CN114804174A - Method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure - Google Patents
Method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure Download PDFInfo
- Publication number
- CN114804174A CN114804174A CN202210179706.3A CN202210179706A CN114804174A CN 114804174 A CN114804174 A CN 114804174A CN 202210179706 A CN202210179706 A CN 202210179706A CN 114804174 A CN114804174 A CN 114804174A
- Authority
- CN
- China
- Prior art keywords
- oxyfluorfen
- calcium chloroaluminate
- hydrated calcium
- chloroaluminate
- reconstructing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
- A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
- A01N33/22—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group having at least one oxygen or sulfur atom and at least one nitro group directly attached to the same aromatic ring system
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The method for synthesizing the oxyfluorfen slow-release agent by reconstructing the hydrated calcium chloroaluminate structure, disclosed by the invention, is to treat the hydrated calcium chloroaluminate by a calcination mode, the calcined calcium chloroaluminate has raised specific surface area, raised pore volume, lowered content of chlorine ion in the interlayer, re-hydration of the composite metal oxide material and simultaneous intercalation of oxygen-containing anion to rebuild the calcium chloroaluminate structure, and almost simultaneous structure rebuilding and anion intercalation, therefore, the equilibrium time of the calcium chloroaluminate obtained through calcination treatment for adsorbing oxyfluorfen is greatly shortened, in addition, the hydrated calcium chloroaluminate is calcined at a proper temperature and then structurally rebuilt with the technical solution of oxyfluorfen to form the oxyfluorfen slow-release agent which is continuously and stably released and has wide acid-base application, so that various specific supermolecular structure oxyfluorfen nano slow-release dosage forms can be obtained.
Description
Technical Field
The invention belongs to the technical field of plant protection, material chemistry, intercalation assembly chemistry and functional nanometer, and particularly relates to a method for synthesizing oxyfluorfen sustained release agent by reconstructing a hydrated calcium chloroaluminate structure.
Background
Layered double metal hydroxides, LDHs for short, are a class of anionic layered compounds, also known as hydrotalcites, which have acidic and basic characteristics, memory effects, exchangeability of interlayer anions, and microporous structures. Since 1970 the first patent on hydrotalcite-like compounds for the preparation of hydrogenation catalysts, hydrotalcite-like compounds have attracted considerable interest. The material is widely applied to the fields of catalysis, adsorption, ion exchange and the like, and in recent years, with further research on the material, the application of the material in the aspects of medicines, coatings, oxyfluorfen, functional polymer materials, oil field development and the like is developed.
At present, hydrated calcium chloroaluminate can be processed to synthesize an oxyfluorfen sustained-release agent, however, in the traditional mode, the hydrated calcium chloroaluminate has long equilibrium time for adsorbing oxyfluorfen, anions in the hydrated calcium chloroaluminate are not easy to replace, and the adsorption amount of the hydrated calcium chloroaluminate is low.
Disclosure of Invention
The invention mainly solves the technical problem of providing a method for synthesizing oxyfluorfen sustained release agent by reconstructing a hydrated calcium chloroaluminate structure, so as to solve the technical problem.
In order to solve the technical problems, the invention adopts a technical scheme that: the method for synthesizing the oxyfluorfen slow-release agent by reconstructing the hydrated calcium chloroaluminate structure is characterized by comprising the following steps of: putting the synthesized hydrated calcium chloroaluminate dry powder into a crucible for calcination to obtain calcined calcium chloroaluminate; dispersing the calcined calcium chloroaluminate into a solution containing oxyfluorfen technical to form a suspension, and adjusting the pH of the suspension by using alkali and acid; the oxyfluorfen sustained release agent is obtained by intercalation reaction, filtration, water washing and drying.
Furthermore, the chemical structural formula of the hydrated calcium chloroaluminate is 3CaO & Al 2 O 3 ·CaCl 2 ·10H 2 O or Ca 4 Al 2 (OH) 12 Cl 2 (H 2 O) 4 Wherein the range of Ca to Al in the hydrated calcium chloroaluminate is 1.5-6: 1.
Further, the range of Ca to Al in the hydrated calcium chloroaluminate is 2-4: 1.
Further, the solution of oxyfluorfen technical comprises an aqueous solution, an oxyfluorfen technical solution and a phase transfer agent.
Further, the alkali is inorganic alkali and alkali salt thereof, and the acid is inorganic acid and acid salt thereof.
Further, the pH range is 4-12, and the temperature range of intercalation reaction is 20-100 ℃.
Further, the optimal range of the pH is 6-10, and the range of the temperature of the intercalation reaction is 35-80 ℃.
Further, the calcination is increased to 700 ℃ at a speed of 10 ℃/30min, and the calcination is maintained at a constant temperature for 2-8 hours.
Further, the optimum calcination is raised to 480-600 ℃ at a rate of 10 ℃/30min and the calcination is maintained at a constant temperature for 3-5 hours.
Further, hydrated calcium chloroaluminate is synthesized by coprecipitation of chlorine-containing aqueous solution under the action of high aluminum salt and calcium salt; dispersing the calcined calcium chloroaluminate into a solution containing oxyfluorfen raw pesticide in a stirring mode or an ultrasonic mode; the temperature range of the drying treatment is 60-80 ℃, and the drying time range of the drying treatment is 8-72 hours.
The invention has the beneficial effects that: different from the situation of the prior art, the method for synthesizing the oxyfluorfen sustained release agent by reconstructing the hydrated calcium chloroaluminate structure disclosed by the invention is characterized in that the hydrated calcium chloroaluminate is treated by a calcination mode, the calcined calcium chloroaluminate improves the specific surface area, the pore volume and the content of chloride ions between layers, the calcium chloroaluminate obtained after calcination comprises a composite metal oxide material rehydration function and a contemporaneous oxoanion intercalation function to reconstruct the calcium chloroaluminate structure, the structure reconstruction and the anion intercalation almost occur simultaneously, so the equilibrium time for adsorbing the oxyfluorfen by the calcium chloroaluminate obtained after calcination treatment is greatly shortened, in addition, the hydrated calcium chloroaluminate forms the oxyfluorfen sustained release agent which is continuously and stably released and has wide acid-base application after being structurally reconstructed with an oxyfluorfen original drug solution after calcination at a proper temperature, can obtain various specific supermolecular structure oxyfluorfen nano sustained-release dosage forms.
Drawings
FIG. 1 is a schematic flow chart of the method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure.
Detailed Description
Referring to fig. 1, the invention discloses a method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure, which comprises the following steps:
step S101: and putting the synthesized hydrated calcium chloroaluminate dry powder into a crucible for calcination to obtain calcined calcium chloroaluminate.
In this example, the chemical formula of the hydrated calcium chloroaluminate is 3 CaO. Al 2 O 3 ·CaCl 2 ·10H 2 O or Ca 4 Al 2 (OH) 12 Cl 2 (H 2 O) 4 。
Preferably, the hydrated calcium chloroaluminate is synthesized by coprecipitation of chlorine-containing aqueous solution under the action of high aluminum salt and calcium salt.
In this example, the Ca to Al ratio of the hydrated calcium chloroaluminate ranges from 1.5 to 6: 1.
Preferably, the Ca to Al ratio of the hydrated calcium chloroaluminate ranges from 2 to 4: 1.
It is noted that the crucible in step S101 is calcined at a rate of 10 deg.C/30 min (min) to 300 deg.C/700 deg.C during the calcination process, and is calcined at a constant temperature for 2-8 hours. It is understood that the calcination of the synthesized hydrated calcium chloroaluminate dry powder in the crucible is mainly used for calcination dehydration, and the calcination is increased to 300-700 ℃ at a rate of 10 ℃ (centigrade)/30 min (min) for interlayer dehydration.
Preferably, the crucible in step S101 is calcined at a speed of 10 ℃/30min to 480-600 ℃ during the best calcination, and is calcined at a constant temperature for 3-5 hours.
Step S102: dispersing the calcined calcium chloroaluminate into a solution containing oxyfluorfen technical to form a suspension, and adjusting the pH of the suspension by using alkali and acid.
Preferably, the calcium chloroaluminate subjected to calcination treatment in the present embodiment is dispersed in the solution containing the technical oxyfluorfen by a stirring method or an ultrasonic method.
In this embodiment, the solution of oxyfluorfen technical includes an aqueous solution, a solution of oxyfluorfen technical and a phase transfer agent.
In step S102, the base is an inorganic base and an alkaline salt thereof, that is, the base for adjusting the pH of the suspension is an inorganic base and an alkaline salt thereof. Preferably, the base used to adjust the pH of the suspension comprises sodium hydroxide, potassium hydroxide, or other hydroxide-containing compounds.
The acid is inorganic acid and its acid salt, that is, the acid for adjusting the pH of the suspension is inorganic acid and its acid salt. Preferably, the acid used to adjust the pH of the suspension includes hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like.
It will be appreciated that the pH of the suspension is adjusted by the use of bases and acids in this example is mainly because the hydrated calcium chloroaluminate is unstable under strong alkaline or strong acidic conditions and therefore needs to be adjusted. Preferably, the pH is in the range of 4 to 12.
Most preferably, the pH is in the range of 6 to 10.
Step S103: the oxyfluorfen sustained release agent is obtained by intercalation reaction, filtration, water washing and drying.
It is to be understood that the temperature of the intercalation reaction in step S103 is in the range of 20-100 ℃.
Preferably, the temperature of the intercalation reaction in step S103 is in the range of 35-80 ℃.
In this example, filtration is used primarily to remove water to leave solids for drying. Further, the water washing is mainly performed by clean water to wash off acid or alkali.
In this embodiment, the temperature range of the drying treatment is 60-80 ℃, and the drying time range of the drying treatment is 8-72 hours.
It is understood that layered double metal hydroxides (LDHs) are anionic layered compounds having exchangeable anions between layers, and mainly include hydrotalcites, hydrotalcite-like compounds, and intercalated pillared hydrotalcites. The structure of the bread is like a sandwich bread, two sides of the bread are composed of divalent and trivalent metal ion positive charge sheets, and the middle of the bread is provided with anions and water molecules. Various anions such as inorganic and organic anions, isopoly and heteropolyanions and anions of metal compounds are introduced between the hydrotalcite layers to obtain pillared hydrotalcites. Because the material has a unique anionic pillared layered structure, unique anion exchangeability and laminate cation collocatability, the diversification of molecular assembly can be realized through modulated metal ions and anions, in other words, under a certain condition, certain functional species can overcome the acting force between layers of layered compounds and can be variably inserted into interlayer gaps, thereby modulating structural parameters and properties such as layer charge density, layer spacing, laminate two-dimensional size and the like in a large range, deriving abundant and various performances and functions, and meeting the design requirements of various functional materials.
The basic property of the LDHs is alkalinity, and stronger alkalinity is often shown in the calcined product, the acidity of different LDHs is related to the acidity of trivalent metal hydroxide and the alkalinity of divalent metal hydroxide in the composition, and the acidity of pillared hydrotalcite is sometimes derived from pillared anions. The thermal stability of the LDHs varies depending on the composition but is substantially similar; when heated to a certain temperature, only crystal water is lost, and the laminated structure is not damaged; when the laminate is heated to a certain temperature, the hydroxyl groups of the laminate shrink and remove anions An-, so that the number of LDHs micropores is increased rapidly, and the specific surface area is also increased; at higher temperatures, a more stable bimetallic oxide can be formed. LDHs also have unique 'structural memory effect', that is, after the structure is changed in a certain way, the LDHs can be reversibly restored to the original structure under a certain condition. In general, higher anions tend to exchange lower anions between layers. In addition, the bimetallic oxide compound obtained after the hydrotalcite compound is calcined at the temperature of 500 ℃ can adsorb anions in the environment through the reconstruction of a layered structure, so that the hydrotalcite compound, particularly the calcined product and pillared hydrotalcite thereof have larger specific surface area and pore volume, are easy to accept objects and can be used as an adsorbent.
The calcination restoration method is a preparation method developed on the basis of the 'memory effect' characteristic of hydrotalcite, wherein the memory effect of hydrotalcite refers to that hydrotalcite samples calcined at a certain temperature are added into an aqueous solution containing certain anions or placed in a water vapor atmosphere, the reconstruction of a hydrotalcite layer-column structure occurs, and the anions enter between layers to form new pillared hydrotalcite. The preparation process includes calcining hydrotalcite in air to certain temperature to produce layered double metal oxide, and setting the layered double metal oxide in the anion solution to be inserted for structure reconstruction to form new layered compound. Finally, filtering, washing and drying the hydrotalcite material to obtain the novel hydrotalcite material. The method eliminates metal salt inorganic anions competing with organic anions for intercalation, and is commonly used for preparing pillared hydrotalcite. The calcined hydrotalcite has good adsorption and regeneration effects.
In the embodiment, the calcium chloroaluminate obtained by calcining the hydrated calcium chloroaluminate increases the specific surface area, increases the pore volume, and reduces the content of chloride ions between layers. The adsorption mechanism of the calcined calcium chloroaluminate comprises the rehydration of the composite metal oxide material and the concurrent intercalation of the oxyanion to reconstruct the calcium chloroaluminate structure, while the adsorption mechanism of the uncalcined hydrated calcium chloroaluminate is only the ion exchange of the interlayer anions. In terms of adsorption capacity, the adsorption mechanism of the uncalcined calcium chloroaluminate is mainly anion exchange, and the adsorption mechanism of the calcium chloroaluminate obtained after calcination is mainly anion intercalation, so that if the anions in the original calcium chloroaluminate are not easily replaced, the adsorption capacity of the uncalcined calcium chloroaluminate is far lower than that of the calcined calcium chloroaluminate. In terms of adsorption power, the ion exchange mechanism of the uncalcined calcium chloroaluminate comprises two steps of film diffusion and hole internal diffusion, but the structure reconstruction and anion intercalation of the calcined calcium chloroaluminate almost simultaneously occur, so the adsorption equilibrium time of the calcined calcium chloroaluminate is greatly shortened.
The specific embodiment is as follows:
preparation of calcined hydrated calcium chloroaluminate: the synthesized hydrated calcium chloroaluminate dry powder is put into a orange peel, the temperature is raised to 500 ℃ at the speed of 10 ℃/30min, and the calcining is carried out for 4 hours at constant temperature, thus obtaining the calcined calcium chloroaluminate.
Scheme 1: 1g (g) of calcined calcium chloroaluminate is taken and dispersed into 40ml ethanol/water (volume ratio is 1:1) solution containing 0.8g of oxyfluorfen; pH of the suspension with HNO 3 Adjusting to 6.5; then, intercalation reaction is carried out for 72 hours at room temperature; filtering, and washing with water to obtain oxyfluorfen nanometer sustained-release agent (i.e. oxyfluorfen sustained-release agent).
Scheme 2:
1g of calcined calcium chloroaluminate is taken and dispersed into 100ml of aqueous solution containing 0.5g of oxyfluorfen; pH of the suspension with HNO 3 Adjusting to 8.0; then, carrying out intercalation reaction for 24 hours at room temperature; filtering and washing with water to obtain the oxyfluorfen nano sustained-release agent.
Scheme 3:
1g of calcined calcium chloroaluminate is taken and dispersed into 60ml of aqueous solution containing 0.1g of oxyfluorfen; pH of the suspension and HNO 3 Adjusting to 8.5; then, intercalation reaction is carried out for 12 hours at room temperature; filtering and washing with water to obtain the oxyfluorfen slow release agent.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure is characterized by comprising the following steps:
putting the synthesized hydrated calcium chloroaluminate dry powder into a crucible for calcination to obtain calcined calcium chloroaluminate;
dispersing the calcined calcium chloroaluminate into a solution containing oxyfluorfen technical to form a suspension, and adjusting the pH of the suspension by using alkali and acid;
the oxyfluorfen sustained release agent is obtained by intercalation reaction, filtration, water washing and drying.
2. The method for synthesizing oxyfluorfen slow release agent by reconstructing hydrated calcium chloroaluminate structure according to claim 1, wherein the chemical structural formula of the hydrated calcium chloroaluminate is 3 CaO-Al 2 O 3 ·CaCl 2 ·10H 2 O or Ca 4 Al 2 (OH) 12 Cl 2 (H 2 O) 4 Wherein the range of Ca to Al in the hydrated calcium chloroaluminate is 1.5-6: 1.
3. The method for synthesizing oxyfluorfen slow release formulation by reconstructing hydrated calcium chloroaluminate structure according to claim 2, wherein the ratio of Ca to Al in the hydrated calcium chloroaluminate is in the range of 2-4: 1.
4. The method for synthesizing oxyfluorfen slow release formulation by structure reconstruction of calcium chloroaluminate hydrate according to claim 1, wherein the solution of oxyfluorfen technical comprises an aqueous solution, a technical solution of oxyfluorfen and a phase transfer agent.
5. The method for synthesizing oxyfluorfen slow release formulation by reconstructing hydrated calcium chloroaluminate structure according to claim 1, wherein the alkali is inorganic alkali and its alkali salt, and the acid is inorganic acid and its acid salt.
6. The method for synthesizing oxyfluorfen slow release formulation by reconstructing hydrated calcium chloroaluminate structure according to claim 1, wherein the pH is in the range of 4-12, and the temperature of intercalation is in the range of 20-100 ℃.
7. The method for synthesizing oxyfluorfen slow release formulation by reconstructing hydrated calcium chloroaluminate structure according to claim 6, wherein the pH is preferably in the range of 6-10, and the temperature of intercalation is in the range of 35-80 ℃.
8. The method for synthesizing oxyfluorfen slow release agent by structure reconstruction of calcium chloroaluminate hydrate as claimed in claim 1, wherein the calcination is carried out at a rate of 10 ℃/30min to 300 ℃ and 700 ℃, and the calcination is carried out for 2-8 hours at a constant temperature.
9. The method for synthesizing oxyfluorfen slow release agent by structure reconstruction of calcium chloroaluminate hydrate as claimed in claim 8, wherein the optimum calcination is increased to 480-600 ℃ at a rate of 10 ℃/30min and the calcination is maintained at a constant temperature for 3-5 hours.
10. The method for synthesizing oxyfluorfen slow release agent by reconstructing hydrated calcium chloroaluminate structure according to claim 8, wherein the hydrated calcium chloroaluminate is synthesized by coprecipitation of chlorine-containing aqueous solution under the action of high aluminum salt and calcium salt; dispersing the calcined calcium chloroaluminate into a solution containing oxyfluorfen raw pesticide in a stirring mode or an ultrasonic mode; the temperature range of the drying treatment is 60-80 ℃, and the drying time range of the drying treatment is 8-72 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210179706.3A CN114804174A (en) | 2022-02-25 | 2022-02-25 | Method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210179706.3A CN114804174A (en) | 2022-02-25 | 2022-02-25 | Method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114804174A true CN114804174A (en) | 2022-07-29 |
Family
ID=82529466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210179706.3A Pending CN114804174A (en) | 2022-02-25 | 2022-02-25 | Method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114804174A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090170705A1 (en) * | 2006-01-14 | 2009-07-02 | Bayer Technology Services Gmbh | Phyllosilicate formulations for the controlled release of active substances |
| CN101519221A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for synthesizing hydrated calcium chloroaluminate |
| CN102088844A (en) * | 2008-07-11 | 2011-06-08 | 日本曹达株式会社 | Method for producing extended-release preparation composition |
| CN103127900A (en) * | 2013-03-07 | 2013-06-05 | 清华大学 | Hydrotalcite precursor adsorbent and preparation method thereof |
| CN104026125A (en) * | 2014-06-18 | 2014-09-10 | 厦门大学 | Method for synthesizing sustained-release agent by intercalating pesticide into calcium chloroaluminate hydrate |
| CN104396949A (en) * | 2014-11-17 | 2015-03-11 | 江苏隆昌化工有限公司 | Method for structural reconstruction of hydrated aluminum chloroaluminate to synthesize pesticide controlled release agent |
| CN110339807A (en) * | 2019-06-04 | 2019-10-18 | 南京工业大学 | A method of preparing hydrated calcium chloroaluminate |
| CN110663683A (en) * | 2019-10-30 | 2020-01-10 | 淄博职业学院 | Slow-release type weeding and sterilizing double-effect pesticide and preparation method thereof |
-
2022
- 2022-02-25 CN CN202210179706.3A patent/CN114804174A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090170705A1 (en) * | 2006-01-14 | 2009-07-02 | Bayer Technology Services Gmbh | Phyllosilicate formulations for the controlled release of active substances |
| CN102088844A (en) * | 2008-07-11 | 2011-06-08 | 日本曹达株式会社 | Method for producing extended-release preparation composition |
| CN101519221A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for synthesizing hydrated calcium chloroaluminate |
| CN103127900A (en) * | 2013-03-07 | 2013-06-05 | 清华大学 | Hydrotalcite precursor adsorbent and preparation method thereof |
| CN104026125A (en) * | 2014-06-18 | 2014-09-10 | 厦门大学 | Method for synthesizing sustained-release agent by intercalating pesticide into calcium chloroaluminate hydrate |
| CN104396949A (en) * | 2014-11-17 | 2015-03-11 | 江苏隆昌化工有限公司 | Method for structural reconstruction of hydrated aluminum chloroaluminate to synthesize pesticide controlled release agent |
| CN110339807A (en) * | 2019-06-04 | 2019-10-18 | 南京工业大学 | A method of preparing hydrated calcium chloroaluminate |
| CN110663683A (en) * | 2019-10-30 | 2020-01-10 | 淄博职业学院 | Slow-release type weeding and sterilizing double-effect pesticide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Efficient removal of fluoride from aqueous solutions using 3D flower-like hierarchical zinc-magnesium-aluminum ternary oxide microspheres | |
| Gao et al. | Hydrothermal synthesis of hierarchical hollow hydroxyapatite microspheres with excellent fluoride adsorption property | |
| Pourfaraj et al. | Synthesis of hexagonal mesoporous MgAl LDH nanoplatelets adsorbent for the effective adsorption of Brilliant Yellow | |
| Wang et al. | 3D porous Ca-modified Mg-Zr mixed metal oxide for fluoride adsorption | |
| Huang et al. | Application of titanate nanoflowers for dye removal: a comparative study with titanate nanotubes and nanowires | |
| KR20200015640A (en) | Mesoporous titanium dioxide nanoparticles and process for their production | |
| CN107638887B (en) | C @ NiFe-LDH catalyst for industrial wastewater treatment and preparation method thereof | |
| CN108311164B (en) | Iron modified photocatalytic material and preparation method and application thereof | |
| JP5568726B2 (en) | Titanium oxide / layered double hydroxide composite and method for producing the same | |
| JP4958293B2 (en) | Adsorbent for bromate ion | |
| CN109414676A (en) | The method for preparing the method for adsorbent material and extracting lithium from salting liquid with the material | |
| CN107787248B (en) | Method for preparing adsorbent material comprising step of precipitating boehmite under specific conditions and method for extracting lithium from salt solution using the same | |
| Ma et al. | Performance and mechanism of Mg-Ca-Fe hydrotalcite-like compounds for fluoride removal from aqueous solution | |
| CN105032342A (en) | Preparation method of stratiform bimetallic oxide sorbent capable of effectively removing low-concentrated phosphate radical | |
| CN104396949A (en) | Method for structural reconstruction of hydrated aluminum chloroaluminate to synthesize pesticide controlled release agent | |
| CN109692648B (en) | Adsorbent for efficiently adsorbing sulfate ions in water and preparation method thereof | |
| KR20210001642A (en) | Method of Preparing Layered Double Hydroxide Based Adsorbent and Method of Removing Heavy Metals in Water Using the Same Prepared thereby | |
| JP5429843B2 (en) | Photocatalytic material having octahedral sheet structure | |
| Wang et al. | Efficient removal and selective recovery of phosphorus by calcined La-doped layered double hydroxides | |
| CN109415219B (en) | Method for preparing adsorption material and method for extracting lithium by using same | |
| CN109692653A (en) | The adsorbent and preparation method thereof of phosphate anion in efficient absorption water | |
| CN114804174A (en) | Method for synthesizing oxyfluorfen sustained release agent by reconstructing hydrated calcium chloroaluminate structure | |
| CN114467953A (en) | Method for synthesizing bispyribac-sodium slow-release agent by reconstructing hydrated calcium chloroaluminate structure | |
| JPH06305724A (en) | Synthetic porous material and its production | |
| CN102674384B (en) | Hydrotalcite like compound-kaolin composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |