CN104509531A - One-step assembly synthesis method of pesticide calcium chloroaluminate sustained release agent - Google Patents
One-step assembly synthesis method of pesticide calcium chloroaluminate sustained release agent Download PDFInfo
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- CN104509531A CN104509531A CN201410652129.0A CN201410652129A CN104509531A CN 104509531 A CN104509531 A CN 104509531A CN 201410652129 A CN201410652129 A CN 201410652129A CN 104509531 A CN104509531 A CN 104509531A
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Abstract
The invention discloses a one-step assembly synthesis method of a pesticide calcium chloroaluminate sustained release agent. The invention is innovative in that on the calcium chloroaluminate hydrate as a main body and the pesticide as an intercalation object are subjected to one-step intercalation assembly to obtain the pesticide calcium chloroaluminate sustained release agent. The pesticide calcium chloroaluminate sustained-release agent obtained through one-step intercalation assembly and synthesis by using hydrated calcium chloroaluminate as the main body and the pesticide as the object, the pesticide is proved to have good release property in water and Na2CO3 solution, and the release mechanism is analyzed preliminarily; and through verification in phosphate buffer solution and mixed inorganic anion solution with different pH values, the pesticide intercalated calcium chloroaluminate hydrate shows stable release performance.
Description
Technical field
The present invention relates to a kind of agricultural chemicals-calcium chloroaluminate sustained release agent one step assembling synthetic method, belong to preparation technique of pesticide field.
Background technology
The extensive use of agricultural chemicals is that agriculture development provides strong support, and current slow-release pesticide can be divided into physical sustained release agent and chemical row sustained release agent two class.In chemical type sustained release agent, agriculture the effective elements of the medicine and matrix are with chemical bonding, form the slow-release pesticide that can progressively discharge under field conditions (factors), which overcoming physical sustained release agent only utilizes the more weak interaction forces such as absorption to be the shortcoming that pesticide active ingredient is combined with matrix, thus, its structural stability, the Selective long-range DEPT of condition to external world, and improve the water-soluble of former agricultural chemicals itself, stability, the deficiency of the aspect such as toxicity and pesticide resistance, but agricultural chemicals is in it is used, owing to drenching, drop is got or incorrect use can cause drug effect to reduce, endanger other crops, polluted surface, the adverse consequencess such as underground water and soil.Therefore, burst size, Time and place are controlled, are important directions of chemical pesticide novel form research always.
Organic compound as pesticide slow-release/controlled release agent matrix comprises synthetic organic polymer (as the cruel polyurethane of poly-Asia peace, multiple cellulose, polypropylene, PVC, pitch, rosin ester, bioactive polymer etc.), natural organic polymeric materials is (as alginates and kaolin, natural lignin, starch, pectin, latex, cellulose, lac etc.) and other organic matter (as lignin, cationic surfactant, humic acid etc.) be that the pesticide slow-releasing agent of matrix achieves agricultural chemicals Co ntrolled release with organic compound.
But, be that the pesticide slow-releasing agent of matrix achieves agricultural chemicals Co ntrolled release with organic compound, and overcome the harm of traditional agricultural chemicals largely, but itself still has the following disadvantages: for the degradable requirement not producing secondary pollution, alternative organic high molecular compound kind is also few; According to the mechanism of action, although agricultural chemicals active principle can interact with the reactive group one_to_one corresponding on macromolecular compound main chain theoretically, by the impact of the factor such as sterically hindered, the supported quantity of part pesticide slow-releasing agent Pesticides active principle is not high; Part pesticide slow-releasing agent, mostly is the sustained release agent that ester class is matrix, under acid and neutrallty condition, have good pesticide slow-release effect, but farm chemical release speed is in the basic conditions too fast; The scope that agricultural chemicals is selected is subject to certain restrictions, and usually can only be applied to agricultural chemicals that is nonpolar or low pole.
As an important branch field of layered double hydroxide, organic intercalation double-metal hydroxide shows very wide application prospect in absorption, catalysis, electrochemistry, photochemistry etc. are many.The body layer board memory of Organo-LDHs is in strong covalent bond effect, be combined by weak interactions such as ionic bond, hydrogen bond and Van der Waals forces between interlayer object with main body LDHs laminate, and main, object all arranges in very orderly mode, this structure becomes the inorganic-organic composite material that a class possesses supramolecular structure.Along with constantly dark people, the in recent years application of (especially in medical controlled release) one of study hotspot becoming this type of material gradually in Co ntrolled release that people are familiar with organo-LDHs supramolecular structure.With the ogrnao-LDHs that medical organic matter (as folic acid, brufen, Diclofenac etc.) is assembled for object intercalation, the Co ntrolled release of medicine can be realized at certain condition, making this type of material break through traditional sustained release agent mainly with macromolecule organic is the limitation of carrier, becomes the new sustained release agent of a class based on inorganic matter.
Hydrated calcium chloroaluminate consists of 3CaO.Al
2o
3. CaCl
2.10H
2the two hydroxyl of stratiform of O closes chloride.Found when within 1897, studying the reactivity of lime and aluminium chloride by Fred the earliest.Afterwards, chemistry of cement research show, the single aluminium sulfate (AFm) in cement gel mutually in also there is this dichloro aluminic acid four calcium compound, they are class hexagon sheet crystal habit.Experiment shows, hydrated calcium chloroaluminate is stable in pH 4 ~ 12 scope, and it belongs to a kind of ion-exchange type layered structure of environment friendly, is a kind of cheap adsorbent.
At present, according to the synthetic method mainly hydro-thermal method of existing bibliographical information hydrated calcium chloroaluminate, its raw material is Ca (OH)
2, Al (OH)
3and CaCl
2.6H
2the mol ratio of O(raw material is 3: 2: 1).The major defect existing for method that existing this hydro-thermal method produces hydrated calcium chloroaluminate is: complex manufacturing, synthesis cost are high, and the specific surface area of products therefrom is little, is not suitable for industrialization synthetic pesticide sustained release agent.Therefore, the method for existing production hydrated calcium chloroaluminate or not ideal enough.
Summary of the invention
The object of the invention is to for deficiency of the prior art, a kind of agricultural chemicals-calcium chloroaluminate sustained release agent one step assembling synthetic method is provided, produce the noval chemical compound synthesis of agricultural chemicals-calcium chloroaluminate one step intercalation assembling synthesis sustained release agent, be applicable to Multiple Pesticides, the supported quantity of agricultural chemicals active principle.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of agricultural chemicals-calcium chloroaluminate sustained release agent one step assembling synthetic method, its innovative point is: based on hydrated calcium chloroaluminate, be intercalated object with agricultural chemicals, adopt a step intercalation assembling to obtain agricultural chemicals-hydrated calcium chloroaluminate sustained release agent.
Further, concrete steps are: by calcium, aluminium, chlorine element according to the ratio of mol ratio Ca:Al:Cl=2:1:1, and arranging three, to add gross mass be clear water quality 30%, throw in clear water and stir, at 20 ~ 110 DEG C, slowly add the agricultural chemicals of mass fraction 2%, control ph 4 ~ 12, carry out insulated and stirred reaction, arranging the reaction time is 8 ~ 168h, by centrifugal method Separation of Solid and Liquid after reaction terminates, finally cures, pulverize, obtain agricultural chemicals-hydrated calcium chloroaluminate sustained release agent.
Further, described calcium, aluminium, chlorine element are the composition of single compound or two or three compounds.
Further, described calcium comprises the oxide of calcium and the natural mineral matter of salt or slaked lime or calcic thereof or the aluminate of calcium.
Further, described aluminium comprises aluminium oxide and salt thereof or meta-aluminic acid and salt thereof or aluminium hydroxide and polymer thereof or containing the mineral matter of aluminium or slag.
Further, described chlorine comprises hydrochloric acid or hypochlorous acid or chloric acid and salt thereof.
Further, the reaction temperature arranged during described insulated and stirred reaction is 65 ~ 90 DEG C.
Further, the reaction time arranged during described insulated and stirred reaction is 24 ~ 72h.
Beneficial effect of the present invention:
(1) pesticide molecule/ion is inserted LDH interlayer as object by the present invention, and assembling agricultural chemicals intercalation LDH, obtain the pesticide slow-release formulation that a class is novel, agricultural chemicals effective content is high, and the release performance of agricultural chemicals is stablized.
(2) agricultural chemicals-calcium chloroaluminate one step intercalation assembling synthesis sustained release agent of the present invention provides a kind of novel agrochemical sustained release agent and preparation method thereof, and breaking through traditional sustained release agent mainly with macromolecule organic is the limitation of carrier, has invented a kind of new intercalation assemble method.
(3) the economic environmental protection of the preparation method of agricultural chemicals of the present invention, production technology is simple, synthesis cost is low, and the specific surface area of products therefrom is large, suitability for industrialized synthetic pesticide sustained release agent.
(4) agricultural chemicals-calcium chloroaluminate one step intercalation assembling synthesis sustained release agent of the present invention is based on hydrated calcium chloroaluminate, is object with agricultural chemicals, and adopt a step assembling to obtain agricultural chemicals intercalation calcium chloroaluminate, warp is at water and Na
2cO
3investigate release performance in solution good, and initial analysis has been done to its releasing mechanism; In phosphate buffer solution and mixing inorganic anion solution, after checking, find that agricultural chemicals intercalation hydrated calcium chloroaluminate release performance of the present invention is stablized with different pH value respectively.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is elaborated.
Embodiment one
In 100ml water, Ca:Al:Cl=2:1:1 in molar ratio, slowly adds the calcium chloride of gross mass 30g, slaked lime and alumina cement, stir, be warming up to 65 DEG C and slowly add 2g methyl α-naphthyl acetate, reinforced complete, control ph 4, carry out insulated and stirred reaction, 85 DEG C of insulated and stirred 48 hours, are separated through conventional centrifugal, dry, pulverize, obtain methyl α-naphthyl acetate-calcium chloroaluminate sustained release agent.
Embodiment two
In 100ml water, Ca:Al:Cl=2:1:1 in molar ratio, slowly adds the calcium chloride of gross mass 30g, slaked lime and aluminium ore powder, stirs, be warming up to 65 DEG C and slowly add 2g indolecarboxylic acid, reinforced complete, control ph 6,85 DEG C of insulated and stirred 72 hours, be separated through conventional centrifugal, dry, pulverize, obtain indolecarboxylic acid-calcium chloroaluminate sustained release agent.
Embodiment three
In 100ml water, Ca:Al:Cl=2:1:1 in molar ratio, slowly adds the calcium chloride of gross mass 30g, slaked lime and aluminium oxide, stirs, slowly add 2g glyphosate, reinforced complete, control ph 8, is warming up to 85 DEG C of insulated and stirred 24 hours, be separated through conventional centrifugal, dry, pulverize, obtain glyphosate-calcium chloroaluminate sustained release agent.
Embodiment four
In 100ml water, Ca:Al:Cl=2:1:1 in molar ratio, slowly adds calcium oxide and the alchlor of gross mass 30g, stirs, slowly add 2g bensulfuron-methyl, reinforced complete, control ph 9, is warming up to 85 DEG C of insulated and stirred 24 hours, be separated through conventional centrifugal, dry, pulverize, obtain bensulfuron-methyl-calcium chloroaluminate sustained release agent.
Embodiment five
In 100ml water, Ca:Al:Cl=2:1:1 in molar ratio, slowly adds calcium chloride and the calcium metaaluminate of gross mass 30g, stirs, slowly add 2g isoproturon, reinforced complete, control ph 10, is warming up to 85 DEG C of insulated and stirred 24 hours, be separated through conventional centrifugal, dry, pulverize, obtain isoproturon-calcium chloroaluminate sustained release agent.
Embodiment six
In 100ml water, Ca:Al:Cl=2:1:1 in molar ratio, slowly adds calcium oxide and the aluminium polychloride of gross mass 30g, stirs, slowly add the 60ml ethanolic solution containing 2g lorox, reinforced complete, control ph 12, is warming up to 85 DEG C of backflow insulated and stirred 24 hours, be separated through conventional centrifugal, dry, pulverize, obtain lorox-calcium chloroaluminate sustained release agent.
Agricultural chemicals in above embodiment-calcium chloroaluminate sustained release agent is at water and Na
2cO
3investigate release performance in solution, in phosphate buffer solution and mixing inorganic anion solution, verify agricultural chemicals intercalation hydrated calcium chloroaluminate release performance with different pH value respectively.
Demonstration test data statistic 1 is as follows:
Table one
Through the agricultural chemicals-calcium chloroaluminate sustained release agent of upper table at water and Na
2cO
3investigate release performance in solution, release performance is good; In phosphate buffer solution and mixing inorganic anion solution, verify agricultural chemicals intercalation hydrated calcium chloroaluminate release performance with different pH value respectively, release performance is stablized.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill of the present invention is modified to technical scheme of the present invention or equivalent replacement; and not departing from aim and the scope of technical scheme, it all should be encompassed in right of the present invention.
Claims (8)
1. agricultural chemicals-calcium chloroaluminate sustained release agent one step assembling synthetic method, it is characterized in that: based on hydrated calcium chloroaluminate, is intercalated object with agricultural chemicals, adopts a step intercalation assembling to obtain agricultural chemicals-hydrated calcium chloroaluminate sustained release agent.
2. agricultural chemicals according to claim 1-calcium chloroaluminate sustained release agent one step assembling synthetic method, it is characterized in that: concrete steps are: by calcium, aluminium, chlorine element is according to the ratio of mol ratio Ca:Al:Cl=2:1:1, arranging three, to add gross mass be clear water quality 30%, throw in clear water and stir, at 20 ~ 110 DEG C, slowly add the agricultural chemicals of mass fraction 2%, control ph 4 ~ 12, carry out insulated and stirred reaction, arranging the reaction time is 8 ~ 168h, by centrifugal method Separation of Solid and Liquid after reaction terminates, finally cure, pulverize, obtain agricultural chemicals-hydrated calcium chloroaluminate sustained release agent.
3. agricultural chemicals according to claim 2-calcium chloroaluminate sustained release agent one step assembling synthetic method, is characterized in that: described calcium, aluminium, chlorine element are the composition of single compound or two or three compounds.
4. the agricultural chemicals according to Claims 2 or 3-calcium chloroaluminate sustained release agent one step assembling synthetic method, is characterized in that: described calcium comprises the oxide of calcium and the natural mineral matter of salt or slaked lime or calcic thereof or the aluminate of calcium.
5. the agricultural chemicals according to Claims 2 or 3-calcium chloroaluminate sustained release agent one step assembling synthetic method, is characterized in that: described aluminium comprises aluminium oxide and salt thereof or meta-aluminic acid and salt thereof or aluminium hydroxide and polymer thereof or containing the mineral matter of aluminium or slag.
6. the agricultural chemicals according to Claims 2 or 3-calcium chloroaluminate sustained release agent one step assembling synthetic method, is characterized in that: described chlorine comprises hydrochloric acid or hypochlorous acid or chloric acid and salt thereof.
7. agricultural chemicals according to claim 2-calcium chloroaluminate sustained release agent one step assembling synthetic method, is characterized in that: the reaction temperature arranged during described insulated and stirred reaction is 65 ~ 90 DEG C.
8. agricultural chemicals according to claim 2-calcium chloroaluminate sustained release agent one step assembling synthetic method, is characterized in that: the reaction time arranged during described insulated and stirred reaction is 24 ~ 72h.
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Cited By (7)
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|---|---|---|---|---|
| CN110339807A (en) * | 2019-06-04 | 2019-10-18 | 南京工业大学 | A method of preparing hydrated calcium chloroaluminate |
| CN111565570A (en) * | 2018-01-12 | 2020-08-21 | 吉武亨将 | Insect repellent and method and apparatus for producing hypochlorous acid aqueous solution |
| CN112806357A (en) * | 2021-01-15 | 2021-05-18 | 中国农业大学 | Mepighiaum controlled-release agent and application thereof in chemical regulation of crops |
| CN114467953A (en) * | 2022-02-25 | 2022-05-13 | 茂名市和亿化工有限公司 | Method for synthesizing bispyribac-sodium slow-release agent by reconstructing hydrated calcium chloroaluminate structure |
| CN114467952A (en) * | 2022-02-25 | 2022-05-13 | 茂名市和亿化工有限公司 | Method for synthesizing slow-release herbicide by using bispyribac-sodium intercalated hydrated calcium chloroaluminate |
| CN114521552A (en) * | 2022-02-25 | 2022-05-24 | 茂名市和亿化工有限公司 | Method for synthesizing slow release agent by one-step intercalation assembly of oxyfluorfen-calcium chloroaluminate |
| CN114600895A (en) * | 2022-02-25 | 2022-06-10 | 茂名市和亿化工有限公司 | Method for synthesizing slow release agent by one-step intercalation assembly of bispyribac-sodium-calcium chloroaluminate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111565570A (en) * | 2018-01-12 | 2020-08-21 | 吉武亨将 | Insect repellent and method and apparatus for producing hypochlorous acid aqueous solution |
| CN110339807A (en) * | 2019-06-04 | 2019-10-18 | 南京工业大学 | A method of preparing hydrated calcium chloroaluminate |
| CN110339807B (en) * | 2019-06-04 | 2022-07-08 | 南京工业大学 | Method for preparing hydrated calcium chloroaluminate |
| CN112806357A (en) * | 2021-01-15 | 2021-05-18 | 中国农业大学 | Mepighiaum controlled-release agent and application thereof in chemical regulation of crops |
| CN114467953A (en) * | 2022-02-25 | 2022-05-13 | 茂名市和亿化工有限公司 | Method for synthesizing bispyribac-sodium slow-release agent by reconstructing hydrated calcium chloroaluminate structure |
| CN114467952A (en) * | 2022-02-25 | 2022-05-13 | 茂名市和亿化工有限公司 | Method for synthesizing slow-release herbicide by using bispyribac-sodium intercalated hydrated calcium chloroaluminate |
| CN114521552A (en) * | 2022-02-25 | 2022-05-24 | 茂名市和亿化工有限公司 | Method for synthesizing slow release agent by one-step intercalation assembly of oxyfluorfen-calcium chloroaluminate |
| CN114600895A (en) * | 2022-02-25 | 2022-06-10 | 茂名市和亿化工有限公司 | Method for synthesizing slow release agent by one-step intercalation assembly of bispyribac-sodium-calcium chloroaluminate |
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