CN115005202A - Surfactant-induced pesticide intercalation attapulgite nano hybrid and preparation method thereof - Google Patents

Surfactant-induced pesticide intercalation attapulgite nano hybrid and preparation method thereof Download PDF

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CN115005202A
CN115005202A CN202210797195.1A CN202210797195A CN115005202A CN 115005202 A CN115005202 A CN 115005202A CN 202210797195 A CN202210797195 A CN 202210797195A CN 115005202 A CN115005202 A CN 115005202A
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attapulgite
surfactant
trimethyl ammonium
pesticide
dodecyl
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张晓光
陈宇祥
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Nankai University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention discloses a surfactant-induced pesticide intercalation attapulgite nano hybrid, which is prepared by mixing and reacting a surfactant micelle wrapping pesticide and an amphoteric surfactant modified attapulgite compound. The method fully utilizes the electrostatic attraction effect and the hydrophobic effect of the surfactant and the attapulgite and the interlayer hydrophobicity of the compound, and improves the drug-loading rate and the sustained-release performance of the hybrid. The drug loading is 3-50% of the nano hybrid by mass percent. The hybrid of the invention has the characteristics of simple preparation process, mild condition, large drug-loading rate, long slow-release time and the like, and can be used for preparing a pesticide slow-release agent.

Description

Surfactant-induced pesticide intercalation attapulgite nano hybrid and preparation method thereof
Technical Field
The invention relates to a pesticide intercalation attapulgite nano hybrid and a preparation method thereof, belonging to the technical field of new materials and pesticide controlled release.
Background
The pesticide is an important production material in agricultural production, and plays an important role in preventing and controlling agricultural diseases, worm and mouse damage and ensuring stable yield and increased yield of grain production. Due to the fact that the pesticide utilization rate is low due to unreasonable use modes, a pesticide use zero-growth action scheme is put forward in 2015 in China. Through the rapid development of water-based formulations, agricultural unmanned aerial vehicle plant protection and the like in recent years, the pesticide utilization rate in China is continuously improved, and the pesticide utilization rate in 2021 years reaches 40.6%, but is lower than 50-60% of that in developed countries. At present, the pesticide formulation is developing towards water-based, granular, slow-release, multifunctional and labor-saving, and the development of the pesticide slow-release agent is an important way for improving the utilization rate of the pesticide. The pesticide slow release agent based on inorganic materials is an important component of the pesticide slow release agent.
Attapulgite (ATP) is a type 2: 1 magnesium aluminum silicate clay mineral, which is fibrous in appearance and has a chain layer structure. The surface of the attapulgite is negatively charged, and a certain amount of metal ions are adsorbed on the surface of the attapulgite in order to balance the charges on the surface of the attapulgite. ATP is generally white, grey white or grey, has fine and smooth soil texture, strong water absorption, large specific surface area, good chemical stability, strong adsorption force, small density and easy suspension, and is usually used as a drug carrier to slowly release.
At present, only a few studies are carried out on the preparation of pesticide hybrid (slow release agent) by taking attapulgite as a carrier, and the slow release agent is mainly the Wuzhengrock topic group of the university of Chinese science and technology. The method utilizes attapulgite with self-polymerization dopamine adsorbed on the surface to adsorb the insecticide chlorpyrifos, and then the surface of the attapulgite is wrapped by cross-linked sodium alginate to obtain porous gel microspheres [ Y.B.Xiaoang, G.L.Zhang, C.W.Chen, B.Liu, D.Q.Cai, Z.Y.Wu, ACS Sustainable Chem.Eng.2018, 6, 1192-]. The microsphere drug-loaded chlorpyrifos has good light stability and continuous slow release performance of pH response. The herbicide glyphosate and photoresponse molecule azobenzene are efficiently loaded by using a porous biological carbon-attapulgite compound, and then the surface of the porous biological carbon-attapulgite compound is coated by amino silicone oil to obtain a pesticide slow release agent with photoresponse [ C.W.Chen, G.L.Zhang, Z.Y.Dai, Y.B.Xiang, B.Liu, P.Bian, K.ZHEN, Z.Y.Wu, D.Q.Cai, chem.Engin.J.2018, 349, 101-plus 110-]. Ultraviolet light, visible light and night did not affect the sustained release, while UV-Vis light (365 and 435nm) promoted glyphosate release. The temperature response type hybrid [ Y.Chi, G.L.Zhang, Y.B.Xiaoang, D.Q.Cai, Z.Y.Wu, ACS Sustainable chem.Eng.2017, 5, 4969-containing 4975 ] with a core-shell structure is obtained by mixing and granulating attapulgite, glyphosate and ammonium bicarbonate to be used as a core, and then coating amino silicone oil and polyvinyl alcohol on the surface of the particle]. The hybrid has sustained release performance, and the release amount is obviously increased along with the temperature rise. Mixing attapulgite, glyphosate, porous carbon and ammonium bicarbonate, granulating, and reusing the surface of the granulesThe cellulose and the silicone oil are wrapped to obtain near infrared light response hybrid [ B.Liu, C.W.Chen, R.Wang, S.Y.Dong, J.Li, G.L.Zhang, D.Q.Cai, S.Y.Zhai, Z.Y.Wu, ACS Sustainable chem.Eng.2019, 7, 14924-material 14932-]. As the porous carbon has the photothermal conversion efficiency of 38 percent, the temperature of the hybrid can be increased by near infrared light, and the decomposition of ammonium bicarbonate into CO is initiated 2 And NH 3 And a large number of pores are formed on the surfaces of the cellulose and the silicone oil, so that the glyphosate is favorably released. The pesticides are adsorbed on the surface of attapulgite, the surface of the attapulgite is provided with a wrap, and the surface of a hybrid has nano/micron-sized holes, so that the pesticide has excellent slow release performance. However, the hybrid has the defects of long preparation route, complex process, long period and the like. The hybrid sustained-release agent is mainly prepared from inorganic materials such as layered hydrotalcite and montmorillonite by a micelle method and a secondary assembly method, however, the attapulgite is rod-shaped fiber, and reports on the preparation of pesticide intercalation attapulgite hybrid by using a surfactant are not seen. The invention prepares the pesticide intercalation nano hybrid by mixing and reacting the micelle containing the pesticide and the attapulgite compound modified by the amphoteric surfactant. The method makes full use of the electrostatic interaction, hydrophobic interaction and composite interlayer hydrophobicity of the surfactant and the laminate, and improves the drug-loading rate and the slow-release performance of the hybrid.
Disclosure of Invention
Aiming at the defects of complex preparation method, long period, high cost and the like of the attapulgite mineral-loaded pesticide hybrid, the invention provides a pesticide intercalation attapulgite nano hybrid and a preparation method thereof, which can be used for pesticide delivery and slow release.
The pesticide intercalated attapulgite nano hybrid is prepared by mixing and reacting a surfactant micelle wrapping pesticide and an amphoteric surfactant modified attapulgite compound to intercalate the pesticide into the attapulgite. Wherein the surfactant for forming the micelle is a cationic or amphoteric surfactant, and the surfactant for preparing the attapulgite compound is an amphoteric surfactant; the pesticide is one of high-efficiency cypermethrin, cyhalothrin, deltamethrin, tebuconazole, hexaconazole, triadimenol, abamectin, emamectin benzoate and the like, and the drug loading is 3-50 percent of the nano hybrid by mass percent.
In the above pesticide intercalation attapulgite nano hybrid: the cationic surfactant forming the pesticide micelle can be one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, one of dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride, one of dodecyl pyridine chloride, tetradecyl pyridine chloride, hexadecyl pyridine chloride, octadecyl pyridine chloride or dodecyl pyridine bromide, tetradecyl pyridine bromide, hexadecyl pyridine bromide and octadecyl pyridine bromide, or didodecyl trimethyl ammonium bromide, ditetradecyl trimethyl ammonium bromide, dihexadecyl trimethyl ammonium bromide, dioctadecyl trimethyl ammonium bromide or didodecyl trimethyl ammonium chloride, One of ditetradecyl trimethyl ammonium chloride, dihexadecyl trimethyl ammonium chloride and dioctadecyl trimethyl ammonium chloride, and the amphoteric surfactant is one of dodecyl sulfobetaine, tetradecyl sulfobetaine, hexadecyl sulfobetaine, dodecyl carboxyl betaine, tetradecyl carboxyl betaine, hexadecyl carboxyl betaine, dodecyl amine oxide, tetradecyl amine oxide and hexadecyl amine oxide. The amphoteric surfactant for modifying attapulgite is one of dodecyl sulfobetaine, tetradecyl sulfobetaine, hexadecyl sulfobetaine, dodecyl carboxybetaine, tetradecyl carboxybetaine, hexadecyl carboxybetaine, dodecyl amine oxide, tetradecyl amine oxide, and hexadecyl amine oxide.
In the pesticide intercalation attapulgite nano hybrid, the mass ratio of the surfactant and the pesticide forming the micelle can be 0.8: 1, 1: 1, 1.5: 1 or 2: 1 according to the properties of the pesticide and the surfactant; the mass ratio of the surfactant and the modified attapulgite forming the micelle may be 0.5: 1, 1: 1, 1.5: 1, or 2: 1.
The preparation method of the nano hybrid is characterized in that the nano hybrid is prepared by mixing, stirring and reacting a micelle coated with pesticide and a surfactant modified attapulgite compound, centrifuging, washing and drying. The method comprises the following specific steps:
(A) weighing an amphoteric surfactant according to a design amount, dispersing the amphoteric surfactant in water without carbon dioxide, adding a certain amount of attapulgite, performing ultrasonic treatment, adjusting the pH value of a system, reacting for 48 hours at 50 ℃, centrifuging, washing and drying to obtain a surfactant modified attapulgite compound; the mass concentration of the surfactant in water is 4-8%; (B) the pesticide is weighed according to the design amount and dissolved in N-methyl pyrrolidone, N-dimethyl formamide or absolute ethyl alcohol with certain volume, and a certain amount of cation or amphoteric surfactant is added into the pesticide to prepare micellar solution. The mass ratio of the surfactant to the pesticide constituting the micelle may be 0.8: 1, 1: 1, 1.5: 1, or 2: 1, depending on the nature of the pesticide and surfactant; (C) the micellar solution and the surfactant-modified attapulgite compound are mixed to obtain a suspension, and the mass ratio of the surfactant to the modified attapulgite forming the micelles is 0.5: 1, 1: 1, 1.5: 1, or 2: 1. (D) Stirring the suspension for 48 hours at 30-60 ℃, centrifuging, washing the precipitate for 3 times by using 95% ethanol respectively, and drying to obtain the pesticide intercalation attapulgite nano hybrid.
The preparation method of the pesticide intercalation attapulgite nano hybrid provided by the invention can use not only the cationic surfactant but also the amphoteric surfactant to prepare the micelle, thereby expanding the selection range of the surfactant. The pesticide intercalation not only has the electrostatic attraction effect, the hydrophobic effect, the hydrogen bond and the like of the surfactant and the laminate, but also has the interlayer hydrophobicity of the compound, thereby greatly increasing the driving force of the pesticide intercalation and improving the drug-loading rate. The preparation method has the characteristics of simple preparation process, high drug loading, stable structure, good slow release performance and the like.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a hybrid of hexadecyl sulfobetaine-modified attapulgite (SB-ATP) prepared in example 1 and hexadecyl sulfobetaine-modified attapulgite intercalated with tetradecyl trimethylammonium bromide containing beta-cypermethrin as a micelle (BCT/TTAB-SB-ATP)
FIG. 2 is a Fourier transform infrared spectrum of the intercalated attapulgite hybrid of beta-cypermethrin (BCT/TTAB-SB-ATP) and beta-cypermethrin (BCT) prepared in example 1
FIG. 3 is an SEM photograph of hexadecyl sultaine-modified attapulgite (SB-ATP) and beta-cypermethrin-intercalated attapulgite hybrid (BCT/TTAB-SB-ATP) (b) prepared in example 1
Fig. 4 is a release profile of the cypermethrin intercalated attapulgite hybrid (BCT/TTAB-SB-ATP) prepared in example 1 in a buffer at pH5.0 and pH 6.8.
Detailed Description
Example 1
Weighing 1.0g of hexadecyl Sulfobetaine (SB) and dissolving in 20ml of carbon dioxide-removed water, adding 1.0g of attapulgite into the water solution under the protection of N2, stirring vigorously, adjusting the end-point pH value of the solution system to 6.0, continuing stirring for 48h at 50 ℃, centrifuging and washing the product, drying for 12h at 80 ℃ in an oven, and grinding to obtain hexadecyl sulfobetaine modified attapulgite (recorded as SB-ATP).
And b, weighing 0.8g of beta-cypermethrin (BCT) original drug, dissolving the beta-cypermethrin (BCT) original drug in 20ml of absolute ethyl alcohol, weighing 1.0g of Tetradecyl Trimethyl Ammonium Bromide (TTAB) to dissolve in the solution, and mixing and stirring the solution and the solution to obtain the micelle which is transparent in appearance and contains the beta-cypermethrin.
And c, weighing 1.0g of SB-ATP powder, dispersing the SB-ATP powder in the micelle prepared in the step b, stirring for 48h at 50 ℃ under the protection of N2, centrifuging, washing the precipitate for 3 times by using 95% ethanol, drying the precipitate for 12h at 70 ℃, and grinding to obtain the high-efficiency cypermethrin intercalated attapulgite hybrid (marked as BCT/TTAB-SB-ATP).
The XRD spectrogram (figure 1) shows that the beta-cypermethrin intercalated attapulgite hybrid has a crystal structure of attapulgite, and the beta-cypermethrin is known to be intercalated between layers from the interlayer spacing. FT-IR spectrum (figure 2) further proves that BCT exists in hybrid, and ultraviolet spectrophotometry is adopted to determine that the content of the efficient cypermethrin in the sample is 16.64%. The sustained-release property of the hybrid was confirmed at pH5.0 and 6.8 from the hybrid sustained-release curve (FIG. 4).
Example 2
Step a weighing 1.0g Dodecyl Carboxyl Betaine (DCB) and dissolving in 20ml carbon dioxide-removed water, N 2 Adding 1.0g of attapulgite into the aqueous solution under protection, stirring vigorously, adjusting the end point pH value of the solution system to 6.0, continuing stirring for 48h, centrifuging and washing the product, drying in an oven at 80 ℃ for 12h, and grinding to obtain the dodecyl carboxyl betaine modified attapulgite (the sample is recorded as DCB-ATP).
And b, weighing 1.0g of beta-cypermethrin technical material, dissolving the raw material into 20ml of N-methyl pyrrolidone, weighing 1.0g of Cetyl Trimethyl Ammonium Bromide (CTAB), dissolving the Cetyl Trimethyl Ammonium Bromide (CTAB) into the solution, and mixing and stirring the cetyl trimethyl ammonium bromide and the CTAB to obtain the micelle with transparent appearance.
Step c 1.0g of DCB-ATP powder was weighed out and dispersed in the micelles prepared in step b, in N 2 Stirring at 50 deg.C for 48h under protection, centrifuging, washing the precipitate with 95% ethanol for 3 times, drying the precipitate at 70 deg.C for 12h, and grinding to obtain intercalated attapulgite hybrid. The ultraviolet spectrophotometry is adopted to determine that the content of the beta-cypermethrin in the sample is 15.5 percent.
Example 3
Step a DCB-ATP was prepared as in step a of example 2.
And b, weighing 1.0g of cypermethrin technical material, dissolving the cypermethrin technical material in 20ml of absolute ethyl alcohol, weighing 1.0g of Dodecyl Trimethyl Ammonium Bromide (DTAB), dissolving the dodecyl trimethyl ammonium bromide and the DTAB in the solution, and mixing and stirring the solution to obtain the micelle with transparent appearance.
Step c weighing 1.0g of DCB-ATP powder to be dispersed in the micelle prepared in the step b, and dispersing in N 2 Stirring for 48h at 50 ℃ under protection, centrifuging, washing the precipitate with 95% ethanol for 3 times, drying for 12h at 70 ℃, and grinding to obtain the beta-cypermethrin intercalated attapulgite hybrid. The ultraviolet spectrophotometry is adopted to determine that the content of the beta-cypermethrin in the sample is 18.0 percent.
Example 4
Step a preparation of SB-ATP As in step a of example 1.
And b, weighing 1.0g of the original drug of the high-efficiency cypermethrin, dissolving the original drug of the high-efficiency cypermethrin in 20ml of absolute ethyl alcohol, weighing 1.0g of Octadecyl Trimethyl Ammonium Bromide (OTAB), dissolving the Octadecyl Trimethyl Ammonium Bromide (OTAB) in the solution, and mixing and stirring the octadecyl trimethyl ammonium bromide and the OTAB to obtain the solubilized high-efficiency cypermethrin micelle with transparent appearance.
Step c weighing 1.0g of SB-ATP powder dispersed in the micelles prepared in step b, in N 2 Stirring for 2 days at 50 ℃ under protection, centrifuging, washing the precipitate with 95% ethanol for 3 times, drying for 12h at 70 ℃, and grinding to obtain the beta-cypermethrin intercalated attapulgite hybrid. The content of the beta-cypermethrin is determined to be 19.30 percent by adopting an ultraviolet spectrophotometry.
Example 5
Step a DCB-ATP was prepared as in step a of example 2.
And b, weighing 1.0g of abamectin original drug, dissolving the abamectin original drug in 20ml of N-methyl pyrrolidone, weighing 1.0g of didodecyltrimethyl ammonium bromide (DDAB), dissolving the didodecyltrimethyl ammonium bromide (DDAB) in the solution, and mixing and stirring the solution and the solution to obtain the solubilized abamectin micelle with transparent appearance.
Step c 1.0g of DCB-ATP powder was weighed out and dispersed in the micelles prepared in step b, in N 2 Stirring for 2 days at 30 ℃ under protection, centrifuging, washing the precipitate with 95% ethanol for 3 times, drying the precipitate at 80 ℃ for 12h, and grinding to obtain the abamectin intercalated attapulgite hybrid.
An XRD spectrogram shows that the abamectin intercalated attapulgite hybrid has a crystal structure of attapulgite, and the interlayer spacing indicates that the abamectin is intercalated between layers. The content of the abamectin is determined to be 6.30 percent by adopting an ultraviolet spectrophotometry.
Example 6
Step a preparation of SB-ATP As in step a of example 1.
And b, weighing 1.0g of abamectin original drug, dissolving the abamectin original drug in 20ml of N-methyl pyrrolidone, weighing 1.0g of Dodecyl Trimethyl Ammonium Bromide (DTAB), dissolving the dodecyl trimethyl ammonium bromide and the DTAB in the solution, and mixing and stirring the two to obtain the micelle with transparent appearance.
Step c weighing 1.0g of SB-ATP powder dispersed in the micelles prepared in step b, N 2 Stirring for 48h at 50 ℃ under protection, centrifuging, washing the precipitate with 95% ethanol for 3 times, drying the precipitate for 12h at 80 ℃, and grinding to obtain the abamectin intercalated attapulgite hybrid. The content of the abamectin in the sample is determined to be 8.0 percent by adopting an ultraviolet spectrophotometry.
Example 7
Step a preparation weighing1.0g of dodecylamine Oxide (OA) dissolved in 20ml of decarbonated water, N 2 Adding the attapulgite into the aqueous solution under protection, stirring vigorously, adjusting the end point pH value of the solution system to 6.0, continuing stirring for 48h, centrifuging and washing the product, drying in an oven at 80 ℃ for 12h, and grinding to obtain the dodecyl amine oxide modified attapulgite (the sample is recorded as OA-ATP).
And b, weighing 1.0g of abamectin original drug, dissolving the abamectin original drug in 20ml of N-methyl pyrrolidone, weighing 1.0g of DTAB, dissolving the DTAB in the solution, and mixing and stirring the solution and the solution to obtain the solubilized abamectin micelle with transparent appearance.
Step c weighing 1.0gOA-ATP powder dispersed in the micelles prepared in step b, in N 2 Stirring for 2 days at 50 ℃ under protection, centrifuging, washing the precipitate with 95% ethanol for 3 times, then drying for 12h at 80 ℃, and grinding to obtain the abamectin intercalated attapulgite hybrid.
An XRD spectrogram shows that the abamectin intercalated attapulgite hybrid has a crystal structure of attapulgite, and the interlayer spacing indicates that the abamectin is intercalated between layers. The content of the abamectin is determined to be 8.65 percent by adopting an ultraviolet spectrophotometry.

Claims (3)

1. A nano-hybrid of intercalated attapulgite for agricultural chemical is prepared from surfactant micelle and modified attapulgite through mixing, stirring and reaction. Wherein the surfactant constituting the micelle is one of a cationic surfactant and an amphoteric surfactant; the attapulgite refers to a magnesium aluminum silicate clay mineral; the pesticide is one of high-efficiency cypermethrin, cyhalothrin, deltamethrin, tebuconazole, hexaconazole, triadimenol, abamectin and emamectin benzoate, and the content of the pesticide is 3 to 50 percent of the nano hybrid by mass percent.
2. The intercalated attapulgite clay nanohybrid of claim 1, wherein: the cationic surfactant for forming the pesticide-coated micelle can be one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, or one of dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride, or dodecyl pyridine chloride, tetradecyl pyridine chloride, hexadecyl pyridine chloride, octadecyl pyridine chloride or dodecyl pyridine bromide, tetradecyl pyridine bromide, hexadecyl pyridine bromide and octadecyl pyridine bromide, or didodecyl trimethyl ammonium bromide, ditetradecyl trimethyl ammonium bromide, dihexadecyl trimethyl ammonium bromide, dioctadecyl trimethyl ammonium bromide or didodecyl trimethyl ammonium chloride, or dodecyl trimethyl ammonium chloride, The amphoteric surfactant can be one of hexadecyl sulfobetaine, tetradecyl sulfobetaine, dodecyl sulfobetaine, hexadecyl carboxyl betaine, tetradecyl carboxyl betaine, dodecyl carboxyl betaine, hexadecyl amine oxide, tetradecyl amine oxide and dodecyl amine oxide. The surfactant for modifying the attapulgite is one of hexadecyl sulfobetaine, tetradecyl sulfobetaine, dodecyl sulfobetaine, hexadecyl carboxyl betaine, tetradecyl carboxyl betaine, dodecyl carboxyl betaine, hexadecyl amine oxide, tetradecyl amine oxide and dodecyl amine oxide.
3. The method for preparing the intercalated attapulgite nano hybrid pesticide as claimed in claim 1, which comprises the following steps: (A) weighing an amphoteric surfactant according to a design amount, dispersing the amphoteric surfactant in water without carbon dioxide, adding a certain amount of attapulgite, performing ultrasonic treatment, adjusting the pH value of a system, reacting for 48 hours at 50 ℃, centrifuging, washing and drying to obtain a surfactant intercalated attapulgite compound; (B) weighing pesticides according to a design amount, dissolving the pesticides in a certain volume of N-methyl pyrrolidone, N-dimethyl formamide or absolute ethyl alcohol, adding a certain amount of cationic surfactant or amphoteric surfactant into the pesticides, and preparing a micellar solution, wherein the mass ratio of the surfactant to the pesticides is 0.8-2: 1; (C) mixing and stirring the micelle solution and the surfactant modified attapulgite composite for 48 hours at 30-60 ℃, centrifuging, washing with 95% ethanol for 3 times respectively, centrifuging, and drying to obtain the pesticide intercalation attapulgite nano hybrid, wherein the mass ratio of the surfactant and the attapulgite forming the micelle is 1-2: 1.
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