simultaneously with about 150 ℃ fusion sulphur, by controlling their spraying throughput ratio, making the average quality mark of sulphur in the sulfur-containing polyurethane mixture film of formation is 60%, and spraying reaches 17% of final finished composite envelope type slow release urea total mass up to the sulfur-containing polyurethane mixture film quality that forms.Make the urethane cures in the rete abundant, promptly get composite envelope type slow release urea.The release period of prepared composite envelope type slow release urea is 145 days.
Embodiment 9
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is 70% sulfur-bearing Resins, epoxy (CYD-115 type) mixture film for the sulphur massfraction, and this rete accounts for 5% of composite envelope type slow release urea total mass.Second rete is coumarone indene resin (softening temperature of coumarone indene resin is 100 a ℃) rete, and this rete accounts for 3% of composite envelope type slow release urea total mass.The tertiary membrane layer is 50% sulfur-bearing tough epoxy resin (national capital YD-171 type) mixture film for the sulphur massfraction, and this rete accounts for 13% of composite envelope type slow release urea total mass.The 4th rete is the CYD-115 type Resins, epoxy rete of plasticizer-containing dibutyl phthalate 10%, and this rete accounts for 3% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 148 days.
Embodiment 10
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the urethane rete that forms, this rete accounts for 2% of composite envelope type slow release urea total mass.Second rete is mixture (mass ratio of polyethylene and paraffin is 6: the 1) rete of polyethylene and paraffin, and this rete accounts for 2% of composite envelope type slow release urea total mass.The tertiary membrane layer is that (massfraction of sulphur is 60% to butyl phthalate benzyl ester plastifying sulfur-bearing S-583 type unsaturated polyester ester mixture, the mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: 4) rete, this rete accounts for 16% of composite envelope type slow release urea total mass.The 4th rete is 4, (trolamine: the mol ratio of butyleneglycol is 0.2: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and butyleneglycol, the mol ratio of-NCO :-OH is 1.1: 1) the urethane rete that forms, this rete accounts for 2% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 142 days.
Embodiment 11
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is a S-583 type unsaturated polyester rete, and this rete accounts for 2% of composite envelope type slow release urea total mass.Second rete is that (massfraction of sulphur is 80% to butyl phthalate benzyl ester plastifying sulfur-bearing S-583 type unsaturated polyester ester mixture, the mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: 7) rete, this rete accounts for 8% of composite envelope type slow release urea total mass.The tertiary membrane layer is paraffin (melting point of paraffin wax is 70 a ℃) rete, and this rete accounts for 2% of composite envelope type slow release urea total mass.The 4th rete is a natural rubber rubber rete, and this rete accounts for 1% of composite envelope type slow release urea total mass.The 5th rete is that (massfraction of sulphur is 50% to butyl phthalate benzyl ester plastifying sulfur-bearing S-772 type unsaturated polyester ester mixture, the mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: 4) rete, this rete accounts for 7% of composite envelope type slow release urea total mass.The 6th rete is butyl phthalate benzyl ester plastifying S-583 type unsaturated polyester resin (mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: a 7) rete, and this rete accounts for 2% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 167 days.
Embodiment 12
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is the styrene-butadiene-styrene block copolymer rete, and this rete accounts for 2% of composite envelope type slow release urea total mass.Second rete is 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the sulfur-containing polyurethane mixture film (massfraction of sulphur is 80%) that forms, this rete accounts for 18% of composite envelope type slow release urea total mass.The tertiary membrane layer is 4, (trolamine: the mol ratio of glycol ether is 0.1: 2 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the urethane rete that forms, this rete accounts for 3% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 152 days.
Embodiment 13
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is that (mass ratio of dibutyl phthalate and Resins, epoxy is 1: 9 to dibutyl phthalate plastifying sulfur-bearing CYD-115 type epoxy resin composition, the massfraction of sulphur is 80%) rete, this rete accounts for 15% of composite envelope type slow release urea total mass.Second rete is a national capital YD-171 type tough epoxy resin film layer, and this rete accounts for 5% of composite envelope type slow release urea total mass.The tertiary membrane layer is the mixture film (mass ratio of polyethylene and cis-1,4-polybutadiene rubber is 4: 1) of polyethylene and cis-1,4-polybutadiene rubber, and this rete accounts for 2% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 149 days.
Embodiment 14
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is 4, (trolamine: the mol ratio of glycol ether is 0.1: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the urethane rete that forms, this rete accounts for 2% of composite envelope type slow release urea total mass.Second rete is 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the sulfur-containing polyurethane mixture film (massfraction of sulphur is 70%) that forms, this rete accounts for 17% of composite envelope type slow release urea total mass.The tertiary membrane layer is the styrene-butadiene-styrene block copolymer rete, and this rete accounts for 3% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 160 days.
Embodiment 15
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the urethane rete that forms, this rete accounts for 2% of composite envelope type slow release urea total mass.Second rete is paraffin and bituminous mixture (paraffin and bituminous mass ratio are 2: 1, and melting point of paraffin wax is 75 ℃) rete, and this rete accounts for 4% of composite envelope type slow release urea total mass.The tertiary membrane layer is 4, (trolamine: the mol ratio of glycol ether is 0.3: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the urethane rete that forms, this rete accounts for 15% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 98 days.
Embodiment 16
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is a S-583 type unsaturated polyester resin rete, and this rete accounts for 19% of composite envelope type slow release urea total mass.Second rete is triphenylphosphate plastifying polystyrene (mass ratio of triphenylphosphate and polystyrene is 1: a 1) rete, and this rete accounts for 3% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 50 days.
Embodiment 17
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is that (massfraction of sulphur is 60% to butyl phthalate benzyl ester plastifying sulfur-bearing S-583 type unsaturated polyester mixture film, the mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: 9), this rete accounts for 23% of composite envelope type slow release urea total mass.Second rete is the high-impact polystyrene rete of montmorillonoid-containing (particle diameter is 25 μ m) 6%, and this rete accounts for 3% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 98 days.
Embodiment 18
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is that (massfraction of sulphur is 60% to butyl phthalate benzyl ester plastifying sulfur-bearing S-583 type unsaturated polyester mixture film, the mass ratio of butyl phthalate benzyl ester and S-583 type unsaturated polyester resin is 1: 9), this rete accounts for 23% of composite envelope type slow release urea total mass.Second rete is for containing the high-impact polystyrene rete of molecular sieve powder (particle diameter is 30 μ m) 15%, and this rete accounts for 3% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 70 days.
Embodiment 19
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is a butyl phthalate benzyl ester plastifying S-583 type unsaturated polyester rete (mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: 9), and this rete accounts for 19% of composite envelope type slow release urea total mass.Second rete is the sulfur-bearing styrene-butadiene-styrene block copolymer mixture film of sulphur massfraction 40%, and this rete accounts for 4% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 134 days.
Embodiment 20
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is that butyl phthalate benzyl ester plastifying contains nano-calcium carbonate S-583 type unsaturated polyester rete (massfraction of nano-calcium carbonate is 30%, the mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: 9), this rete accounts for 22% of composite envelope type slow release urea total mass.Second rete is the styrene-butadiene-styrene block copolymer mixture film (massfraction of nano-calcium carbonate is 50%) that contains nano-calcium carbonate, and this rete accounts for 5% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 136 days.
Embodiment 21
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the urethane rete that forms, this rete accounts for 2% of composite envelope type slow release urea total mass.Second rete is petroleum resin (softening temperature of petroleum resin is 100 ℃) retes, and this rete accounts for 2% of composite envelope type slow release urea total mass.The tertiary membrane layer is a butyl phthalate benzyl ester plastifying S-583 type unsaturated polyester rete (mass ratio of butyl phthalate benzyl ester and unsaturated polyester resin is 1: 9), and this rete accounts for 8% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 82 days.
Embodiment 22
The raw material urea that adopts is that particle diameter is the granular industrial urea of 2.0～4.0mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Granular Urea surface first rete outward is a S-583 type unsaturated polyester resin rete, and this rete accounts for 2% of composite envelope type slow release urea total mass.Second rete is the high-impact polystyrene rete, and this rete accounts for 1.5% of composite envelope type slow release urea total mass.The tertiary membrane layer is a butyl phthalate benzyl ester plastifying S-583 type unsaturated polyester rete (mass ratio of butyl phthalate benzyl ester and S-583 type unsaturated polyester resin is 1: 9), and this rete accounts for 5% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 63 days.
Embodiment 23
The raw material urea that adopts is the sheet urea of Φ 8 * 3mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Sheet urea surface first rete outward is petroleum resin (softening temperature is 90 ℃) retes, and this rete accounts for 2.5% of composite envelope type slow release urea total mass.Second rete is a butyl phthalate benzyl ester plastifying S-583 type unsaturated polyester rete (mass ratio of butyl phthalate benzyl ester and S-583 type unsaturated polyester resin is 1: 6), and this rete accounts for 14% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 223 days.
Embodiment 24
The raw material urea that adopts is the sheet urea of Φ 8 * 3mm, and each rete coating method can adopt above-mentioned corresponding method or other suitable method.Sheet urea surface first rete outward is paraffin (paraffin melting point is 70 a ℃) rete, and this rete accounts for 1.5% of composite envelope type slow release urea total mass.Second rete is 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 to the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) the sulfur-containing polyurethane mixture film (massfraction of sulphur is 20%) that forms, this rete accounts for 22% of composite envelope type slow release urea total mass.The release period of prepared composite envelope type slow release urea is 203 days.
Comparative example 1
With particle diameter is in the granular industrial urea adding fluidized-bed encapsulation tool of 2.0～4.0mm, and makes Granular Urea be in boiling state, and the Granular Urea temperature remains on 75 ℃ in the fluidized-bed.With 4, (trolamine: the mol ratio of glycol ether is 0.2: 1 for the mixture of 4-diphenylmethanediisocyanate MDI, trolamine and glycol ether, the mol ratio of-NCO :-OH is 1.1: 1) melt spray is in the Granular Urea surface, and spraying is 20% until the polyurethane coated massfraction that forms.Make urethane cures fully make membrane wrapping sustained-release urea, its release period is 32 days.
Comparative example 2
With particle diameter is in the granular industrial urea adding fluidized-bed encapsulation tool of 2.0～4.0mm, and makes Granular Urea be in boiling state, and the Granular Urea temperature remains on 75 ℃ in the fluidized-bed.The S-583 type unsaturated polyester prepolymer that will contain butyl phthalate benzyl ester plasticizer (contains benzoyl peroxide 1.5% and little amount of catalyst, the mass ratio of butyl phthalate benzyl ester and S-583 type unsaturated polyester prepolymer is 1: 9) be sprayed at the Granular Urea surface, spraying is 20% until the plasticising unsaturated polyester resin coating massfraction that forms.Unsaturated polyester resin is solidified fully make membrane wrapping sustained-release urea, its release period is 40 days.
Claims (7)
1. composite envelope type slow release fertilizer, coating by fertilizer core [1] and fertilizer core outside is formed, it is characterized in that: coating comprises (a) high gas barrier organic film [2], and (b) sulfur-bearing thermosetting polymer mixture film [4] has or do not have (c) thermosetting polymer rete [3]; Wherein, high gas barrier organic film is nonpolar organic film, and thermosetting polymer is one or more in urethane, Resins, epoxy, unsaturated polyester, resol and the furane resin.
2. composite envelope type slow release fertilizer according to claim 1 is characterized in that: nexine or middle layer that high gas barrier organic film is a whole coating.
3. composite envelope type slow release fertilizer according to claim 1 is characterized in that: nonpolar organic film material is lower molecular weight nonpolar organic matter and/or high molecular non-polar polymer; The lower molecular weight nonpolar organic matter is to be in solid wax and the petroleum resin one or more under the room temperature; The high molecular non-polar polymer is one or more in polyolefine, cis-1,4-polybutadiene rubber, natural rubber, polyisoprene rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, ethylene-propylene rubber(EPR) and terpolymer EP rubber, styrene-butadiene-styrene block copolymer and the styrene isoprene styrene block copolymer (SIS).
4. composite envelope type slow release fertilizer according to claim 1 is characterized in that: the average quality mark of sulphur is 20%～95% in the sulfur-bearing thermosetting polymer mixture film.
5. composite envelope type slow release fertilizer according to claim 1 is characterized in that: contain slowly-releasing conditioning agent and/or extender in the high gas barrier organic film.
6. composite envelope type slow release fertilizer according to claim 5 is characterized in that: the slowly-releasing conditioning agent is one or more in softening agent, plant powder, rosin and ester thereof, pitch, clay, talcum powder, molecular sieve powder and the bone meal.
7. composite envelope type slow release fertilizer according to claim 5 is characterized in that: extender is one or more in sulphur, lime carbonate, carbon black, process white and the silicon-dioxide.
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| US7771505B2 (en) * | 2008-07-16 | 2010-08-10 | Agrium Inc. | Controlled release fertilizer composition |
| CN101747123B (en) * | 2009-12-19 | 2012-06-27 | 山西学产研化工产业技术中心(有限公司) | Method for preparing polyurethane-polyurea coated fertilizer |
| CN102320883B (en) * | 2011-06-22 | 2014-08-13 | 冯岁寒 | Polyurethane/epoxy resin compound material coated controlled release fertilizer and preparation method thereof |
| CN102603398B (en) * | 2012-03-01 | 2013-12-25 | 兰州大学 | Slow release fertilizer and preparation method thereof |
| CN102775234B (en) * | 2012-08-16 | 2014-06-04 | 菏泽金正大生态工程有限公司 | Controlled-release zinc fertilizer and preparation method thereof |
| CN104447016A (en) * | 2014-12-09 | 2015-03-25 | 徐同珊 | Production method of controlled release chemical fertilizer based on hylocereus undulatus leaves |
| CN104521951A (en) * | 2014-12-24 | 2015-04-22 | 陕西上格之路生物科学有限公司 | Pesticide granules with slow release effect |
| CN108586060B (en) * | 2018-06-25 | 2021-08-13 | 山东农业大学 | Functional composite coated controlled-release fertilizer with polyolefin wax as base coat and production method thereof |
| CN111825504A (en) * | 2020-07-30 | 2020-10-27 | 张立强 | Resin coated fertilizer and preparation method thereof |
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