WO2004054361A1 - Formulation de glycophosphate a liberation lente a structure supermoleculaire, et procede de preparation correspondant - Google Patents

Formulation de glycophosphate a liberation lente a structure supermoleculaire, et procede de preparation correspondant Download PDF

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Publication number
WO2004054361A1
WO2004054361A1 PCT/CN2003/000617 CN0300617W WO2004054361A1 WO 2004054361 A1 WO2004054361 A1 WO 2004054361A1 CN 0300617 W CN0300617 W CN 0300617W WO 2004054361 A1 WO2004054361 A1 WO 2004054361A1
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WO
WIPO (PCT)
Prior art keywords
gly
glyphosate
ldhs
release agent
sustained
Prior art date
Application number
PCT/CN2003/000617
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English (en)
Chinese (zh)
Inventor
Xue Duan
Jinhong Meng
Hui Zhang
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Beijing University Of Chemical Technology
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Publication date
Application filed by Beijing University Of Chemical Technology filed Critical Beijing University Of Chemical Technology
Priority to AU2003248230A priority Critical patent/AU2003248230A1/en
Publication of WO2004054361A1 publication Critical patent/WO2004054361A1/fr

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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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the invention relates to a pesticide slow-release agent and a preparation method thereof, and particularly to a supramolecular structure glyphosate slow-release agent and a preparation method thereof.
  • the creation of new formulations based on traditional pesticides to achieve controllable quantity, time and space of pesticide release has become an important direction of pesticide research in recent years.
  • the sustained-release formulations of pesticides can maintain a specific concentration at a point of action for a long time with fewer side effects. Therefore, they have the following advantages: (1) Slow release of pesticides and prolonged (2) Reduce toxicity; (3) Reduce drug damage; (4) Reduce environmental pollution; (5) Reduce reactivity; (6) Reduce drift; (7) Easy to operate, save labor, etc. .
  • Existing pesticide controlled release formulations can be divided into physical and chemical agricultural release agents based on host-guest interactions. The interaction between the effective components of pesticides and the parent in physical slow translation agents is weak. Chemical pesticide slow release agents can achieve controlled release of pesticides to a certain extent. However, most of the currently studied chemical pesticide slow release agents are mainly There are micro-particulate pesticide slow-release dosage forms and pesticide slow-release dosage forms based on polymer materials. Although they have good pesticide slow-release effects, there are still many shortcomings: First, they are usually only suitable for oil-solubility. Insecticides limit the scope of application of pesticides. Second, due to the degradability requirements that do not produce secondary pollution, there are not many types of matrix materials to choose from.
  • the solid loading of the effective components of the pesticide is not high. Fourth, although the slow release of the pesticide can be achieved, the performance of controlling the release of the pesticide from the release time and quantity is low.
  • Patent US5576008 mechanically mixing urea-formaldehyde resin, pesticide, and vegetable oil to prepare microcapsule slow-release agent, but this method is only applicable to oil-soluble pesticides.
  • the synthetic microcapsule has a low pesticide content (about 1.3%), and is prepared. A large amount of vegetable oil (0.1-0.6g / ml prepolymer) is consumed during the process.
  • Patent US5516520 adds boron to a gelatinized mixture of starch, urea, water, and pesticides to convert the mixture into rubber blocks. After pulverization, a granular pesticide sustained-release dosage form is obtained. This formulation increases the pesticide loading to 1-25%, but its more suitable range is 3-10%. The pesticide loading is still low, and the formulation is still only suitable for oil-soluble pesticides.
  • Patent EP0843963 uses biodegradable polymers as the matrix (comonomers are dicarboxylic acids and alcohols) to synthesize pesticide sustained release dosage forms.
  • This dosage form can be applied to water-soluble pesticides, but its scope of application is only pesticides.
  • this dosage form cannot be applied to pesticides with low melting points (generally not lower than 70 ° C).
  • Glyphosate is a broad-spectrum, soluble, ionic, and highly effective post-emergent herbicide, and belongs to the 4-fouling organism of amino acids. Due to its versatility in many agricultural and non-agricultural settings, it has become a global herbicide. Since its introduction in the early 1970s, glyphosate has become the world's leading and fastest growing pesticide. In China, glyphosate is widely used due to its excellent resistance and is the most widely used herbicide in China. However, according to the indoor biotoxicity test, it is known that the effective dose of this pesticide is very small, and in actual application, due to repeated spraying, the dosage is multiplied. 'In addition to the environmental impact, the loss and decomposition of the pesticide are serious.
  • the purpose of the present invention is to prepare a glyphosate sustained-release dosage form that can effectively control the release rate and duration of the glyphosate, and the application of the slow-release agent is not limited by soil acidity and alkalinity.
  • the anionic layered material LDH is used as the main body and glyphosate is used as the intercalation object.
  • the hydrophilic herbicide glyphosate is intercalated between LDH layers by different synthetic methods to obtain a supermolecular structure of glyphosate. Release agent GLY-LDHs.
  • GLY-LDHs supramolecular structure of the crystal structure of the crystal structure of the hydrotalcite-like material, having the formula: (M 2+), - X (M 3+) X (OH) 2 (GLY-) al (GLY 2 -) ⁇ (GLY 3- ), ⁇ mH 2 0.
  • M 2+ may be any one of Mg 2+ , Zn 2+ , Cu 2+ , Ni 2+ , Co 2+ , Ca 2+ , Mn 2+ , Fe 2+ , Li +, preferably Mg 2+ , Zn 2+ , Li + ;
  • M 3+ may be any of Al 3+ , Cr ⁇ Fe 3+ , V 3+ , Co 3+ , Ga 3+ , Ti 3+ , preferably Al 3+ , Fe 3+ ;
  • GLY-, GLY 2 _, GLY 3 represent interlayer monovalent, divalent, and trivalent glyphosate anions, respectively. At least one of GLY-, GLY 2 ⁇ GLY 3 -exists in the chemical formula of GLY-LDHs;
  • ⁇ ⁇ - is an inorganic anion with a charge of ⁇ .
  • B n - may be absent or C0 3 2- , N0 3- , Cl ', Br-, ⁇ , OH-, H 2 P0 4- Any one, two or three of them;
  • the mass percentage content of glyphosate pesticide in this slow-release agent is 8-5Q%, preferably 10-30%; the mass percentage content of water is 1-35%, preferably 5-25%; release
  • the validity period can reach 0.2-24 months, and generally can reach 0.3-11 months.
  • GLY-LDHs can be applied to soils with a wide pH range, and by changing the type of the main layer element, GLY-LDHs can be further applied to soils with a pH value in the range of 3-13, especially suitable for pH values in the range of 5-12 Soil within range.
  • ZnAl, ZnCr, and ZnFe-type GLY-LDHs are suitable for soils with a pH value in the range of 3-10
  • MgAl and MgFe-type GLY-LDHs are suitable for soils with a pH value in the range of 5-12.
  • the present invention can realize the control of the structure, composition, release amount and release duration of GLY-LD_Hs.
  • the layered structure of GLY-LDHs and the high hydrophilicity of the main body make the sustained-release agent have a strong affinity with the natural environment, and the high water content between GLY-LDHs layers and the surface makes it practical when applied Reduced requirements for environmental water supply.
  • Step 2 Pour Solution A and Solution B simultaneously into the rotating liquid film reactor at a rate of 10-500ml / min, set the slit of the rotating liquid film reactor to 2-15 ⁇ ⁇ , and rotate the rotor of the liquid film reactor
  • the rotation speed is 1500-7000rpm, and the rotation speed is preferably 2500-6000rpm. After 1-10min of reaction, the material is discharged and transferred to the crystallization kettle;
  • Step 3 Protect with N 2 in the crystallization kettle, crystallize the slurry at 15-150 ° C for 2-72h, and then suction filtration, washing with water to neutrality, and drying at 15-150 ° C for 2-72h to obtain ⁇ GLY-LDHs ; All water is decarbonated and deionized water.
  • Steps 1 and 3 are the same as method 1.
  • Step 2 uses a co-precipitation method for nucleation, that is, under the protection of N 2 , add solution A to the vigorously stirred solution B at a rate of 0.001 to 1 ml / s until the pH of the obtained mixed slurry is 4-12, preferably The pH of the slurry is 7-11.
  • the preferred molar ratio of M 2+ / M 3+ is 1.5-4: 1; the preferred molar ratio of NaOH and glyphosate is 3-7: 1; the preferred crystallization temperature is 25. -100 ° C, the preferred crystallization time is 4-26h; the preferred drying temperature is 25-100 ° C, and the drying time is 4-32h.
  • M 2+ may be any one of Mg 2+ , Zn 2+ , Cu 2+ , Ni 2+ , Co 2+ , Ca 2+ , Mn 2+ , Fe 2+ , Li +
  • M 3+ may be Al 3+ , Cr 3+ , Fe 3+ , V 3+ , Co 3+ , Ga 3+ , Ti 3+ Any of these is preferably Al 3+ or Fe 3+ .
  • the anions of the soluble M 2+ and M 3+ salts may be NO 3- , Cr, Br-, ⁇ , OH-, H 2 P0 4 ", C0 3 2 —, among which NO 3- , Cl- are preferred.
  • Method 1 was invented by our laboratory (see patent application 00132145.5) and was first applied to synthetic organic intercalation LDH.
  • this method nucleates quickly, which overcomes the disadvantage of uneven particle size of the product obtained by the traditional organic intercalation LDHs assembly method and ensures the uniform grain size during the crystallization It is easy to obtain uniform and fine particles, which is beneficial to control the performance of GLY-LDHs to release glyphosate.
  • the preparation process is convenient, the reaction time is short, the operation is easy to control, the cost is economical, and it is easy to industrialize
  • the synthesis process of Method 2 is relatively simple, and it is easy to regulate the performance of the slow-release agent by finely adjusting the pH value of the synthesis process.
  • GLY-LDHs is a supramolecular intercalation structure, there is a strong covalent bond in its main layer, and the interlayer is a weak interaction force. Its layered structure is important for interlayer species (especially C0 3 2- ) GLY-LDHs has molecular recognition ability and its laminate structure is relatively stable, so after the application of GLY-LDHs in air and soil (0 2 and water or other inorganic anions in the soil, the interlayer glyphosate can Was gradually driven out to achieve the purpose of controlled release (see Figure 1, Figure 3).
  • the host material LDH of the GLY-LDHs of the present invention has various types.
  • a glyphosate sustained-release agent suitable for different acid and alkaline soils can be further obtained, for example: Mg, A1 GLY-LDHs with Mg or Fe as laminate elements, whose main laminates are not easily stripped under alkaline conditions, GLY-LDHs with Zn and Al, Zn and Fe, Li and Al, and Zn and Cr as laminate elements Its main laminate is not easily peeled off under weakly acidic or acidic conditions. Therefore, the GLY-LDHs of the present invention can be widely applied to soils having a pH range of 3-13 by changing the type of the main layer element.
  • the GLY-LDHs structure, composition, release amount and release sustaining effect can be achieved Period of control.
  • the layered structure and high hydrophilicity of the GLY-LDHs of the present invention make the sustained-release agent have a strong affinity with the natural environment, and the high water content between the layers and the surface of the GLY-LDHs makes it practical The requirements for the amount of environmental water supply during application are reduced.
  • Figure 1 shows the intercalation assembly and glyphosate release model of the superstructure substructure glyphosate sustained-release agent GLY-LDHs.
  • a is a salt of soluble M 2+ and M 3+ forming the GLY-LDHs main laminate Mixed solution;
  • b is an alkaline solution of the herbicide glyphosate;
  • c is a supramolecular structure of GLY-LDHs;
  • d is an interlayer guest LDH which is mainly an inorganic anion;
  • e is glyphosate which is gradually released.
  • the interlayer is a weak interaction force, and its layered structure has the characteristics of interlayer species (especially co 3 2- ). molecular recognition ply structure and which is relatively stable, so that the release agent is applied in air and soil C0 2, under the action of water or other inorganic anion in the soil, the interlayer glyphosate driven out gradually, and therefore, GLY-LDHs can achieve the purpose of controlled release.
  • Fig. 2 is an X-ray powder diffraction pattern of GLY-LDHs under the assembly conditions of Example 1. As can be seen from Fig. 2, the GLY-LDHs has a crystal structure of a hydrotalcite-based material.
  • Figure 3 shows the rate curve of glyphosate release from GLY-LDHs in Example 2 and Example 5 assembled in sodium carbonate solution, as can be seen from Figure 3: GLY-LDHs has a slower performance than the herbicide glyphosate. ; Two products with the same crystallization time but the same glyphosate content have different glyphosate release rates.
  • FIG. 4 is a graph of the release rate of glyphosate from GLY-LDHs in different pH buffer solutions under assembly conditions in Example 2.
  • FIG. 4 reflects that GLY-LDHs have a slow release of glyphosate in different pH environments. ability. Specific implementation plan
  • the product was analyzed using TG / DTA ICP and elemental analysis methods.
  • the chemical formula / composition of the product and the content of glyphosate in it were as follows:
  • Mg (N0 3 ) 2 ⁇ 6H 2 0 and A1 ( ⁇ 0 3 ) 3 ⁇ 9H 2 0 were mixed into a mixed solution A at a molar ratio of Mg / Al equal to 2, and the molar ratio of the original NaOH / glyphosate drug was 8 Formulated into solution B with the same volume as solution A.
  • the resulting slurry was crystallized under the protection of N 2 for 22 h, and then filtered through suction, washed with water to neutrality, and dried at 100 ° C. for 10 h.
  • the herbicide glyphosate was intercalated with magnesium and aluminum LDH. Deionized water.
  • Example 2 According to the synthesis process of Example 1, Mg (N0 3 ) 2 ⁇ 60 was replaced by Zn (N0 3 ) 2 '6H 2 0. The crystallization temperature, crystallization time, drying temperature, and drying time were 40 ° C. 20h 25 ° C 32h, glyphosate intercalation zinc aluminum LDH can be obtained. Glyphosate content is 18%
  • Example 1 According to the synthesis process of Example 1, the pH value of the slurry after controlling the dropwise addition was controlled to be about 8.5, and the remaining conditions were the same as those of Example 1 to obtain a glyphosate intercalated magnesium aluminum LDH.
  • Product chemical formula / composition is:
  • Example 2 According to the synthesis process of Example 2, the crystallization time was changed to 4 hours, and the remaining conditions were the same as those of Example 2. The glyphosate intercalated magnesium aluminum LDH was obtained. The glyphosate content (20%) in the product was the same as in the product of Example 2.
  • Example 2 and Example 5 Take 1 lg of each of the products of Example 2 and Example 5 and disperse them in 200 ml of sodium carbonate solution in a flask. Then place the Erlenmeyer flask in a water bath constant temperature shaker to continue shaking. A small amount of suspension was taken at a certain time interval. After the obtained suspension was centrifuged, the concentration of glyphosate in the supernatant was determined by UV spectrophotometry according to GB12686-90. This was used to examine the product's slow release of glyphosate.
  • GLY-LDHs with different release rates of glyphosate can be obtained by changing the crystallization time of the synthesis process.
  • Example 2 Take 3 parts of the product of Example 2 (each lg) and disperse them in three conical flasks with different pH buffer solutions (pH 5.5 6.6 7.6). Then place the Erlenmeyer flask in a water bath thermostat and shake continuously. Take a small amount of suspension at a certain time interval. After the separated suspension is separated by centrifugation, the concentration of glyphosate in the supernatant is determined by UV spectrophotometry according to GB12686-90. Based on this, the performance of the product's slow release of glyphosate was investigated. The rate of glyphosate release from the product of Example 2 in buffer solutions with different pH values (see Figure 4) shows that GLY-LDHs have the ability to slowly release glyphosate in different pH environments.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

La présente invention concerne une formulation de glycophosphate à libération lente à structure supermoléculaire et le procédé de préparation correspondant. La solution de sels mélangés de deux sels de métaux solubles est associée en composé en une opération avec la solution basique de glycophosphate donnant des GLY-LDH avec un supermoléculaire dont la formule chimique est (M2+)1-x(M3+)x(OH)2(GLY-)al(GLY2-)a2(GLY3-)a3(Bn-)b.mH2O, une couche de LDH anionique constituant le corps principal, le glycophosphate étant l'objet interstratifié. Dans la formulation, le glycophosphate représente 8 à 50 % de la masse, l'eau comptant pour 1 à 35% de la masse. La libération du glycophosphate peut durer de 0,2 à 24 mois. De tels GLY-LDH conviennent à des sols aux plages de pH sauvages, tels que 3-13.
PCT/CN2003/000617 2002-12-13 2003-08-01 Formulation de glycophosphate a liberation lente a structure supermoleculaire, et procede de preparation correspondant WO2004054361A1 (fr)

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AU2003248230A AU2003248230A1 (en) 2002-12-13 2003-08-01 A slow-released glyphosate formulation with supermolecular structure and the preparation method thereof

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CN02155466.8 2002-12-13
CN 02155466 CN1245079C (zh) 2002-12-13 2002-12-13 一种超分子结构草甘膦缓释剂及其制备方法

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CN1299616C (zh) * 2004-09-21 2007-02-14 北京化工大学 一种缓释型食品防腐剂插层材料及其制备方法
CN1293832C (zh) * 2005-07-06 2007-01-10 北京化工大学 一种磁性插层结构缓释型山梨酸及其制备方法
CN100383197C (zh) * 2006-06-09 2008-04-23 北京化工大学 超分子插层结构磺基水杨酸及其制备方法和用途
CN101530620B (zh) * 2009-03-18 2012-05-23 北京化工大学 一种三磷酸腺苷插层水滑石薄膜及其制备方法
CN101773487B (zh) * 2010-01-15 2011-12-07 北京化工大学 外来植物黄顶菊有效成分绿原酸插层水滑石及其制备方法
CN104823970B (zh) * 2014-04-15 2016-08-17 海南大学 一种载药Pickering乳液的制备方法
CN104396949A (zh) * 2014-11-17 2015-03-11 江苏隆昌化工有限公司 一种水化氯铝酸钙结构重建合成农药缓释剂方法
CN104509531A (zh) * 2014-11-17 2015-04-15 江苏隆昌化工有限公司 一种农药-氯铝酸钙缓释剂一步组装合成方法
CN112806357B (zh) * 2021-01-15 2022-12-20 中国农业大学 一种甲哌鎓控释剂及其在作物化学调控中的应用

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CN1272806A (zh) * 1997-10-02 2000-11-08 水农业德国有限公司 制造阴离子交换矿物的方法以及该矿物的用途
CN1287967A (zh) * 1999-09-14 2001-03-21 北京化工大学 一种层状双羟基复合金属氧化物粉体的表面处理方法
CN1288078A (zh) * 1999-09-14 2001-03-21 北京化工大学 均分散超细阴离子层状材料的新合成方法
JP3278631B2 (ja) * 1999-04-06 2002-04-30 科学技術振興事業団 アニオン−層状複水酸化物層間化合物の製法及びその製造物
WO2002047729A2 (fr) * 2000-12-14 2002-06-20 Isis Innovation Limited Systeme d'apport de medicaments
CN1404460A (zh) * 2000-01-28 2003-03-19 联邦科学和工业研究组织 肥料,土壤处理剂,土壤处理方法和无土介质

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CN1057211A (zh) * 1990-06-08 1991-12-25 密歇根州州立大学托管委员会 用吸着剂从烟道气和其他气流中除去硫氧化物的方法
CN1272806A (zh) * 1997-10-02 2000-11-08 水农业德国有限公司 制造阴离子交换矿物的方法以及该矿物的用途
JP3278631B2 (ja) * 1999-04-06 2002-04-30 科学技術振興事業団 アニオン−層状複水酸化物層間化合物の製法及びその製造物
CN1287967A (zh) * 1999-09-14 2001-03-21 北京化工大学 一种层状双羟基复合金属氧化物粉体的表面处理方法
CN1288078A (zh) * 1999-09-14 2001-03-21 北京化工大学 均分散超细阴离子层状材料的新合成方法
CN1404460A (zh) * 2000-01-28 2003-03-19 联邦科学和工业研究组织 肥料,土壤处理剂,土壤处理方法和无土介质
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CN1245079C (zh) 2006-03-15
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