CN104145987A - Preparation and application of ethephon controllable sustained-release material - Google Patents
Preparation and application of ethephon controllable sustained-release material Download PDFInfo
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- CN104145987A CN104145987A CN201410387266.6A CN201410387266A CN104145987A CN 104145987 A CN104145987 A CN 104145987A CN 201410387266 A CN201410387266 A CN 201410387266A CN 104145987 A CN104145987 A CN 104145987A
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Abstract
The invention discloses preparation and application of an ethephon controllable sustained-release material, which solve the problem of pesticide residue in the use process of the ethephon and improve the use efficiency of the ethephon in crops. The material is a composite membrane prepared from an alkaline polymer and the ethephon. The alkaline polymer comprises chitosan, polyacrylate, sodium alginate and the like, and the mass ratio of the alkaline polymer to the ethephon is (10-30):(90-70). The ethephon controllable sustained-release material can be used in an air medium or a buffer solution, and the controlled-release speed is affected by the air humidity, the content of the ethephon, and the pH value of the buffer solution. The material is not in direct contact with the crops when in use, so that the pesticide residue is reduced, the use efficiency of the ethephon in the crops is improved due to the controlled-release effect, the controllable ripening acceleration of fruits and vegetables can be realized, and the material is expected to be used for accelerating the ripening of the household fruits and vegetables.
Description
Technical field
The invention belongs to fruits and vegetables ripening technique field, be specifically related to preparation and the application of ethrel controllable sustained-release material.
Background technology
Ethrel is high-quality and efficient plant growth regulator, main have promotion fruit maturation as agricultural plant growth stimulant, stimulates bleeding, regulate the effects such as sex conversion, its Main Function has: promote Female flower differentiation, promote fruit maturation, promote plant dwarfing and break plant dormancy.Traditional usage of ethrel is for spraying and soaking, as: tomato is accelerated the ripening, can use the ethrel of 300mg/kg to be applied to bennet, be coated in 400mg/kg ethrel on the sepal and near fruit face thereof of white ripe fruit flower, can also after gathering, be placed in the ethephon solution of 200mg/kg and soak 1 minute, then urge red; If process 2 times with 300mg/kg ethephon solution in the time of tomato seedling 3 leaf 1 heart sheets to 5 slice true leaf, can control growth of seedling, control tomato growing way, strengthen resistance, early yield increases.And nonstandard use ethrel still can be detrimental to health, ethrel can have spread effect to skin, eyes after wrongly taking, and mucous membrane is had to acid corrosion action.Wrongly take and occur burn feeling, occur feeling sick later, vomiting, vomitus is brownish black, and cholinesterase activity reduces, and 3.5h left and right patient is comatose state, can also cause that children's sexual precocity and Ms's face play spot, and more serious can be carcinogenic.Although national regulation the residue limits standard of ethrel be 2mg/kg, the residual supervision of the domestic ethrel to various crops is at present also not in place, still great risk under cover.At present, there is the much research for ethrel slow releasing function, can make ethrel rationally discharge ethene and directly do not spray or soak crops or fruits and vegetables, although can accomplish safe noresidue, also exist many defects simultaneously:
1, China Patent No.: 201010539101.8, denomination of invention is: a kind of disclosure of the invention of gel of releasing ethylene gas a kind of gel of releasing ethylene gas, comprise following material component: ethrel 50-90, gel 5-20, stabilizing agent 8-25, ethrel decomposition accelerating agent 5-35; Described ethrel is solid pure product ethrel solid; Described gel is a kind of or its mixture in polyacrylate, crosslinked polyethylene glycol oxide, alginates; Described stabilizing agent is a kind of or its mixture in anhydrous magnesium sulfate, anhydrous magnesium chloride, anhydrous potassium sulfate; Described ethrel decomposition accelerating agent is a kind of or its mixture in sodium hydroxide, slaked lime, sodium carbonate, sodium bicarbonate.The gel of releasing ethylene gas provided by the invention can make ethylene gas and fruits and vegetables even contact to be accelerated the ripening, and reaches the object of evenly accelerating the ripening.Although can meeting water, the gel described in above patent discharges ethene, but use the strong alkaline substances such as sodium hydroxide to still have potential safety hazard as releasing agent, as dissolved rapidly mineral salt and highly basic wherein after meeting water when this gel, cause local alkaline grow, ethene rate of release is too fast, and gel also exists the defects such as packing, processing difficulties, storage requirement harshness.
2, China Patent No.: 201210171894.1, denomination of invention is: a kind of disclosure of the invention of the cartridge bag that can discharge ethene a kind of cartridge bag that can discharge ethene, formed by packaging material and medicament, medicament in cartridge bag comprises ethrel, releasing agent, hygroscopic agent and auxiliary material, medicament in cartridge bag evenly mixes according to a certain percentage, packaging material is heat-sealing filter paper, extrusion coating paper, nonwoven, composite membrane, reticulate pattern paper, one in Du Pont's paper, charging sequence is auxiliary material, ethrel, releasing agent, hygroscopic agent, cartridge bag method for releasing is for meeting water contact, described water can be the moisture of liquid state or gaseous state, the aqueous vapor that preferably fruits and vegetables respiration produces.The cartridge bag of the release ethene described in foregoing invention, has easy to use, stable storage, the effective feature that discharges, but also has the high problem of storage difficulty.In order to be convenient in use, moisture enters and ethene discharges, the material that the packaging material using is good water permeability, and this material makes cartridge bag easily absorb release ethene at lay up period, causes the difficulty of storage.In addition, thereby the moisture that this cartridge bag mainly relies on fruits and vegetables self to distribute in the time discharging contacts cartridge bag promotes that ethrel is decomposed into ethene and discharges, and various fruit and warehouse environment are uncontrollable key element, the release that probably causes ethene is irregular, in embodiment 6, ethrel cartridge bag just can all discharge complete by ethene in 5 days in addition, release period control is shorter, easily causes that warehouse storage fruits and vegetables accelerate the ripening too fast, and the shelf-life is short.
Visible, only control ethene release and can't solve existing issue completely.How developing one " intelligence " ethene releasable material, can control Ethylene Production Rate by regulation and control environment for use, and can guarantee fruits and vegetables and Crop securify noresidue, is to be badly in need of the important topic that solves in crops and preserving fruit and vegetable utilizing and the field of accelerating the ripening.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of ethrel controllable sustained-release material, can control Ethylene Production Rate by regulation and control environment for use, accelerate the ripening the time thereby control preserving fruit and vegetable utilizing and crops, finally realize the raising of economic benefit.Ethrel controllable sustained-release material development of the present invention is simple, controls release conditions accurate, can solve current ethrel pollution and ethene and discharge uncontrollable defect.
The present invention is achieved through the following technical solutions:
Ethrel controllable sustained-release material, is made up of following material component by weight: ethrel 70-90, alkaline polymer 10-30, auxiliary material 50-500; Described material is the composite membrane that alkaline polymer and ethrel are made.
Described alkaline polymer is shitosan, polyacrylate or sodium alginate.
Described auxiliary material is a kind of or its mixture in gelatin, rosin, polystyrene acrylic emulsion, starch.
Described material can use in air dielectric or buffer solution, and the rate of release of ethene is by air humidity, ethrel content and pH value of buffer solution control.The rate of release of ethrel controllable sustained-release composite membrane has above 3 governing factors to determine, rate of release, release time, the burst size of ethene can be effectively controlled in the effect alone or synergistically of 3 factors, thereby regulates the degree of accelerating the ripening, the freshness date length etc. of crops.
Preferably, ethrel controllable sustained-release material can discharge ethene when the water in ingress of air in air dielectric, and in the time that air humidity 50% is above, ethene rate of release reaches optimum state.Under closed environment, such as between warehouse, storage, the green house of good seal, can artificially regulate the humidity of closed environment, reach 50% when above in air humidity, can effectively regulate the decomposition of ethrel, the rate of release of ethene can reach about 17 days, and presented the comparatively release profiles of rule.
Preferably, ethrel controllable sustained-release material discharges ethene in the time of buffer solution pH4-7, and in the time of buffer solution pH6-7, releasing effect reaches optimum state.Ethrel controllable sustained-release composite membrane can be placed in to regulation pH and be worth buffer solution, when ethrel controllable sustained-release composite membrane system reaches pH4 when above, ethene meeting slow release, in the time of buffer solution pH6-7, reach optimum state, under specific damp condition, release time can be effectively, rule be controlled at 179h.Buffer solution is effective governing factor that ethrel controllable sustained-release composite membrane discharges, and can have various strong acid weak base salts formulated.
Inventor studies discovery, and mass data shows, the ethrel composite membrane of this invention development has following controlled rule: ethene slow release speed is directly proportional to air humidity, is inversely proportional to ethrel content, and pH is directly proportional to buffer solution.
The preparation method of described composite membrane comprises the following steps:
(1), by former ethrel medicine ultramicro grinding, cross 800-1000 mesh sieve.
(2) the alkaline polymer solution that compound concentration is 0.3-1.5%, mixes as solvent by weight 1:2 using glycerine and 2-3.5% acetum, regulates below pH3.5, adds required auxiliary material, and high-speed stirred 10 minutes is for subsequent use; Regulate pH below 3.5%, control ethrel and in composite membrane, can not decompose and lose efficacy.
(3) under high-speed stirred, in alkaline polymer solution, add ethrel in batches, within 10 minutes, to add a collection ofly, the every batch of addition is total amount 20%, continues to stir 20 minutes after interpolation, makes viscous liquid; Ethrel is water-soluble larger, reaches 1kg/L, adds ethrel can ensure its dispersity in system in batches, and ethrel can dissolve gradually in adition process, and then disperses wherein, and the viscosity of system also can be along with the addition of ethrel increases and retrogradation.
(4) viscous liquid making is poured in mould, put into 45-50 DEG C of baking oven dry, demoulding, obtains ethrel controllable sustained-release composite membrane.Made ethrel controllable sustained-release composite membrane moisture control is, below 0.05%, to detect discovery through inventor, and composite membrane system ethrel under 0.05% moisture is non-degradable, and this is because 0.05% water deficient is so that system ionizes out OH
-, system pH can not raise.
Described mold shape can be rectangle or circle, can control the thickness of composite membrane.Mould generally adopts glassware, can play good demoulding effect, rectangle or circle are according to actual service condition or selection mold shape attractive in appearance, the control of thickness has determined the sphere of action in this ethrel composite membrane use, thickness is larger, and ethrel medicine carrying amount is larger, and controlled range is larger, otherwise controlled range is less.
Described ethrel controllable sustained-release material, the application in controlled the accelerating the ripening of crops or fruits and vegetables, in use promotes ethene to discharge by condition, does not directly contact safe noresidue with crops.
beneficial effect of the present invention:
1, the ethrel controllable sustained-release material of this invention development, safety, environmental protection, pollution-free, noresidue, to crop and operator's safety.
2, the ethrel controllable sustained-release material of this invention development, makes the form of composite membrane, can ensure that fully the mixing of ethrel and carrier, dispersity are high, thereby ensure the controllability of ethrel in the time of release.
3, the ethrel controllable sustained-release material of this invention development discharges in air dielectric and buffer solution, can effectively control the release of ethene, has solved prior art ethene and has discharged erratic shortcoming.
4, the ethrel controllable sustained-release material of this invention development, can control ethene rate of release by the character of content, dissolution medium, thereby has extended ethene release time, and the preserving fruit and vegetable utilizing time is increased; Effective Regulation process of crop growth, environmental protection, safe and efficient.
5, the ethrel controllable sustained-release material of this invention development, processing technology is simple, controls release key element clear and definite, is comparatively typical " intelligence " type product.
embodiment;
embodiment 1 10% ethrel composite membrane preparation
(1) take the former medicine ultramicro grinding of 100kg ethrel, cross 800-1000 mesh sieve.
(2) take 10kg shitosan, compound concentration is 1% chitosan solution, mixes as solvent by weight 1:2 using glycerine and 2% acetum, regulates below pH3.5, add 880kg auxiliary material (starch: polystyrene acrylic emulsion 2:8) high-speed stirred 10 minutes, for subsequent use.
(3) under high-speed stirred, in alkaline polymer solution, add ethrel in batches, within 10 minutes, to add a collection ofly, the every batch of addition is total amount 20%, continues to stir 20 minutes after interpolation, makes viscous liquid.
(4) viscous liquid making is poured in mould, put into 45-50 DEG C of baking oven dry, skinning, obtains 10% ethrel controllable sustained-release composite membrane.
embodiment 2 15% ethrel composite membrane preparations
(1) take the former medicine ultramicro grinding of 150kg ethrel, cross 800-1000 mesh sieve.
(2) take 10kg Sodium Polyacrylate, compound concentration is 0.3% sodium polyacrylate solution, mixes as solvent by weight 1:2 using glycerine and 3.5% acetum, regulates below pH3.5, add 840kg auxiliary material (rosin: polystyrene acrylic emulsion 4:6) high-speed stirred 10 minutes, for subsequent use.
(3) under high-speed stirred, in alkaline polymer solution, add ethrel in batches, within 10 minutes, to add a collection ofly, the every batch of addition is total amount 20%, continues to stir 20 minutes after interpolation, makes viscous liquid.
(4) viscous liquid making is poured in mould, put into 50 DEG C of baking ovens dry, skinning, obtains 15% ethrel controllable sustained-release composite membrane.
embodiment 3 20% ethrel composite membrane preparations
(1) take the former medicine ultramicro grinding of 200kg ethrel, cross 800-1000 mesh sieve.
(2) take 30kg sodium alginate, compound concentration is 1.5% sodium alginate soln, mixes as solvent by weight 1:2 using glycerine and 3% acetum, regulates below pH3.5, add 770kg auxiliary material (gelatin: polystyrene acrylic emulsion 2.5:7) high-speed stirred 10 minutes, for subsequent use.
(3) under high-speed stirred, in alkaline polymer solution, add ethrel in batches, within 10 minutes, to add a collection ofly, the every batch of addition is total amount 20%, continues to stir 20 minutes after interpolation, makes viscous liquid.
(4) viscous liquid making is poured in mould, put into 50 DEG C of baking ovens dry, skinning, obtains 20% ethrel controllable sustained-release composite membrane.
embodiment 4 50% ethrel composite membrane preparations
(1) take the former medicine ultramicro grinding of 500kg ethrel, cross 800-1000 mesh sieve.
(2) take 98kg shitosan, the chitosan solution (solvent is glycerine: water 1:2) that compound concentration is 0.8%, water is 2% acetum, regulates below pH3.5, adds 400kg polystyrene acrylic emulsion, high-speed stirred 10 minutes is for subsequent use.
(3) under high-speed stirred, in alkaline polymer solution, add ethrel in batches, within 10 minutes, to add a collection ofly, the every batch of addition is total amount 20%, continues to stir 20 minutes after interpolation, makes viscous liquid.
(4) viscous liquid making is poured in mould, put into 50 DEG C of baking ovens dry, skinning, obtains 50% ethrel controllable sustained-release composite membrane.
embodiment 5 different content ethrel composite membranes ethene slow release speed in different air humiditys is measured
Test site: dan port, Nanning banana storage warehouse
Test period: on July 3rd, 2012
Test medicine: embodiment 1-3
Test method: be that 10% ethrel controllable sustained-release composite membrane, 15% ethrel controllable sustained-release composite membrane and 20% ethrel controllable sustained-release composite membrane are put in respectively in the warehouse of storage banana by embodiment 1-3, adjusting air humidity, then regularly detects acetate releasing quantity.Result is as follows:
The aerial sustained release rate of composite membrane that table 1 ethrel content is 10%
The aerial sustained release rate of composite membrane that table 2 ethrel content is 15%
The aerial sustained release rate of composite membrane that table 3 ethrel content is 20%
As can be seen from the above table, when adjusting air humidity is 54.6%, 74.9% and 97.7% time, the composite membrane ethene rate of release of differing ethylene profit content increases with air humidity, and under same air humidity, ethene slowly-releasing rate increases and reduces with ethrel content.
, show through detecting, in ethrel composite membrane, ethene release rate can reach 17 days and just can release complete meanwhile, and this has also effectively been avoided too fast the banana ripe and corrupt risk rapidly that causes of the disposable release of ethene.
the rate of release of embodiment 6 ethrel composite membranes in buffer solution
Inventor is set as 50% ethrel composite membrane in embodiment 4, under 50% prerequisite, being positioned in the buffer solution of pH6.0, pH6.5, pH7.0 in air humidity, regularly detect acetate releasing quantity, and result is as follows:
Table 4 in pH=6.0 buffer solution, the speed of composite membrane slowly-releasing ethene
Table 5 in pH=6.5 buffer solution, the speed of composite membrane slowly-releasing ethene
Table 6 in pH=7.0 buffer solution, the speed of composite membrane slowly-releasing ethene
In table, data show, ethrel composite membrane, along with pH value of buffer solution raises and rate of release quickening, is 7.0 o'clock at pH, and 71h ethene release rate reaches 98%, and pH6.0 and 6.5 only discharges 57.4% and 74.7% at 71h, is released to 93.8% and 98.4% after 179h.
Can be found out by embodiment 5 and 6, the release of ethrel composite membrane in ethrel different content, air humidity and buffer solution is rendered as rule and discharges, be embodied in: ethene slow release speed is directly proportional to air humidity, be inversely proportional to ethrel content, pH is directly proportional to buffer solution.Be in particular in; Ethrel controllable sustained-release material can discharge ethene when the water in ingress of air in air dielectric, and in the time that air humidity 50% is above, ethene rate of release reaches optimum state; Ethrel controllable sustained-release material discharges ethene in the time of buffer solution pH4-7, and in the time of buffer solution pH6-7, releasing effect reaches optimum state.
the embodiment 7 ethrel residues detection in fruit that accelerates the ripening
Banana in embodiment 5 is detected according to People's Republic of China's agricultural industry criteria " the mensuration gas chromatography of ethrel residual quantity amount in NY/T1016-2006 fruit and vegetable ", but all do not detect that ethrel is residual.
Claims (10)
1. an ethrel controllable sustained-release material, is characterized in that: described material is composite membrane, is made up of by weight following material component: ethrel 70-90 part, alkaline polymer 10-30 part and auxiliary material 50-500 part.
2. ethrel controllable sustained-release material according to claim 1, is characterized in that: described alkaline polymer is shitosan, polyacrylate or sodium alginate.
3. ethrel controllable sustained-release material according to claim 1, is characterized in that: described auxiliary material is a kind of or its mixture in gelatin, rosin, polystyrene acrylic emulsion, starch.
4. ethrel controllable sustained-release material claimed in claim 1, is characterized in that: described material can use in air dielectric or buffer solution, the rate of release of ethene is by air humidity, ethrel content and pH value of buffer solution control.
5. according to ethrel controllable sustained-release material according to claim 4, it is characterized in that: described material using method in air dielectric is: when the water of ethrel controllable sustained-release material in ingress of air, can discharge ethene, in the time that air humidity 50% is above, ethene rate of release reaches optimum state.
6. according to ethrel controllable sustained-release material according to claim 4, it is characterized in that: described material using method in buffer solution is: ethrel controllable sustained-release material discharges ethene in the time of buffer solution pH4-7, in the time of buffer solution pH6-7, releasing effect reaches optimum state.
7. ethrel controllable sustained-release material according to claim 4, is characterized in that: the slow release speed of described material is directly proportional to air humidity, is inversely proportional to ethrel content, and pH is directly proportional to buffer solution.
8. the preparation method of ethrel controllable sustained-release material claimed in claim 1, is characterized in that: comprise the following steps:
(1), by former ethrel medicine ultramicro grinding, cross 800-1000 mesh sieve;
(2) the alkaline polymer solution that compound concentration is 0.3-1.5%, mixes as solvent by weight 1:2 using glycerine and 2-3.5% acetum, regulates below pH3.5, adds required auxiliary material, and high-speed stirred 10 minutes is for subsequent use;
(3) under high-speed stirred, in alkaline polymer solution, add ethrel in batches, within 10 minutes, to add a collection ofly, the every batch of addition is total amount 20%, continues to stir 20 minutes after interpolation, makes viscous liquid;
(4) viscous liquid making is poured in mould, put into 45-50 DEG C of baking oven dry, skinning, obtains ethrel controllable sustained-release composite membrane.
9. the preparation method of ethrel controllable sustained-release material according to claim 8, is characterized in that: described mold shape can be rectangle or circle, can control as required the thickness of composite membrane.
10. ethrel controllable sustained-release material claimed in claim 1, the application in controlled the accelerating the ripening of crops or fruits and vegetables.
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| CN104604933A (en) * | 2015-02-11 | 2015-05-13 | 四川国光农化股份有限公司 | Plant ethylene regulation composite, preparation and applications thereof |
| CN104996187A (en) * | 2015-08-25 | 2015-10-28 | 钱夕华 | Flower soaking method of low-concentration NAA and glycerin jelly |
| CN105145556A (en) * | 2015-09-29 | 2015-12-16 | 南宁汉和生物科技有限公司 | Method for preparing mulched plant growth regulator added to powder water-soluble fertilizer |
| CN105815441A (en) * | 2016-04-08 | 2016-08-03 | 华南农业大学 | Fruit and vegetable ripener and application thereof |
| CN106171585A (en) * | 2016-07-27 | 2016-12-07 | 赵姣玲 | A kind of healthy effective Fructus Lycopersici esculenti forced ripening method |
| CN110218386A (en) * | 2019-07-01 | 2019-09-10 | 南京财经大学 | A kind of key technology of Ripening of Banana |
| CN110607016A (en) * | 2019-09-05 | 2019-12-24 | 中国药科大学 | Ethephon ripening packaging bag and preparation method thereof |
| CN112931510A (en) * | 2021-02-01 | 2021-06-11 | 河北科技师范学院 | Chitosan and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105145556A (en) * | 2015-09-29 | 2015-12-16 | 南宁汉和生物科技有限公司 | Method for preparing mulched plant growth regulator added to powder water-soluble fertilizer |
| CN105815441A (en) * | 2016-04-08 | 2016-08-03 | 华南农业大学 | Fruit and vegetable ripener and application thereof |
| CN106171585A (en) * | 2016-07-27 | 2016-12-07 | 赵姣玲 | A kind of healthy effective Fructus Lycopersici esculenti forced ripening method |
| CN110218386A (en) * | 2019-07-01 | 2019-09-10 | 南京财经大学 | A kind of key technology of Ripening of Banana |
| CN110607016A (en) * | 2019-09-05 | 2019-12-24 | 中国药科大学 | Ethephon ripening packaging bag and preparation method thereof |
| CN112931510A (en) * | 2021-02-01 | 2021-06-11 | 河北科技师范学院 | Chitosan and preparation method thereof |
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