CN101234922A - Environment-friendly type slow release fertilizer - Google Patents
Environment-friendly type slow release fertilizer Download PDFInfo
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- CN101234922A CN101234922A CNA2007100068381A CN200710006838A CN101234922A CN 101234922 A CN101234922 A CN 101234922A CN A2007100068381 A CNA2007100068381 A CN A2007100068381A CN 200710006838 A CN200710006838 A CN 200710006838A CN 101234922 A CN101234922 A CN 101234922A
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Abstract
The invention discloses an environment-friendly slow release fertilizer, which consists of fertilizer core and film with which the fertilizer core is covered. The covering film is degradable polymer sulphur-contained compound film or compound film of degradable polymer film and degradable polymer sulphur-contained film. An average massfraction of sulphur in the covering film ranging from 50 to 98 percent is favorable and an average massfraction of 80 percent to 95 percent is optimal. The degradable polymer can be one or more among amino resin, unsaturated oleoresin, polyvinyl alcohol, polymer acetal resin, natural polymer, and derivatives. The slow release fertilizer covering film also has an organic film with high permeability resistance, which is suggested to be a non-polarity organic film. The average thickness of the covering film can range from 20 to 150Mum, and the thickness of the organic film can range from 0 to 30Mum. The environment-friendly slow release fertilizer has the advantages of longer release period, low cost, and no or few environmental pollutions.
Description
One, technical field
The present invention relates to a kind of coating type sustained-release chemical fertilizer, particularly a kind of environment-friendly type slow release fertilizer belongs to the chemical fertilizer industry field.
Two, background technology
At present, release controlled fertilizer is the developing direction of world agriculture chemical fertilizer.Particularly, coated fertilizer is environment Wholly-degradable or absorbable complete environmental friendliness coating type sustained-release chemical fertilizer, will be the main direction of release controlled fertilizer from now on.
But, fully the degradable or the absorbable polymer that adopt of environmental friendliness coating type sustained-release chemical fertilizer all is the high-permeability material, so adopt the release period of the complete environmental friendliness coating type sustained-release chemical fertilizer that degradable polymer (such as urea-formaldehyde resin, tung oil resin etc.) prepares all shorter separately.Such as, the simple release period of complete environmental friendliness coating type sustained-release chemical fertilizer in water of urea-formaldehyde resin coating that adopt generally has only several days, adopts the release period of complete environmental friendliness coating type sustained-release chemical fertilizer in water of tung oil coating generally also to have only about 20 days merely.Release period not length is the difficult problem that complete environmental friendliness coating type sustained-release chemical fertilizer is not resolved always.In addition, the cost of the complete environmental friendliness coating type sustained-release chemical fertilizer that independent employing degradable polymer (such as tung oil resin, urea-formaldehyde resin etc.) prepares is higher, being unfavorable for applying, is another problem that complete environmental friendliness coating type sustained-release chemical fertilizer exists.
Three, summary of the invention
The object of the present invention is to provide a kind of release period long, coating fully or almost completely degradable and the relatively low environment-friendly type slow release fertilizer of cost.
The technical solution that realizes the object of the invention is: a kind of environment-friendly type slow release fertilizer, coating by chemical fertilizer core and chemical fertilizer core outside is formed, wherein coating is the degradable polymer sulfur-containing mixture film, or the composite film of degradable polymer sulfur-containing mixture film and degradable polymer rete.
The degradable polymer that adopts in the environment-friendly type slow release fertilizer coating of the present invention is non-water-soluble degradable polymer, can be in aminoresin, unsaturated oil resin, polyvinyl alcohol and multipolymer Derlin and natural polymer and the derivative thereof etc. one or more.Wherein, natural polymer and derivative thereof can be one or more in nitrocellulose, lac, cellulose acetate, cross-linking starch, chitin derivativ and the lignin derivative etc.
In the coating of environment-friendly type slow release fertilizer of the present invention, sulphur average quality mark is good with 50%～98%, is preferably 80%～95%.When coating was the composite film of degradable polymer sulfur-containing mixture film and degradable polymer rete, the degradable polymer sulfur-containing mixture film is the nexine or the middle layer of whole coating preferably.Especially, preferably exist in the degradable polymer sulfur-containing mixture film sulphur massfraction be 90%～99.9% around the sealing surface of chemical fertilizer core.
In the degradable polymer sulfur-containing mixture film of environment-friendly type slow release fertilizer of the present invention, the best distribution gradient of sulphur massfraction, Gradient distribution mode preferably from the chemical fertilizer core outward the sulphur massfraction reduce gradually.
In the coating of environment-friendly type slow release fertilizer of the present invention, except that containing the degradable polymer sulfur-containing mixture film, perhaps except that containing degradable polymer sulfur-containing mixture film and degradable polymer rete, high gas barrier organic film can also be arranged.Wherein, high gas barrier organic film can be the outermost layer of whole coating, but the preferably nexine of whole coating or middle layer.High gas barrier organic film is preferably nonpolar organic film, and nonpolar organic film material can be non-polar low molecular weight organism and/or non-polar polymer.The non-polar low molecular weight organism can be one or more in petroleum resin of the polyolefine of wax, fusing point or softening temperature 〉=40 ℃ of fusing point 〉=40 ℃ and molecular weight≤2000 or polystyrene and softening temperature 〉=40 ℃ etc.Non-polar polymer can be one or more in polyolefine, polystyrene, 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.For environment-friendly type slow release fertilizer of the present invention, high gas barrier organic film is when having high gas barrier polymer film in high gas barrier polymer film or the high gas barrier organic film, the equilibrium swelling rate that the elongation at break of high gas barrier polymer film whole coating when the environment-friendly type slow release fertilizer of its coating is immersed in the water expands.
The coating overall average thickness of environment-friendly type slow release fertilizer of the present invention can be 20～150 μ m, and the degradable polymer thicknesses of layers can be 0～30 μ m, and high gas barrier organic film thickness can be 0～30 μ m.Wherein, coating overall average thickness is preferably 30～120 μ m, and the degradable polymer thicknesses of layers is preferably 0～20 μ m, and high gas barrier organic film thickness is preferably 0～20 μ m.
Compare with the prior art that independent employing degradable polymer coating chemical fertilizer prepares release controlled fertilizer, environment-friendly type slow release fertilizer of the present invention has remarkable advantage.Because sulphur is the nutriment in a fertilizer that plant needs, so the same environmentally safe of release controlled fertilizer of the present invention, is complete environment-friendly type release controlled fertilizer.Simultaneously, because sulphur has high gas barrier to water and chemical fertilizer, the release period that therefore adopts degradable polymer and sulphur to mix to coat the release controlled fertilizer of the present invention that chemical fertilizer prepares is longer than adopting degradable polymer to coat the release period of the release controlled fertilizer that chemical fertilizer prepares separately.In addition, sulphur itself is inorganic adhesive, and its fusing point is lower, has good coating characteristic, can be separately as the coating thing, also can be compound as tackiness agent with other tackiness agent, and in the chemical fertilizer coating, can't show adhesive effect and compare with the inorganic additives of coating characteristic and have obvious advantage.Particularly its price is more much lower than the price of degradable polymer, even also lower by about 50% than urea price, the cost that therefore adopts degradable polymer and sulphur to mix to coat the release controlled fertilizer of the present invention that chemical fertilizer prepares is more much lower than adopting degradable polymer to coat the cost of the release controlled fertilizer that chemical fertilizer prepares separately.
Compare with the prior art (USA 6,617,412) that adopts the fertile preparation of urethane and the membranization of sulphur hybrid packet release controlled fertilizer, environment-friendly type slow release fertilizer of the present invention has remarkable advantage equally.The first, urethane are not the environmentally degradable polymkeric substance, therefore adopt the release controlled fertilizer of the fertile preparation of urethane and the membranization of sulphur hybrid packet that environment is had pollution, are not complete environment-friendly type slow release fertilizers.It two is, the price of urethane, Resins, epoxy etc. is very high, and the price comparison of degradable polymers such as urea-formaldehyde resin, melamine formaldehyde resin, polyvinyl alcohol and multipolymer Derlin thereof that the present invention adopts and unsaturated oil (such as tung oil) resin is inexpensive.Such as, the cost index of pure urea is by 100, then the cost index of sulphur is about 50, the cost index of urea-formaldehyde resin, melamine formaldehyde resin, polyvinyl acetal resin and tung oil resin is about 450,600,1200 and 900 respectively, and the cost index of urethane, Resins, epoxy is about respectively about 2500 and 2000, so the cost of environment-friendly type slow release fertilizer of the present invention is much lower.Particularly, when adopting urea-formaldehyde resin or melamine formaldehyde resin, because they itself are that (nitrogen content of urea-formaldehyde resin and melamine formaldehyde resin is about 30% and 54% respectively to slow-release nitrogen fertilizer, and the nitrogen content of urea is about 45%), this moment, environment-friendly type slow release fertilizer of the present invention was with the fertilizer integument type release controlled fertilizer, the nutriment in a fertilizer height, thus release controlled fertilizer to amount to cost lower.
Compound high gas barrier organic film has outstanding advantage in the coating of environment-friendly type slow release fertilizer of the present invention.Because high gas barrier organic film to the gas barrier height of water and chemical fertilizer, therefore makes the environment-friendly type slow release fertilizer of the present invention of compound high gas barrier organic film can have long release period.When particularly high gas barrier organic film is nonpolar organic film, because nonpolar organic film is very low to the transmitance of water and chemical fertilizer, water and chemical fertilizer mainly only see through from nonpolar organic film fault location, and therefore thin nonpolar organic film just can give environment-friendly type slow release fertilizer of the present invention very long release period.Simultaneously, during compound high gas barrier organic film, can adopt the way of in high gas barrier organic film, adding the slowly-releasing conditioning agent, flexibly, effectively and economically the adjustment release phase in the coating.If high gas barrier organic film adopts low perviousness (such as nonpolar) low-molecular-weight organic matter, polyolefine or polystyrene and petroleum resin etc. such as wax, molecular weight≤2000, because low-molecular-weight organic matter is generally all biodegradable in environment, therefore the environment-friendly type slow release fertilizer of the present invention of compound high gas barrier organic film can be complete environment-friendly type release controlled fertilizer equally.Even high gas barrier organic film adopts high gas barrier polymkeric substance, although they are difficult degradations,, to compare with the prior art release controlled fertilizer because their usage quantity is very little, its pollution to environment is very little, has obvious advantage equally.
Four, embodiment
Environment-friendly type slow release fertilizer of the present invention is made up of the coating of chemical fertilizer core and chemical fertilizer core outside, and wherein coating is the degradable polymer sulfur-containing mixture film, or the composite film of degradable polymer rete and degradable polymer sulfur-containing mixture film.
The chemical fertilizer core of environment-friendly type slow release fertilizer of the present invention can be nitrogenous fertilizer, phosphate fertilizer, potash fertilizer or compound fertilizer etc.The shape of chemical fertilizer core can be granular, sheet etc., but with granular be good, preferably spherical.
The sulphur massfraction should not be low excessively in the coating of environment-friendly type slow release fertilizer of the present invention, and the release period of crossing environment-friendly type slow release fertilizer when hanging down is shorter, and since degradable polymer consumption height, the cost height of environment-friendly type slow release fertilizer.Therefore, the average quality mark of sulphur is preferably between 80%～95% to be good between 50%～98% in the coating.Certainly, being lower than 50% also is fine.
In the environment-friendly type slow release fertilizer of the present invention, the degradable polymer sulfur-containing mixture film is meant the mixture film of degradable polymer and sulphur.In the degradable polymer sulfur-containing mixture film of environment-friendly type slow release fertilizer of the present invention, the best distribution gradient of sulphur massfraction, Gradient distribution mode preferably from the chemical fertilizer core outward the sulphur massfraction reduce gradually, even be reduced to zero.Like this, even in coating under the sulphur average quality mark condition with higher, the sulphur content of the outer layer segment of coating still can be lower, makes outer layer segment have high toughness.Otherwise even under the situation that sulphur average quality mark is lower in coating, coating inside can have the higher sealer coat of sulfur mass fraction equally, brings into play high gas barrier effect, to give long release period.For environment-friendly type slow release fertilizer of the present invention, if coating is the composite film of degradable polymer rete and degradable polymer sulfur-containing mixture film, the degradable polymer sulfur-containing mixture film can be the skin of whole composite film, but preferably be in the nexine or the middle layer of composite film, and the degradable polymer rete is good with the skin as whole composite film.Particularly, sulphur average quality mark height in coating, such as 80% when above, degradable polymer sulfur-containing mixture film skin can have the not sulfureted degradable polymer rete of one deck thin (such as being lower than 20 μ m), and the degradable polymer rete that toughness is high relatively like this can be given the shock resistance of coating necessity.
Especially, preferably exist in the degradable polymer sulfur-containing mixture film sulphur massfraction be 90%～99.9% around the sealing surface of chemical fertilizer core.If have the sulphur massfraction in the coating and be 90%～99.9% sealing surface around the chemical fertilizer core, even sulphur average quality mark not high (shock resistance of coating is better) in the coating, the slow pathway that but the sulphur massfraction is 90%～99.9% sealing surface becomes that control fertilizer sees through, so environment-friendly type slow release fertilizer of the present invention still can have long release period.
The degradable polymer that adopts in the environment-friendly type slow release fertilizer coating of the present invention can be in the high degree of acetalization Derlin of aminoresin, unsaturated oil resin, polyvinyl alcohol and multipolymer thereof and natural polymer and the derivative thereof etc. one or more.Wherein, natural polymer and derivative thereof can be one or more in nitrocellulose, lac, cellulose acetate, cross-linking starch, chitin derivativ and the lignin derivative etc.Certainly, can be the modified resin of above-mentioned degradable polymer, can also be the degradable polymer that maybe can contain other.Degradable polymer in the environment-friendly type slow release fertilizer coating of the present invention is non-water-soluble, although perhaps the prepolymer of Cai Yonging is water miscible, but the degradable polymer in the final rete that forms should become non-water-soluble, such as the prepolymer that forms urea-formaldehyde resin and melamine formaldehyde resin can be water miscible, but the urea-formaldehyde resin and the melamine formaldehyde resin that form through curing cross-linked become non-water-soluble.Like this, environment-friendly type slow release fertilizer of the present invention degradable polymer can not occur and be fallen so that make coating lose problem to the gas barrier effect of water and chemical fertilizer by water-soluble after applying Tian Tuzhong, makes environment-friendly type slow release fertilizer of the present invention can obtain long release period.
In described degradable polymer, aminoresin is preferred, especially urea-formaldehyde resin and melamine formaldehyde resin (comprising modified urea-formaldehyde resin and modified cyanurotriamide-formaldehyde resin), they itself are exactly that slow-release nitrogen fertilizer and price are low, therefore adopt the nutriment in a fertilizer content height of the environment-friendly type slow release fertilizer of the present invention of their preparations, it is low to amount to cost.The unsaturated oil resin is the resin that is formed by the unsaturated oil crosslinking reaction, because can be without solvent in the unsaturated oil coating process, so the unsaturated oil resin also can be preferred.Unsaturated oil is meant the natural oil that contains two keys in the molecular structure, crosslinking reaction can take place, such as tung oil, soybean oil, oleum lini or dehydrated castor wet goods, wherein tung oil is the lower unsaturated oil of price, the tung oil resin film layer that it is cross-linked to form is also stronger to the gas barrier of water and chemical fertilizer, therefore be preferred unsaturated oil, the environment-friendly type slow release fertilizer of the present invention of its coating preparation has the release period of growing.Secondly, the high degree of acetalization Derlin (degree of acetalization 〉=50%) of non-water-soluble polyvinyl alcohol and multipolymer thereof and nitrocellulose also are to consider the degradable coated fertilizer selected for use.The Derlin of polyvinyl alcohol and multipolymer thereof can be methylal resin, acetate resin, butyral resin of polyvinyl alcohol and multipolymer thereof etc.
In order to regulate film performance (such as toughness etc.), in degradable polymer rete or degradable polymer sulfur-containing mixture film, can add low-molecular-weight organic matter (as softening agent) etc., such as adding the plasticizer phthalic acid dibutylester in the nitrocellulose, add plasticizer phthalic acid butyl ester benzyl ester etc. in polyvinyl alcohol and the multipolymer Derlin thereof.In addition, in degradable polymer rete or degradable polymer sulfur-containing mixture film, can also add a spot of sterilant or fungistat (being preferably water-insoluble sterilant or fungistat) and chemical fertilizer inhibitor (such as the urea inhibitor) etc.Certainly, also can in degradable polymer rete or degradable polymer sulfur-containing mixture film, sneak into toughness polymer and improve rete toughness, but, not be preferred therefore because of toughness polymer mostly is the difficult degradation polymkeric substance.
For environment-friendly type slow release fertilizer of the present invention, coating removes and contains the degradable polymer sulfur-containing mixture film, perhaps except that containing degradable polymer sulfur-containing mixture film and degradable polymer rete, can also contain high gas barrier organic film.Wherein, the outermost rete that high gas barrier organic film can be a whole coating, but the preferably nexine or the middle layer of whole coating.
High gas barrier organic film in the environment-friendly type slow release fertilizer coating of the present invention, be meant the rete that the transmitance of water and chemical fertilizer is lower than simple degradable polymer rete, be high gas barrier organic film material to the transmitance of water and chemical fertilizer be lower than in the coating the degradable polymer that adopts to the transmitance of water and chemical fertilizer, in high gas barrier organic film material and the coating the degradable polymer that adopts should be enough big to the gap between the transmitance of water and chemical fertilizer, such as high gas barrier organic film material to the transmitance of water and chemical fertilizer should with less than in the coating the degradable polymer that adopted 1/2nd of water and chemical fertilizer transmitance is advisable, gap is more better.
High gas barrier organic film material can be high gas barrier polarity low-molecular-weight organic matter, such as low perviousness polar organic matters (for degradable polymer) such as coumarone-indene resin and composition thereof, pitch and composition thereof or rosin (ester) and composition thereof, also can be the difficult degradation polar polymer of high gas barrier, such as acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride, paracril low perviousness polarity addition polymer (for degradable polymer) such as (low acrylonitrile contents).
But, because nonpolar organic film is very low to the transmitance of water and chemical fertilizer, water and chemical fertilizer mainly only see through from nonpolar organic film fault location, thin nonpolar organic film just can give environment-friendly type slow release fertilizer of the present invention long release period, so for environment-friendly type slow release fertilizer of the present invention, the preferably nonpolar organic film of high gas barrier organic film of employing.Can adopt non-polar low molecular weight organism, non-polar polymer or existing non-polar low molecular weight organism non-polar polymer to be arranged again to form nonpolar organic film.
Because the non-polar low molecular weight organic film is easy to generate crackle, so the non-polar low molecular weight organic film can compound high gas barrier polymer film, forms the saturating property of high resistant organic film jointly.That is, the high gas barrier organic film of environment-friendly type slow release fertilizer of the present invention can also be the composite film of nonpolar low-molecular-weight organic matter rete and high gas barrier polymer film.The non-polar low molecular weight organic film is preferably nexine in composite film.Wherein, high gas barrier polymkeric substance can be low perviousness polarity addition polymer such as acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride or paracril, also can be low perviousness polarity polycondensates such as urethane, Resins, epoxy or unsaturated polyester, preferably non-polar polymer.
In addition, for environment-friendly type slow release fertilizer of the present invention, high gas barrier organic film can also be the composite film of non-polar polymer rete and low perviousness polarity addition polymer retes such as acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride or paracril, perhaps can be the composite film of low perviousness polarity polycondensate retes such as non-polar polymer rete and urethane, Resins, epoxy or unsaturated polyester.At this moment, the non-polar polymer rete preferably is in the nexine of high gas barrier organic hybrid films layer.
Therefore, for environment-friendly type slow release fertilizer of the present invention, high gas barrier organic film can be high gas barrier low-molecular-weight organic matter rete (such as, high gas barrier polarity low-molecular-weight organic matter rete or non-polar low molecular weight organic film etc.), also can be high gas barrier polymer film (such as, high gas barrier polar polymer rete, perhaps non-polar polymer rete, the perhaps composite film of non-polar polymer rete and high gas barrier polar polymer rete, Deng), the composite film that can also be high gas barrier low-molecular-weight organic matter rete and high gas barrier polymer film is (such as the composite film of non-polar low molecular weight organic film and high gas barrier polar polymer rete, the perhaps composite film of non-polar low molecular weight organic film and non-polar polymer rete, Deng), can also be high gas barrier low-molecular-weight organic matter and high gas barrier mixture of polymers rete.High gas barrier low-molecular-weight organic matter can be high gas barrier polarity low-molecular-weight organic matter or non-polar low molecular weight organism, and high gas barrier polymkeric substance can be high gas barrier polar polymer or non-polar polymer.
For environment-friendly type slow release fertilizer of the present invention, organic fusing point of non-polar low molecular weight or softening temperature that the non-polar low molecular weight organic film adopts should be higher than room temperature, the non-polar low molecular weight organism is in solid-stately all the time in environment-friendly type slow release fertilizer application of the present invention like this, can bring into play the gas barrier effect to water and chemical fertilizer all the time.At this moment, the non-polar low molecular weight organism can be one or more in the petroleum resin etc. of the low-molecular-weight polyolefin of wax, fusing point or softening temperature 〉=40 ℃ of fusing point 〉=40 ℃ and molecular weight≤2000 or low-molecular-weight polystyrene and softening temperature 〉=40 ℃.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 polyisobutylene.The molecular weight of low-molecular-weight polyolefin or low-molecular-weight polystyrene is preferred≤and 2000, because the polyolefine of molecular weight≤2000 or polystyrene have biodegradable characteristics.Certainly, the molecular weight of low-molecular-weight polyolefin or low-molecular-weight polystyrene 〉=2000 also are fine.Here, organic fusing point of non-polar low molecular weight or softening temperature for well, are good, best 〉=85 ℃ with 〉=60 ℃ with higher wherein.
For environment-friendly type slow release fertilizer of the present invention, the nonpolar organic film material that high resistant permeable membrane layer is adopted can also be a non-polar polymer, can be in polyolefine, polystyrene, 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 (SBS) and the styrene isoprene styrene block copolymer (SIS) etc. one or more.Wherein, polyolefine comprises polyethylene, polypropylene and polyisobutene etc.When nonpolar organic film is the rubber rete, during such 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.When the strong rubber raw rubber rete of cold bonding (promptly not crosslinked rete) as high resistant permeable membrane layer, and the outermost rete that is in whole coating is (such as cold tough cis-1,4-polybutadiene rubber, the rubber rete of natural rubber or polyisoprene rubber is as the outermost rete of whole coating) time, under environment-friendly type slow release fertilizer particle normal temperature of the present invention, stick together, the rubber raw rubber film surface that is in coating outermost rete can adhere to an amount of mineral filler, such as lime carbonate, talcum powder, clay, magnesiumcarbonate or other mineral filler, the particle diameter of mineral filler is preferably Nano filling more better.
For environment-friendly type slow release fertilizer of the present invention, the mixture that the nonpolar organic film material that high resistant permeable membrane layer is adopted can also be nonpolar low-molecular-weight organic matter and non-polar polymer, organic fusing point of non-polar low molecular weight or the softening temperature that adopt this moment can be lower than room temperature.
For environment-friendly type slow release fertilizer of the present invention; when being compounded with high resistant permeable membrane layer in the coating; high resistant permeable membrane layer mainly plays gas barrier, and bear the chemical fertilizer wicking absorbent expand the support expansive force produced, guarantee that whole coating is unlikely and be bursting at the collision required coating mechanical strength and rigidity is mainly provided by degradable polymer sulfur-containing mixture film (perhaps also comprising the degradable polymer rete).Because degradable polymer all has higher water-intake rate usually, its rete can expand because of suction, environment-friendly type slow release fertilizer of the present invention is after Tian Tuzhong meets water simultaneously, the chemical fertilizer wicking absorbent also can produce support to coating and expand, in order to give full play to the gas barrier ability of high gas barrier organic film, the high gas barrier organic film of environment-friendly type slow release fertilizer of the present invention had better not have the place that is bursting at the collision, therefore preferably select for use high gas barrier polymkeric substance (mixture that comprises high gas barrier polymkeric substance and low-molecular-weight organic matter) as high gas barrier organic film material, independent high gas barrier polymer film is preferably arranged, such as the composite film of non-polar low molecular weight organic film and high gas barrier polymer film in the perhaps high gas barrier organic film.And, the equilibrium swelling rate that the elongation at break of high gas barrier polymer film whole coating when the environment-friendly type slow release fertilizer of its coating is immersed in the water expands, just being unlikely to high gas barrier organic film to occur because whole coating expands when environment-friendly type slow release fertilizer is immersed in the water like this has the crackle of bursting.Therefore, high gas barrier organic film is preferably selected the big high gas barrier polymkeric substance of elongation at break for use, such as elastomerics, rubber blend or plasticized polymer, certainly preferably select the big non-polar polymer of elongation at break for use, such as nonpolar elastomerics or nonpolar rubber blend or plasticising non-polar polymer.
When being compounded with high gas barrier organic film in the coating of environment-friendly type slow release fertilizer of the present invention, can release period can freely be designed by in high gas barrier organic film, adding the release period that the slowly-releasing conditioning agent is regulated environment-friendly type slow release fertilizer of the present invention.The slowly-releasing conditioning agent kind that can add has many, every can improve high gas barrier organic film can to the additive of water and chemical fertilizer perviousness, such as softening agent (softening agent all is the polarity low molecule organic matter basically), water-soluble substances (comprising water-soluble low molecular weight organism, water-soluble inorganic salt, water-soluble polymers, chemical fertilizer itself etc.), plant powder (comprising starch, wood powder, plant debris etc.), clay, talcum powder, molecular sieve powder or bone meal etc., also comprise rosin and ester thereof, pitch isopolarity organic compound certainly.Can adopt a kind of slowly-releasing conditioning agent, also can adopt more than one slowly-releasing conditioning agent.Such as, in the non-polar polymer rete, add softening agent, water-soluble substances, plant powder, clay, talcum powder, molecular sieve powder or bone meal etc., all can improve the permeability of high gas barrier organic film, to regulate the release period of environment-friendly type slow release fertilizer of the present invention to water and chemical fertilizer.Also such as, in the non-polar low molecular weight organic film, 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 substances, plant powder, clay, talcum powder, molecular sieve powder or bone meal etc.Certainly, also can be other additive, even can be degradable polymer.
The coating overall average thickness of environment-friendly type slow release fertilizer of the present invention can be 20～150 μ m, and the degradable polymer thicknesses of layers can be 0～30 μ m, and high gas barrier organic film thickness can be 0～30 μ m.Wherein, coating overall average thickness is preferably 30～120 μ m, and the degradable polymer thicknesses of layers is preferably 0～20 μ m, and high gas barrier organic film thickness is preferably 0～20 μ m.Certainly, coating overall average thickness and high gas barrier organic film thickness etc. can be bigger than above-mentioned ceiling value.Above-mentioned film thickness value is bigger, and then the release period of environment-friendly type slow release fertilizer of the present invention can be longer.
Can also add other additive in the environment-friendly type slow release fertilizer coating of the present invention, to reach such as certain performance of further adjusting coating or the purpose that reduces cost etc.Such as, the gas barrier filler of incrementals such as adding lime carbonate, perhaps add auxiliary agent and sterilant or the fungistat (being preferably water-insoluble sterilant or fungistat) that reduces the degradable polymer degradation speed, perhaps add and suppress the inhibitor (such as the urea inhibitor) that chemical fertilizer decomposes, etc.
Be example with urea as the environment-friendly type slow release urea of chemical fertilizer core below, the specific implementation method and the invention effect of environment-friendly type slow release fertilizer of the present invention is described.Adopt stripping method evaluation sustained release performance in the water, stripping method is a dissolution rate of measuring environment-friendly type slow release urea of the present invention urea in water the time in the water, specific practice is: 10 grams environment-friendly 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.Initial stage solubility rate ψ
1Be meant that the urea quality of stripping in the 24h that begins at first to soak accounts for the percentage ratio of the urea total mass in the 10 grams environment-friendly type slow release urea of the present invention of getting, and average differential solubility rate ψ
mThen be the percentage ratio that accounts for the urea total mass the 10 grams environment-friendly type slow release urea of the present invention of getting from the urea quality that soaks average stripping every day in the 2nd day to the 7th day.According to initial stage solubility rate ψ
1With average differential solubility rate ψ
m, calculate the release period t of environment-friendly type slow release urea of the present invention in water (my god):
Embodiment 1
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.The melamine formaldehyde resin prepolymer aqueous solution (the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 3.5 trimeric cyanamide gets with the formaldehyde reaction preparation) and 150 ℃ of left and right sides fusion sulphur are slowly sprayed toward the Granular Urea surface simultaneously from two groups of different nozzles respectively, the spraying throughput ratio of melamine formaldehyde resin prepolymer and sulphur is controlled to be 3: 17, promptly sulphur average quality mark is 85% in the melamine formaldehyde resin sulfur-containing mixture coating of Xing Chenging, and spraying reaches 20% of final finished environment-friendly type slow release urea total mass up to the melamine formaldehyde resin sulfur-containing mixture film quality that forms.At last, make the coating thorough drying, and melamine formaldehyde resin is solidified fully, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 67 days.
Embodiment 2
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.The melamine formaldehyde resin prepolymer aqueous solution (the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 3 trimeric cyanamide gets with the formaldehyde reaction preparation) and 150 ℃ of left and right sides fusion sulphur are slowly sprayed toward the Granular Urea surface simultaneously from two groups of different nozzles respectively, the spraying throughput ratio of sulphur and melamine formaldehyde resin prepolymer reduces gradually by rule, make sulphur massfraction distribution gradient in the melamine formaldehyde resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 90% sulphur massfraction when fading to spraying gradually and finishing is 20%, and make that sulphur average quality mark is 80% in the melamine formaldehyde resin sulfur-containing mixture film, melamine formaldehyde resin sulfur-containing mixture film quality is 20% of a final finished environment-friendly type slow release urea total mass.At last, make the coating thorough drying, and melamine formaldehyde resin is solidified fully, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 75 days.
Embodiment 3
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.The urea-formaldehyde resin prepolymer aqueous solution (the urea-formaldehyde resin prepolymer is a urea: formaldehyde mole ratio is that 1: 1.95 urea gets with the formaldehyde reaction preparation) and 150 ℃ of left and right sides fusion sulphur are slowly sprayed toward the Granular Urea surface simultaneously from two groups of different nozzles respectively, the spraying throughput ratio of sulphur and urea-formaldehyde resin prepolymer reduces gradually by rule, make sulphur massfraction distribution gradient in the urea-formaldehyde resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 95% sulphur massfraction when fading to spraying gradually and finishing is 25%, and make that sulphur average quality mark is 80% in the urea-formaldehyde resin sulfur-containing mixture film, urea-formaldehyde resin sulfur-containing mixture film quality is 16% of a final finished environment-friendly type slow release urea total mass.Then, stop to spray fusion sulphur, continue slowly to spray the urea-formaldehyde resin prepolymer aqueous solution (the urea-formaldehyde resin prepolymer is a urea: formaldehyde mole ratio is that 1: 1.2 urea and formaldehyde reaction preparation gets), reach 3% of final finished environment-friendly type slow release urea total mass up to the urea-formaldehyde resin film quality that forms.At last, make the coating thorough drying, and urea-formaldehyde resin is solidified fully, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 72 days.
Embodiment 4
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 80 ℃ in the fluidized-bed.Tung oil is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with 150 ℃ of left and right sides fusion sulphur, the spraying throughput ratio of sulphur and tung oil reduces gradually by rule, make sulphur massfraction distribution gradient in the tung oil resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 90% sulphur massfraction when fading to spraying gradually and finishing is zero, and make that sulphur average quality mark is 50% in the tung oil resin sulfur-containing mixture film, tung oil resin sulfur-containing mixture film quality is 20% of a final finished environment-friendly type slow release urea total mass.At last, make in the coating tung oil resin solidification abundant, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 110 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 80 ℃ in the fluidized-bed.Tung oil is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with asphalt mixture (tung oil and bituminous mass ratio are 8: 1) melt and 150 ℃ of left and right sides fusion sulphur, sulphur reduces by rule gradually with the spraying throughput ratio of tung oil and asphalt mixture, make sulphur massfraction distribution gradient in the tung oil-pitch sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 85% sulphur massfraction when fading to spraying gradually and finishing is 20%, and make that sulphur average quality mark is 60% in tung oil-pitch sulfur-containing mixture film, tung oil-pitch sulfur-containing mixture film quality is 20% of a final finished environment-friendly type slow release urea total mass.At last, tung oil in the coating-asphalt mixture is solidified fully, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 103 days.
Embodiment 6
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 80 ℃ in the fluidized-bed.Tung oil (dibutyl phthalate is 1: 9 with the mass ratio of tung oil) and 150 ℃ of left and right sides fusion sulphur of plasticizer-containing dibutyl phthalate are slowly sprayed toward the Granular Urea surface simultaneously from two groups of different nozzles respectively, sulphur reduces by rule gradually with the spraying throughput ratio that contains dibutyl phthalate tung oil, make the sulphur massfraction distribution gradient in the dibutyl phthalate tung oil resin sulfur-containing mixture film that contains of formation, from the sulphur massfraction that begins most is that 92% sulphur massfraction when fading to spraying gradually and finishing is 30%, and make to contain that sulphur average quality mark is 70% in the dibutyl phthalate tung oil resin sulfur-containing mixture film, containing dibutyl phthalate tung oil resin sulfur-containing mixture film quality is 20% of final finished environment-friendly type slow release urea total mass.At last, make in the coating tung oil resin solidification abundant, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 114 days.
Embodiment 7
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 80 ℃ in the fluidized-bed.Tung oil is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with 150 ℃ of left and right sides fusion sulphur, the spraying throughput ratio of tung oil and sulphur is controlled to be 3: 17, promptly the sulphur massfraction is 85% in the tung oil resin sulfur-containing mixture film of Xing Chenging, and spraying reaches 17% of final finished environment-friendly type slow release urea total mass up to the tung oil resin sulfur-containing mixture film quality that forms.Then, stop to spray fusion sulphur, continue to reach 3% of final finished environment-friendly type slow release urea total mass up to the tung oil resin film layer quality that forms toward tung oil resin sulfur-containing mixture film surface spraying tung oil (siccative that contains tung oil quality 0.4%).At last, make in the coating tung oil resin solidification abundant, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 109 days.
Embodiment 8
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 60 ℃ in the fluidized-bed.Cellulose nitrate cellulose solution (solvent is ethanol, acetone and pentyl acetate three's a mixed solvent) is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with 150 ℃ of left and right sides fusion sulphur, the spraying throughput ratio of nitrocellulose and sulphur is controlled to be 1: 4, promptly the sulphur massfraction is 80% in the nitrocellulose sulfur-containing mixture film of Xing Chenging, and spraying reaches 16% of final finished environment-friendly type slow release urea total mass up to the nitrocellulose sulfur-containing mixture film quality that forms.Then, stop to spray fusion sulphur, (solvent is ethanol, acetone and pentyl acetate three's a mixed solvent to the cellulose nitrate cellulose solution of the past nitrocellulose sulfur-containing mixture film of continuation surface spraying plasticizer-containing triphenylphosphate, the mass ratio of triphenylphosphate and nitrocellulose is 1: 6), reach 3% of final finished environment-friendly type slow release urea total mass up to the phosphoric acid triphenylmethyl methacrylate nitrocellulose rete quality that forms.At last, thorough drying is removed and is desolvated, and promptly gets environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 72 days.
Embodiment 9
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 65 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.(the polyvinyl alcohol trade mark is 1799 types with vinyl-formal resin, degree of acetalization is 90%) solution (solvent is ethanol-toluene mixed solvent) and 150 ℃ of left and right sides fusion sulphur slowly spray toward the Granular Urea surfaces simultaneously from two groups of different nozzles respectively, the spraying throughput ratio of sulphur and vinyl-formal resin reduces gradually by rule, make sulphur massfraction distribution gradient in the vinyl-formal resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 95% sulphur massfraction when fading to spraying gradually and finishing is 25%, and make that sulphur average quality mark is 80% in the vinyl-formal resin sulfur-containing mixture film, vinyl-formal resin sulfur-containing mixture film quality is 18% of a final finished environment-friendly type slow release urea total mass.Then, stop to spray fusion sulphur, past vinyl-formal resin sulfur-containing mixture film surface is spraying polyethylene butyral resin (the polyvinyl alcohol trade mark is that 1799 types, degree of acetalization are 55%) ethanolic soln slowly, reaches 5% of final finished environment-friendly type slow release urea total mass up to the polyvinyl butyral resin film quality that forms.At last, make the coating thorough drying, polyvinyl alcohol contracts the curing of first (fourth) urea formaldehyde fully, promptly gets environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 84 days.
Embodiment 10
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.The melamine formaldehyde resin prepolymer aqueous solution (the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 3.5 trimeric cyanamide and formaldehyde reaction preparation gets) slowly is sprayed at the Granular Urea surface, and spraying reaches 2% of final finished environment-friendly type slow release urea total mass up to the melamine formaldehyde resin film quality that forms.Then, slowly spray the melamine formaldehyde resin prepolymer aqueous solution (the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 3 trimeric cyanamide and formaldehyde reaction preparation gets) and 150 ℃ of left and right sides fusion sulphur respectively toward the melamine formaldehyde resin film surface simultaneously from two groups of different nozzles, the spraying throughput ratio of melamine formaldehyde resin prepolymer and sulphur is controlled to be 1: 4, promptly sulphur average quality mark is 80% in the melamine formaldehyde resin sulfur-containing mixture film of Xing Chenging, and spraying reaches 10% of final finished environment-friendly type slow release urea total mass up to the melamine formaldehyde resin sulfur-containing mixture film quality that forms.Then, slowly spray tung oil (siccative that contains tung oil quality 0.4%), reach 8% of final finished environment-friendly type slow release urea total mass up to the tung oil resin film layer quality that forms toward melamine formaldehyde resin sulfur-containing mixture film surface.At last, make the coating thorough drying, and make melamine formaldehyde resin and tung oil resin solidification abundant, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 77 days.
Embodiment 11
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 80 ℃ in the fluidized-bed.Tung oil is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with 150 ℃ of left and right sides fusion sulphur, the spraying throughput ratio of sulphur and tung oil reduces gradually by rule, make sulphur massfraction distribution gradient in the tung oil resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 95% sulphur massfraction when fading to spraying gradually and finishing is 60%, and make that sulphur average quality mark is 85% in the tung oil resin sulfur-containing mixture film, tung oil resin sulfur-containing mixture film quality is 11% of a final finished environment-friendly type slow release urea total mass.At last, make in the rete tung oil resin solidification abundant, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 101 days.
Embodiment 12
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 80 ℃ in the fluidized-bed.Tung oil is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with 150 ℃ of left and right sides fusion sulphur, the spraying throughput ratio of sulphur and tung oil reduces gradually by rule, make sulphur massfraction distribution gradient in the tung oil resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 98% sulphur massfraction when fading to spraying gradually and finishing is 40%, and make that sulphur average quality mark is 75% in the tung oil resin sulfur-containing mixture film, tung oil resin sulfur-containing mixture film quality is 8% of a final finished environment-friendly type slow release urea total mass.At last, make in the rete tung oil resin solidification abundant, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 71 days.
Embodiment 13
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.The cyanurotriamide modified urea resin prepolymer aqueous solution is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with 150 ℃ of left and right sides fusion sulphur, the spraying throughput ratio of sulphur and cyanurotriamide modified urea resin prepolymer reduces gradually by rule, make sulphur massfraction distribution gradient in the cyanurotriamide modified urea resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 90% sulphur massfraction when fading to spraying gradually and finishing is 30%, and make that sulphur average quality mark is 80% in the cyanurotriamide modified urea resin sulfur-containing mixture film, cyanurotriamide modified urea resin sulfur-containing mixture film quality is 18% of a final finished environment-friendly type slow release urea total mass.Then, toward cyanurotriamide modified urea resin sulfur-containing mixture film surface spraying ethanol modified cyanurotriamide-formaldehyde resin prepolymer aqueous solution, reach 3% of final finished environment-friendly type slow release urea total mass up to the ethanol modified cyanurotriamide-formaldehyde resin film quality that forms.At last, make the coating thorough drying, and cyanurotriamide modified urea resin and ethanol modified cyanurotriamide-formaldehyde resin are solidified fully, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 70 days.
Embodiment 14
With particle diameter is that the granular industrial urea of 2.0～4.0mm adds in the rotary drum encapsulation tool of 95 ℃ of temperature controls, rotates rotary drum (rotating speed 40r/min) Granular Urea is flowed in rotary drum.The propyl carbinol modified urea-formaldehyde resin prepolymer aqueous solution is slowly sprayed toward the Granular Urea surface from two groups of different nozzles respectively simultaneously with 150 ℃ of left and right sides fusion sulphur, the spraying throughput ratio of sulphur and propyl carbinol modified urea-formaldehyde resin prepolymer reduces gradually by rule, make sulphur massfraction distribution gradient in the propyl carbinol modified urea-formaldehyde resin sulfur-containing mixture film of formation, from the sulphur massfraction that begins most is that 90% sulphur massfraction when fading to spraying gradually and finishing is 25%, and make that sulphur average quality mark is 80% in the propyl carbinol modified urea-formaldehyde resin sulfur-containing mixture film, propyl carbinol modified urea-formaldehyde resin sulfur-containing mixture film quality is 18% of a final finished environment-friendly type slow release urea total mass.Then, slowly spray ethanol-polyvinyl alcohol modification melamine formaldehyde resin prepolymer aqueous solution toward propyl carbinol modified urea-formaldehyde resin sulfur-containing mixture film surface, reach 4% of final finished environment-friendly type slow release urea total mass up to the ethanol-polyvinyl alcohol modification melamine formaldehyde resin film quality that forms.At last, make the coating thorough drying, and propyl carbinol modified urea-formaldehyde resin and ethanol-polyvinyl alcohol modification melamine formaldehyde resin are solidified fully, promptly get environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 79 days.
Embodiment 15
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 80 ℃ in the fluidized-bed.At Granular Urea film surface spraying petroleum resin (softening temperature is 110 ℃) benzole soln, reach 3% of final finished environment-friendly type slow release urea total mass up to the petroleum resin film quality that forms.Then, the fusion sulphur of cellulose nitrate cellulose solution (solvent is ethanol, acetone and pentyl acetate three's a mixed solvent) with about 150 ℃ is slowly sprayed toward the petroleum resin film surface simultaneously from two groups of different nozzles respectively, by controlling their spraying throughput ratio, making the average quality mark of sulphur in the nitrocellulose sulfur-containing mixture film of formation is 75%, and spraying reaches 17% of final finished environment-friendly type slow release urea total mass up to the nitrocellulose sulfur-containing mixture film quality that forms.At last, stop to spray fusion sulphur, continue spraying cellulose nitrate cellulose solution, reach 2% of final finished environment-friendly type slow release urea total mass up to the nitrocellulose rete quality that forms.Thorough drying is removed solvent in the rete, promptly gets environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 113 days.
Embodiment 16
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 80 ℃ in the fluidized-bed.(the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 3 trimeric cyanamide and formaldehyde reaction preparation gets with the sulfureted melamine formaldehyde resin prepolymer aqueous solution, sulphur: the mass ratio of melamine formaldehyde resin prepolymer is 4: 1) be sprayed at urea surface, reach 8% of final finished environment-friendly type slow release urea total mass up to this layer melamine formaldehyde resin sulfur-containing mixture film quality that forms, thorough drying is removed water in the rete.Then, at melamine formaldehyde resin sulfur-containing mixture film surface spraying high-impact polystyrene benzole soln, reach 3% of final finished environment-friendly type slow release urea total mass up to the high-impact polystyrene film quality that forms, thorough drying is removed benzene in the rete.Then, again the melamine formaldehyde resin prepolymer aqueous solution (the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 3 trimeric cyanamide gets with the formaldehyde reaction preparation) and about 150 ℃ fusion sulphur are slowly sprayed toward the high-impact polystyrene film surface simultaneously from two groups of different nozzles respectively, by controlling their spraying throughput ratio, making the average quality mark of sulphur in the melamine formaldehyde resin sulfur-containing mixture film of formation is 80%, and spraying reaches 8% of final finished environment-friendly type slow release urea total mass up to this layer melamine formaldehyde resin sulfur-containing mixture film quality that forms.At last, stop to spray fusion sulphur, continue slowly to spray the melamine formaldehyde resin prepolymer aqueous solution (the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 1.6 trimeric cyanamide and formaldehyde reaction preparation gets), reach 2% of final finished environment-friendly type slow release urea total mass up to this layer melamine formaldehyde resin film quality that forms.Thorough drying is removed in the rete moisture, and the melamine formaldehyde resin in the rete is solidified fully, promptly gets environment-friendly type slow release urea.The release period of prepared environment-friendly type slow release urea is 146 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 adopts the corresponding described method of previous embodiment.Granular Urea surface first rete outward is melamine formaldehyde resin rete (adopt trimeric cyanamide: formaldehyde mole ratio is that the prepared melamine formaldehyde resin prepolymer aqueous solution of 1: 3.5 trimeric cyanamide and formaldehyde reaction sprays the film forming after fixing and gets), and this rete accounts for 3% of final finished environment-friendly type slow release urea total mass.Second rete is that (adopting the melamine formaldehyde resin prepolymer aqueous solution and fusion sulphur to spray the film forming after fixing simultaneously gets for 80% melamine formaldehyde resin sulfur-containing mixture film for the sulphur massfraction, the melamine formaldehyde resin prepolymer is a trimeric cyanamide: formaldehyde mole ratio is that 1: 3 trimeric cyanamide and formaldehyde reaction preparation gets), this rete accounts for 16% of final finished environment-friendly type slow release urea total mass.The tertiary membrane layer is styrene-butadiene-styrene block copolymer rete (adopting the solution spraying film forming of the toluene-ethyl acetate mixed solvent of styrene-butadiene-styrene block copolymer to get), and this rete accounts for 2% of final finished environment-friendly type slow release urea total mass.The release period of prepared environment-friendly type slow release urea is 110 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 adopts the corresponding described method of previous embodiment.Granular Urea surface first rete outward is urea-formaldehyde resin rete (adopt urea: formaldehyde mole ratio is that the urea-formaldehyde resin prepolymer aqueous solution that 1: 1.8 urea and formaldehyde reaction preparation gets sprays the film forming after fixing and gets), and this rete accounts for 2% of environment-friendly type slow release urea total mass.Second rete is acrylonitrile-butadiene-styrene copolymer rete (adopting the dichloroethane solution spraying film forming of acrylonitrile-butadiene-styrene copolymer ABS to get), and this rete accounts for 3% of environment-friendly type slow release urea total mass.The tertiary membrane layer is that (adopting the urea-formaldehyde resin prepolymer aqueous solution and fusion sulphur to spray the film forming after fixing simultaneously gets for 80% urea-formaldehyde resin sulfur-containing mixture film for the sulphur massfraction, the urea-formaldehyde resin prepolymer is by urea: formaldehyde mole ratio is that 1: 1.6 urea and formaldehyde reaction preparation gets), this rete accounts for 10% of environment-friendly type slow release urea total mass.The 4th rete is urea-formaldehyde resin rete (adopt urea: formaldehyde mole ratio is that the urea-formaldehyde resin prepolymer aqueous solution that 1: 1.05 urea and formaldehyde reaction preparation gets sprays the film forming after fixing and gets), and this rete accounts for 2% of environment-friendly type slow release urea total mass.The release period of prepared environment-friendly type slow release urea is 87 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 adopts the described method of previous embodiment or other suitable method.Granular Urea surface first rete outward is melamine formaldehyde resin rete (adopt by trimeric cyanamide: formaldehyde mole ratio is that the prepared melamine formaldehyde resin prepolymer aqueous solution of 1: 2.5 trimeric cyanamide and formaldehyde reaction sprays the film forming after fixing and gets), and this rete accounts for 1.5% of environment-friendly type slow release urea total mass.Second rete is 80% propyl carbinol modified urea-formaldehyde resin sulfur-containing mixture film (adopting the propyl carbinol modified urea-formaldehyde resin prepolymer aqueous solution and fusion sulphur to spray the film forming after fixing simultaneously gets) for the sulphur massfraction, and this rete accounts for 8% of environment-friendly type slow release urea total mass.The tertiary membrane layer is high-impact polystyrene rete (adopting high-impact polystyrene benzole soln spraying film forming to get), and this rete accounts for 2% of environment-friendly type slow release urea total mass.The 4th rete is ethanol modified cyanurotriamide-formaldehyde resin rete (adopting ethanol modified cyanurotriamide-formaldehyde resin aqueous solution spraying film forming after fixing to get), and this rete accounts for 8% of environment-friendly type slow release urea total mass.The release period of prepared environment-friendly type slow release urea is 130 days.
In the foregoing description, high-impact polystyrene is the FRH-1 of a Beijing Yanshan Petrochemical Company type, styrene-butadiene-styrene block copolymer (SBS) trade mark is a Kraton D1101 type, ABS is Lanzhou Petrochemical Company ABS-301, tung oil be come from Qiu north, Yunnan, acid number is the commercially available tung oil of 5.0mgKOH/g, pitch is the AH-70 shell pitch that Singapore produces.
In the foregoing description, the urea-formaldehyde resin prepolymer aqueous solution is urea and formaldehyde reaction preparation and getting, urea and formaldehyde mole ratio can be 1: (1～3) scope, known to the common knowledge of the technician of affiliated professional domain, usually with 1: be advisable (1～2), adds the ammonium chloride solidifying agent of urea-formaldehyde resin prepolymer quality 2% before filming.The cyanurotriamide modified urea resin prepolymer aqueous solution is urea, trimeric cyanamide, formaldehyde reaction preparation and get, urea: trimeric cyanamide: formaldehyde mole ratio is 1: 1: 4, adds the ammonium chloride solidifying agent of cyanurotriamide modified urea resin prepolymer quality 2% before filming.The propyl carbinol modified urea-formaldehyde resin prepolymer aqueous solution is urea, formaldehyde, propyl carbinol prepared in reaction and get urea: formaldehyde: the propyl carbinol mol ratio is 1: 1.37: 1, adds the ammonium chloride solidifying agent of propyl carbinol modified urea-formaldehyde resin prepolymer quality 2% before filming.
In the foregoing description, the melamine formaldehyde resin prepolymer aqueous solution is trimeric cyanamide and formaldehyde reaction preparation and getting, trimeric cyanamide and formaldehyde mole ratio can be 1: (1～4) scope, known to the common knowledge of the technician of affiliated professional domain, usually with 1: be advisable (1.5～3.5), adds the ammonium chloride solidifying agent of melamine formaldehyde resin prepolymer quality 2% before filming.Ethanol modified cyanurotriamide-formaldehyde resin prepolymer aqueous solution is trimeric cyanamide, formaldehyde, ethanol synthesis preparation and get, trimeric cyanamide: formaldehyde: the ethanol mol ratio is 1: 2.5: 2, adds the ammonium chloride solidifying agent of ethanol modified cyanurotriamide-formaldehyde resin prepolymer quality 2% before filming.Ethanol-polyvinyl alcohol modification melamine formaldehyde resin prepolymer aqueous solution is trimeric cyanamide, formaldehyde, ethanol, polyvinyl alcohol prepared in reaction and get, trimeric cyanamide: formaldehyde: ethanol: the polyvinyl alcohol mass ratio is 100: 67: 12: 2.5, and the ammonium chloride solidifying agent of adding ethanol-polyvinyl alcohol modification melamine formaldehyde resin prepolymer quality 2% before filming.
Known to the common knowledge of the technician of affiliated professional domain, modified urea-formaldehyde resin and modified cyanurotriamide-formaldehyde resin belong to urea-formaldehyde resin and melamine formaldehyde resin respectively, and the modified urea-formaldehyde resin that is adopted in the foregoing description and modified cyanurotriamide-formaldehyde resin are respectively indivedual representatives of modified urea-formaldehyde resin and modified cyanurotriamide-formaldehyde resin only, modified urea-formaldehyde resin that is adopted and the preparation of modified cyanurotriamide-formaldehyde resin prescription also just can adopt an example of prescription, formation scope of the present invention are not limited.Melamine resin in the aminoresin is except that aforementioned (modification) melamine formaldehyde resin, can adopt oxalic dialdehyde and furfural etc. to replace the corresponding melamine resin of prepared formaldehyde, the unlisted related embodiment of this specification sheets embodiment part, but such melamine resin still belongs to invention scope of the present invention.
Claims (11)
1. environment-friendly type slow release fertilizer, coating by chemical fertilizer core and chemical fertilizer core outside is formed, it is characterized in that: coating is the degradable polymer sulfur-containing mixture film, perhaps is the composite film of degradable polymer sulfur-containing mixture film and degradable polymer rete.
2. environment-friendly type slow release fertilizer according to claim 1 is characterized in that: degradable polymer is one or more in aminoresin, unsaturated oil resin, polyvinyl alcohol and multipolymer Derlin thereof and natural polymer and the derivative thereof; Wherein, natural polymer and derivative thereof are one or more in nitrocellulose, lac, cellulose acetate, cross-linking starch, chitin derivativ and the lignin derivative.
3. environment-friendly type slow release fertilizer according to claim 1 is characterized in that: sulphur average quality mark is 50%～98% in the coating.
4. environment-friendly type slow release fertilizer according to claim 3 is characterized in that: exist in the degradable polymer sulfur-containing mixture film sulphur massfraction be 90%～99.9% around the sealing surface of chemical fertilizer core.
5. environment-friendly type slow release fertilizer according to claim 1 is characterized in that: sulphur massfraction distribution gradient in the degradable polymer sulfur-containing mixture film, the Gradient distribution mode for from the chemical fertilizer core outward the sulphur massfraction reduce gradually.
6. environment-friendly type slow release fertilizer according to claim 1 is characterized in that: also have high gas barrier organic film in the coating.
7. environment-friendly type slow release fertilizer according to claim 6 is characterized in that: high gas barrier organic film is nonpolar organic film, and nonpolar organic film material is non-polar low molecular weight organism and/or non-polar polymer.
8. environment-friendly type slow release fertilizer according to claim 7 is characterized in that: the non-polar low molecular weight organism is one or more in the petroleum resin of the polyolefine of wax, fusing point or softening temperature 〉=40 ℃ of fusing point 〉=40 ℃ and molecular weight≤2000 or polystyrene and softening temperature 〉=40 ℃.
9. environment-friendly type slow release fertilizer according to claim 7 is characterized in that: non-polar polymer is one or more in polyolefine, polystyrene, 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).
10. according to each described environment-friendly type slow release fertilizer of claim 6～9, it is characterized in that: high gas barrier organic film is when having high gas barrier polymer film in high gas barrier polymer film or the high gas barrier organic film, the equilibrium swelling rate that whole coating expanded when the elongation at break of high gas barrier polymer film was immersed in the water greater than the environment-friendly type slow release fertilizer of its coating.
11. according to each described environment-friendly type slow release fertilizer of claim 1～9, it is characterized in that: coating overall average thickness is 20～150 μ m, and the degradable polymer thicknesses of layers is 0～30 μ m, and high gas barrier organic film thickness is 0～30 μ m.
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| CNA2007100068381A CN101234922A (en) | 2007-01-31 | 2007-01-31 | Environment-friendly type slow release fertilizer |
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| CNA2007100068381A CN101234922A (en) | 2007-01-31 | 2007-01-31 | Environment-friendly type slow release fertilizer |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2007100068381A Pending CN101234922A (en) | 2007-01-31 | 2007-01-31 | Environment-friendly type slow release fertilizer |
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| Country | Link |
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| CN (1) | CN101234922A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948352A (en) * | 2010-09-15 | 2011-01-19 | 廖大中 | Method for preparing sustained-release fertilizer |
| CN103539526A (en) * | 2013-09-29 | 2014-01-29 | 济南大学 | Slow-release chemical fertilizer with composite layer and preparation method thereof |
| CN104496650A (en) * | 2014-11-28 | 2015-04-08 | 深圳市芭田生态工程股份有限公司 | Total-nutrient water-retaining degradable mechanically-applied coated fertilizer |
| CN104557260A (en) * | 2014-12-14 | 2015-04-29 | 青岛锐志农业技术服务有限公司 | Preparation method of sulfur-spread coated slow-release fertilizer |
| CN110183274A (en) * | 2019-06-18 | 2019-08-30 | 吉林农业大学 | A kind of coated fertilizer and preparation method thereof with slow control-release function |
| WO2021103941A1 (en) * | 2019-11-27 | 2021-06-03 | 湖北富邦科技股份有限公司 | Environmental-friendly medium trace element mixing agent and application |
-
2007
- 2007-01-31 CN CNA2007100068381A patent/CN101234922A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948352A (en) * | 2010-09-15 | 2011-01-19 | 廖大中 | Method for preparing sustained-release fertilizer |
| CN101948352B (en) * | 2010-09-15 | 2013-05-22 | 廖大中 | Method for preparing sustained-release fertilizer |
| CN103539526A (en) * | 2013-09-29 | 2014-01-29 | 济南大学 | Slow-release chemical fertilizer with composite layer and preparation method thereof |
| CN103539526B (en) * | 2013-09-29 | 2016-03-23 | 济南大学 | A kind of Slow-release chemical fertilizer with composite layer and preparation method thereof |
| CN104496650A (en) * | 2014-11-28 | 2015-04-08 | 深圳市芭田生态工程股份有限公司 | Total-nutrient water-retaining degradable mechanically-applied coated fertilizer |
| CN104557260A (en) * | 2014-12-14 | 2015-04-29 | 青岛锐志农业技术服务有限公司 | Preparation method of sulfur-spread coated slow-release fertilizer |
| CN110183274A (en) * | 2019-06-18 | 2019-08-30 | 吉林农业大学 | A kind of coated fertilizer and preparation method thereof with slow control-release function |
| WO2021103941A1 (en) * | 2019-11-27 | 2021-06-03 | 湖北富邦科技股份有限公司 | Environmental-friendly medium trace element mixing agent and application |
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