CN1507778A - Supermolecular structure glyphosate slow release agent and preparing method thereof - Google Patents
Supermolecular structure glyphosate slow release agent and preparing method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
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Abstract
The present invention relates to a glyphosate slowly-releasing agent with supermolecular structure and its preparation method. Said invention uses anionic layer material LDH as main body, and uses glyphosate as intercalation guest, makes the mixed salt solution prepared by two soluble metal salts and alkali solution of glyphosate undergo the process of one-step assembling treatment to obtain GLY-LDHs with supermolecular structure, its chemical formula is :(M2+)1-x(M3+)x(OH)2(GLY_)al(GLY2-)a2(GLY3-)as(Bn-)b.mH2O. The mass percentage content of glyphosate pesticide in said slowly-releasing agent is 8-50%, and mass percentage content of water is 1-35%, and its release continuous effective period can be up to 0.2-24 months. It is applicable to soil whose pH value is in the range of 3-13.
Description
Technical field:
The present invention relates to a kind of pesticide slow-releasing agent and preparation method thereof, be specifically related to a kind of supramolecular structure controlled-release fomulation of glyphosate and preparation method thereof.
Background technology:
At present,,, realize that agricultural chemicals burst size, release time and Free up Memory are controlled, become the important directions of pesticide research in recent years with traditional agricultural chemicals initiative novel form at developing safety, efficient, economic, the requirement of environment friendly agricultural easily.When using, can keep a particular concentration for a long time on an application point and side effect is less based on the pesticide slow-release formulation of traditional pesticide manufacturing, therefore, it has following advantage: (1) slowly discharges agricultural chemicals, prolongs to hold effect; (2) reduce toxicity; (3) alleviate poisoning; (4) reduce environmental pollution; (5) reduce reactivity; (6) reduce drift; (7) easy operating is saved labour etc.
Existing agricultural chemicals sustained release formulation can be divided into physical and chemical type pesticide slow-releasing agent by host-guest interaction.In the physical sustained release agent between agricultural chemicals active principle and the parent active force a little less than, the chemical type pesticide slow-releasing agent can be realized the sustained release to agricultural chemicals to a certain extent, yet study at present that more chemical type pesticide slow-releasing agent mainly contains the microencapsulation of pesticide slow release formulation and be the pesticide slow-release formulation of matrix with the macromolecular material, though the two has pesticide slow-release effect preferably, but still there are many weak points: one, usually only be applicable to the oil-soluble insecticide, make the range of application of agricultural chemicals be subjected to certain limitation; Its two, for the degradable requirement that does not produce secondary pollution, alternative matrix material kind is also few; Its three, be subjected to the influence of factor such as sterically hindered, the supported quantity of agricultural chemicals active principle is not high; Its four, though can realize slow release, realize lower to the performance of agricultural chemicals sustained release from release time and burst size to agricultural chemicals.
Patent US5576008 prepares controlled release formulation of capsule with urea-formaldehyde resin, agricultural chemicals, vegetable oil mechanical mixture, but this method is only applicable to oil-soluble pesticide, pesticide concentration lower (being about 1.3%) in the synthetic microcapsules, and need to consume a large amount of vegetable oil (0.1-0.6g/ml prepolymer) in the preparation process.
Patent US5516520 adds borax in the gelatinize mixture of starch, urea, water, agricultural chemicals makes mixture be converted into block rubber, obtains granular pesticide slow-release formulation after crushed.This formulation is increased to 1-25% with the agricultural chemicals load capacity, but its suitable scope is 3-10%, and the agricultural chemicals load capacity is still on the low side, and this formulation still only is applicable to the oil-soluble insecticide.
Patent EP0843963 is matrix (comonomer is a dicarboxylic acids and alcohol) synthetic pesticide slow release formulation with biodegradable polymer.This formulation can be applicable to the part water soluble pesticide, but its scope of application only is insecticide.In addition, be subjected to the restriction of synthetic method, this formulation can not be applied to low melting point (generally being not less than 70 ℃) agricultural chemicals.
Glyphosate is a steriland herbicide after wide spectrum, solubility, ionic, the shoot buds, belongs to amino acid whose derivative.Because in the versatility of many agriculturals and non-agricultural occasion, it has become global weed killer herbicide.Since promoting the beginning of the seventies, glyphosate has become agricultural chemicals advanced in the world and fastest-rising.In China, glyphosate is able to extensive use owing to resistance is good, is the weed killer herbicide of China's usage amount maximum.But, learn according to indoor biological virulence test, the effective dose of this agricultural chemicals is very little, and in actual the using, owing to spray repeatedly, dosage is multiplied, the influence of environment in addition, the loss of agricultural chemicals and decomposition are serious, not only there is potential pollution in water body resources such as rivers,lakes and seas, also can cause selectivity to poison problem.But, to overcome the weak point that it is used, there is no report both at home and abroad at present with traditional glyphosate technicals initiative controlled-release fomulation of glyphosate type.
Summary of the invention:
The objective of the invention is: prepare a kind of controlled-release fomulation of glyphosate type that can effectively control the rate of release of glyphosate and discharge the lasting period, and the application of this sustained release agent is not subjected to the restriction of soil ph.
The present invention is based on anion laminated material LDH, and glyphosate is the intercalation object, by different synthetic methods hydrophilic herbicide glyphosate intercalation is assembled into the LDH interlayer, obtains supramolecular structure controlled-release fomulation of glyphosate GLY-LDHs.
Supramolecular structure GLY-LDHs crystal structure is the crystal structure of houghite material, and its chemical formula is: (M
2+)
1-x(M
3+)
x(OH)
2(GLY
-)
A1(GLY
2-)
A2(GLY
3-)
A3(B
N-)
bMH
2O.
M wherein
2+Can be Mg
2+, Zn
2+, Cu
2+, Ni
2+, Co
2+, Ca
2+, Mn
2+, Fe
2+, Li
+In any, that preferable is Mg
2+, Zn
2+, Li
+
M
3+Can be Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, Al preferably
3+, Fe
3+
GLY
-, GLY
2-, GLY
3-Represent interlayer monovalence, divalence, trivalent glyphosate anion respectively, GLY in the GLY-LDHs chemical formula
-, GLY
2-, GLY
3-Has a kind of existence at least;
B
N-For carrying capacity is the inorganic anion of n, B in the GLY-LDHs chemical formula
N-Can not exist or for CO
3 2-, NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -In any, two kinds or three kinds;
0.1＜x＜0.8, better suited scope are 0.2＜x＜0.5; A1, a2, a3, b are respectively GLY
-, GLY
2-, GLY
3-, B
N-Quantity, and a1+2 * a2+3 * a3+n * b=x; M is water of crystallization quantity and 0.01＜m＜4, and better suited scope is 0.1＜m＜1.5.
Glyphosate pesticide quality percentage composition is 8-50% in this sustained release agent, and that preferable is 10-30%; The quality percentage composition of water is 1-35%, and that preferable is 5-25%; The release lasting period can reach the 0.2-24 month, generally can reach the 0.3-11 month.
GLY-LDHs is applicable to the soil of pH wider range, and can further make GLY-LDHs be applicable to the soil of pH value in the 3-13 scope by the kind that changes the body layer plate element, is particularly useful for the soil of pH value in the 5-12 scope.Be applicable to the soil of pH value in the 3-10 scope as ZnAl type, ZnCr type, ZnFe type GLY-LDHs, MgAl, MgFe type GLY-LDHs are applicable to the soil of pH value in the 5-12 scope.
The present invention can realize GLY-LDHs structure, composition, burst size and the control of release lasting period by adjusting the synthesis condition of GLY-LDHs.
The higher hydrophily of the layer structure of GLY-LDHs and main body makes this sustained release agent and natural environment have stronger compatibility, and the higher water content of GLY-LDHs interlayer and surface reduces its requirement to the environment output when actual using.
Controlled-release fomulation of glyphosate of the present invention can realize that concrete preparation process is as follows by following two kinds of methods:
Method 1: full back-mixing liquid film reactor nucleation process
Step 1: with soluble M
2+, M
3+Salt press M
2+/ M
3+=1-7: 1 mol ratio is made into mixing salt solution A, in addition with NaOH and glyphosate technicals by 2-9: 1 mol ratio is mixed with and A equal-volume aqueous slkali B;
Step 2: solution A and solution B are poured in the rotation liquid film reactor by 10-500ml/min speed simultaneously equably, setting rotation liquid film reactor slit is 2-15 μ m, rotation liquid film reactor rotary speed of rotator is 1500-7000rpm, the preferred 2500-6000rpm of rotating speed, discharging behind the reaction 1-10min changes crystallizing kettle over to;
Step 3: in crystallizing kettle, use N
2The protection, make slurries at 15-150 ℃ of crystallization 2-72h, again through suction filtration, be washed to neutrality, 15-150 ℃ of dry 2-72h obtains GLY-LDHs; Institute's water is the carbon dioxide removal deionized water.
Method 2: coprecipitation
Step 1 is identical with method 1 with step 3.
In above-mentioned two kinds of methods, M
2+/ M
3+More excellent mol ratio is 1.5-4: 1; The more excellent mol ratio of NaOH and glyphosate technicals is 3-7: 1; Preferable crystallization temperature is 25-100 ℃, and preferable crystallization time is 4-26h; Preferable baking temperature is 25-100 ℃, and be 4-32h drying time.
In above-mentioned two kinds of methods, M
2+Can be Mg
2+, Zn
2+, Cu
2+, Ni
2+, Co
2+, Ca
2+, Mn
2+, Fe
2+, Li
+In any, that preferable is Mg
2+, Zn
2+, Li
+M
3+Can be A1
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, Al preferably wherein
3+, Fe
3+Soluble M
2+, M
3+The anion of salt can be NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -, CO
3 2-, wherein be preferably NO
3 -, Cl
-
Method 1 is this research department's invention (seeing patent application 00132145.5), and first Application is in synthesis of organic substance intercalation LDH.Nucleation is rapid on the one hand for this method, overcome the inhomogenous shortcoming of traditional organic matter intercalation LDHs assemble method products therefrom particle diameter, guaranteed the uniformity of crystallite dimension in the crystallization process, be easy to obtain the even and tiny particle of size, and then help the performance of GLY-LDHs release glyphosate is controlled; On the other hand, preparation process is easy, the reaction time is short, easy operating is controlled, cost is comparatively economical and be easy to industrialization, and the building-up process of method 2 is also simpler, and is easy to by the pH value of regulating and control building-up process subtly the performance of this sustained release agent be regulated and control.
Because GLY-LDHs is supermolecular intercalation structure, its body layer board memory is in strong covalent bond effect, and interlayer then is a kind of weak interaction force, and its layer structure is to interlayer species (CO particularly
3 2-) have molecule distinguishability and its veneer structure is relatively stable, so GLY-LDHs uses back CO in air and soil
2Under water effect effect following or other inorganic anion in soil, the interlayer glyphosate can progressively be displaced, and reaches the purpose (seeing Fig. 1, accompanying drawing 3) of sustained release.
The material of main part LDH of GLY-LDHs of the present invention has polytype, can further obtain being applicable to the controlled-release fomulation of glyphosate of different Acidity of Aikalinity soil by the kind of adjusting body layer sheetmetal element among the GLY-LDHs, for example: Mg, Al or Mg, Fe are the GLY-LDHs of laminate element, its main body laminate is difficult for being stripped under alkali condition, is that its main body laminate of GLY-LDHs of laminate element is difficult for being stripped under faintly acid or acid condition with Zn and Al, Zn and Fe, Li and Al, Zn and Cr.Therefore, can make GLY-LDHs of the present invention be widely used in the soil that pH is the 3-13 scope by the kind that changes the body layer plate element.
By adjusting the assembling condition of GLY-LDHs, for example: change M
2+/ M
3+The pH value of mol ratio, building-up process, synthesis temperature, generated time etc. can be realized GLY-LDHs structure, composition, burst size and the control of release lasting period.
The higher hydrophily of the layer structure of GLY-LDHs of the present invention and main body makes this sustained release agent and natural environment have stronger compatibility, and the higher water content of GLY-LDHs interlayer and surface reduces its requirement to the environment output when actual using.
Description of drawings
Fig. 1 is assembling of hyperon separation structure controlled-release fomulation of glyphosate GLY-LDHs intercalation and glyphosate dispose procedure model.Wherein a is for forming the soluble M of GLY-LDHs main body laminate
2+, M
3+The mixed solution of salt; B is the aqueous slkali of herbicide glyphosate; C is supramolecular structure GLY-LDHs; D is mainly the LDH of inorganic anion for the interlayer object; The glyphosate of e for progressively being discharged.
Comprise two processes among Fig. 1:
(1) intercalation assembling process (f among the figure): assembling obtains supramolecular structure GLY-LDHs through a step for the mixed solution of two kinds of soluble metallic salts and the aqueous slkali of glyphosate;
(2) the slow dispose procedure of glyphosate (g among the figure): the CO of GLY-LDHs in air, soil
2, water and inorganic anion effect under, its interlayer object glyphosate is progressively displaced.
As seen from Figure 1 since GLY-LDHs body layer board memory in strong covalent bond effect, interlayer is a kind of weak interaction force, its layer structure is to interlayer species (CO particularly
3 2-) have molecule distinguishability and its veneer structure is relatively stable, so this sustained release agent is used back CO in air and soil
2, water or in soil under the effect of other inorganic anion, the interlayer glyphosate can progressively be displaced, therefore, GLY-LDHs can reach the purpose of sustained release.
Fig. 2 is the X-ray powder diffraction figure of GLY-LDHs under embodiment 1 assembling condition, and as seen from Figure 2, this GLY-LDHs has the crystal structure of hydrotalcite-like material.
Fig. 3 is the rate curve that GLY-LDHs discharges glyphosate under embodiment 2, example 5 assembling conditions in sodium carbonate liquor, and as seen from Figure 3: GLY-LDHs has the performance of slow release herbicide glyphosate; The crystallization time difference, but two kinds of identical products of glyphosate content have different glyphosate rates of release.
Fig. 4 is the rate diagram that GLY-LDHs discharges glyphosate under embodiment 2 assembling conditions in different pH value buffer solution, reflects that from Fig. 4 GLY-LDHs all has the ability of slow release glyphosate in different pH environment.
Embodiment:
Embodiment 1
With Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O equals 2 by the Mg/Al mol ratio and is made into mixed solution A, and the NaOH/ glyphosate technicals is equaled 8 in molar ratio is mixed with solution B in addition.N
2Protection is added drop-wise to the speed of solution A by 10ml/min in the solution B of vigorous stirring down, and it is about 10.5 that control drips the pH value that finishes rear slurry.The gained slurries are in N
2Protection is crystallization 22h down, again through suction filtration, be washed to neutrality, the dry 7h of 100C, herbicide glyphosate intercalation magnalium LDH.Institute's water is the carbon dioxide removal deionized water in the process.
Adopt TG/DTA, ICP and elemental analysis method that product is analyzed, it is as follows to obtain the glyphosate content that chemical formula/compositions of product reach wherein:
Mg
0.681Al
0.319(OH)
2[(OOCCH
2NHCH
2PO
3)
3-]
0.055[(OOCCH
2NH
2CH
2PO
3)
2-]
0.049[(CO
3 2-)]
0.0280.57H
2O, glyphosate content are 19%;
With Mg (NO
3)
26H
2O and Al (NO
3)
39H
2O equals 2 by the Mg/Al mol ratio and is made into mixed solution A, in addition the NaOH/ glyphosate technicals is equaled 8 in molar ratio and is mixed with and the isopyknic solution B of solution A.Setting rotation liquid film reactor slit is 9 μ m, and rotation liquid film reactor rotary speed of rotator is 4000rpm, solution A is poured into by the speed of 600ml/min simultaneously equably with solution B rotated in the liquid film reactor, react about 4min after, the gained slurries are at N
2Protection is crystallization 22h down, again through suction filtration, be washed to neutrality after, 100 ℃ of dry 10h, herbicide glyphosate intercalation magnalium LDH.Institute's water is the carbon dioxide removal deionized water in the process.
Method with embodiment 1 is analyzed product, determines its chemical formula/composed as follows:
Mg
0.639Al
0.361(OH)
2[(OOCCH
2NHCH
2PO
3)
3-]
0.099[(OOCCH
2NHCH
2PO
3)
2-]
0.020[(CO
3 2-)]
0.0121.1H
2O, glyphosate content wherein is 20%.
Embodiment 3
Press the building-up process of embodiment 1, with Mg (NO
3)
26H
2O replaces with Zn (NO
3)
26H
2O adopts crystallization temperature, crystallization time, baking temperature, drying time 40 ℃, 20h, 25 ℃, 32h respectively, can get glyphosate intercalation zinc-aluminium LDH.Glyphosate content wherein is 18%.
Embodiment 4
Press embodiment 1 building-up process, it is about about 8.5 that control drip to finish the pH value of rear slurry, and all the other conditions are with embodiment 1, glyphosate intercalation magnalium LDH.Product chemical formula/consist of:
Mg
0.658Al
0.342(OH)
2[(OOCCH
2NHCH
2PO
3)
3-]
0.048[(OOCCH
2NHCH
2PO
3)
2-]
0.095[(CO
3 2-)]
0.0040.78H
2O, glyphosate content are 25%.
Embodiment 1 is compared with the product of embodiment 4, when the identical but pH value of other synthesis conditions not simultaneously, can obtain the different GLY-LDHs of glyphosate content.
Illustrate and utilize different pH synthesis conditions can obtain the GLY-LDHs of different glyphosate load capacity.
Press embodiment 2 building-up processes, the change crystallization time is 4h, and all the other conditions get glyphosate intercalation magnalium LDH with embodiment 2.Glyphosate content (20%) in the product is identical with embodiment 2 products.
Get each 1g of product of embodiment 2 and embodiment 5, be scattered in respectively in the 200ml sodium carbonate liquor in the conical flask.Then conical flask is put into the continuous oscillation of constant temperature water bath oscillator.By the certain hour suspension that takes a morsel at interval, institute's suspension of getting is after centrifugation, according to GB 12686-90, with the concentration of glyphosate in the determined by ultraviolet spectrophotometry supernatant.Investigate the performance that product slowly discharges glyphosate with this.The product of embodiment 2 and embodiment 5 discharges the rate diagram of glyphosate and sees Fig. 3 in sodium carbonate liquor, show to have identical glyphosate content, but two kinds of different products of crystallization time have different glyphosate rates of release.
Explanation can obtain to have the GLY-LDHs of the rate of release of different glyphosates by the crystallization time that changes building-up process.
Embodiment 6
Get the product (each 1g) of 3 parts of embodiment 2, be scattered in respectively in three conical flasks that different pH value buffer solution (the pH value is respectively 5.5,6.6,7.6) are housed.Then conical flask is put into the continuous oscillation of constant temperature water bath oscillator.By the certain hour suspension that takes a morsel at interval, institute's suspension of getting is after centrifugation, according to GB12686-90, with the concentration of glyphosate in the determined by ultraviolet spectrophotometry supernatant.Investigate the performance that product slowly discharges glyphosate with this.The product of embodiment 2 discharges the rate diagram (see figure 4) of glyphosate in different pH value buffer solution, show that GLY-LDHs all has the ability of slow release glyphosate in different pH environment.
Claims (8)
1. supramolecular structure controlled-release fomulation of glyphosate GLY-LDHs, its crystal structure is a hydrotalcite-like compound, its chemical formula is:
(M
2+)
1-x(M
3+)
x(OH)
2(GLY
-)
a1(GLY
2-)
a2(GLY
3-)
a3(B
n-)
b·mH
2O
M wherein
2+Can be Mg
2+, Zn
2+, Cu
2+, Ni
2+, Co
2+, Ca
2+, Mn
2+, Fe
2+, Li
+In any;
M
3+Can be Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any;
GLY
-, GLY
2-, GLY
3-Represent interlayer monovalence, divalence, trivalent glyphosate anion respectively, GLY in the GLY-LDHs chemical formula
-, GLY
2-, GLY
3-Has a kind of existence at least;
B
N-For carrying capacity is the inorganic anion of n, B in the GLY-LDHs chemical formula
N-Can not exist or for CO
3 2-, NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -In any, two kinds or three kinds;
0.1＜x＜0.8; A1, a2, a3, b are respectively GLY
-, GLY
2-, GLY
3-, B
N-Quantity, a1+2 * a2+3 * a3+n * b=x; M is a water of crystallization quantity, 0.01＜m＜4.
Glyphosate pesticide quality percentage composition is 8-50% in this sustained release agent, and the quality percentage composition of water is 1-35%; The release lasting period can reach the 0.2-24 month; Applicable to the soil of pH value in the 3-13 scope.
2. controlled-release fomulation of glyphosate GLY-LDHs as claimed in claim 1, M in its structural formula
2+Preferred Mg
2+, Zn
2+, Li
+, M
3+Preferred Al
3+, Fe
3+, the preferable scope of x is 0.2＜x＜0.5, the preferable scope of m is 0.1＜m＜1.5;
That glyphosate pesticide quality percentage composition is preferable is 10-30%, and that the quality percentage composition of water is preferable is 5-25%, and the release lasting period generally can reach the 0.3-11 month; More be applicable to the soil of pH value in the 5-12 scope.
3. the preparation method of a supramolecular structure controlled-release fomulation of glyphosate GLY-LDHs as claimed in claim 1, concrete preparation process is as follows:
Step 1: with soluble M
2+, M
3+Salt press M
2+/ M
3+The mol ratio of=1-7 is made into mixing salt solution A, in addition with NaOH and glyphosate technicals by 2-9: 1 mol ratio is mixed with and A equal-volume aqueous slkali B;
Step 2: solution A and solution B are poured in the rotation liquid film reactor by 10-500ml/min speed simultaneously equably, setting rotation liquid film reactor slit is 2-15 μ m, rotation liquid film reactor rotary speed of rotator is 1500-7000rpm, changes crystallizing kettle over to behind the reaction 1-10min;
Step 3: in crystallizing kettle, use N
2The protection, make slurries at 15-150 ℃ of crystallization 2-72h, again through suction filtration, be washed to neutrality, 15-150 ℃ of dry 2-72h obtains GLY-LDHs; Institute's water is the carbon dioxide removal deionized water.
4. the preparation method of a controlled-release fomulation of glyphosate GLY-LDHs as claimed in claim 3, wherein M
2+/ M
3+The preferred 1.5-4 of mol ratio: 1, NaOH and the preferred 3-7 of glyphosate technicals mol ratio: 1; Preferable crystallization temperature is 25-100 ℃, and preferable crystallization time is 4-26h; Preferable baking temperature is 25-100C, and be 4-32h preferable drying time.
5. the preparation method of a controlled-release fomulation of glyphosate GLY-LDHs as claimed in claim 3, M in the step 1
2+Can be Mg
2+, Zn
2+, Cu
2+, Ni
2+, Co
2+, Ca
2+, Mn
2+, Fe
2+, Li
+In any, M
3+Can be Al
3+, Cr
3+, Fe
3+, V
3+, Co
3+, Ga
3+, Ti
3+In any, soluble M
2+, M
3+The anion of salt can be NO
3 -, Cl
-, Br
-, I
-, OH
-, H
2PO
4 -, CO
3 2-
6. preparation method as claim 3,5 described controlled-release fomulation of glyphosate GLY-LDHs, M in the step 1
2+Preferred Mg
2+, Zn
2+, Li
+, M
3+Preferred Al
3+, Fe
3+, soluble M
2+, M
3+The preferred NO of the anion of salt
3 -, Cl; The preferred 2500-6000rpm of rotation liquid film reactor rotary speed of rotator in the step 2.
7. the preparation method of a supramolecular structure controlled-release fomulation of glyphosate GLY-LDHs as claimed in claim 3, wherein step 2 also can adopt coprecipitation to carry out nucleation, promptly at N
2Protection press solution A in the solution B of 0.001-1ml/s speed adding vigorous stirring down, to the pH value of gained mixed serum be 4-12.
8. the preparation method of a supramolecular structure controlled-release fomulation of glyphosate GLY-LDHs as claimed in claim 7, preferable slurry pH value is 7-11.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155466 CN1245079C (en) | 2002-12-13 | 2002-12-13 | Supermolecular structure glyphosate slow release agent and preparing method thereof |
| AU2003248230A AU2003248230A1 (en) | 2002-12-13 | 2003-08-01 | A slow-released glyphosate formulation with supermolecular structure and the preparation method thereof |
| PCT/CN2003/000617 WO2004054361A1 (en) | 2002-12-13 | 2003-08-01 | A slow-released glyphosate formulation with supermolecular structure and the preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155466 CN1245079C (en) | 2002-12-13 | 2002-12-13 | Supermolecular structure glyphosate slow release agent and preparing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1507778A true CN1507778A (en) | 2004-06-30 |
| CN1245079C CN1245079C (en) | 2006-03-15 |
Family
ID=32514448
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|---|---|
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| AU (1) | AU2003248230A1 (en) |
| WO (1) | WO2004054361A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293832C (en) * | 2005-07-06 | 2007-01-10 | 北京化工大学 | Magnetic sandwiching layer structure slow-releasing type sorbic acid, and its prepn. method |
| CN1299616C (en) * | 2004-09-21 | 2007-02-14 | 北京化工大学 | Intercalator of slow-releasing food preservative substance, and its prepn. method |
| CN100383197C (en) * | 2006-06-09 | 2008-04-23 | 北京化工大学 | Sulfosalicylic with super molecular inserting layer structure, its preparation process and use |
| WO2010105454A1 (en) * | 2009-03-18 | 2010-09-23 | 北京化工大学 | Adenosine triphosphate intercalated hydrotalcite film and preparation method therefor |
| CN101773487B (en) * | 2010-01-15 | 2011-12-07 | 北京化工大学 | Exotic plant Flaveria bidentis active ingredient chlorogenic acid intercalation hydrotalcite and preparation method thereof |
| 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 |
| CN104509531A (en) * | 2014-11-17 | 2015-04-15 | 江苏隆昌化工有限公司 | One-step assembly synthesis method of pesticide calcium chloroaluminate sustained release agent |
| CN104823970A (en) * | 2014-04-15 | 2015-08-12 | 海南大学 | Preparation method of drug-loading Pickering emulsion |
| 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 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5114691A (en) * | 1990-01-18 | 1992-05-19 | Board Of Trustees Operating Michigan State University | Process using sorbents for the removal of SOx from flue gas |
| DE19743606A1 (en) * | 1997-10-02 | 1999-04-15 | Hydro Agri Deutschland Gmbh | Use of anion-exchanging minerals |
| JP3278631B2 (en) * | 1999-04-06 | 2002-04-30 | 科学技術振興事業団 | Process for producing anion-layered double hydroxide intercalation compound and product thereof |
| CN1288078A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Method for synthesis of well-dispersed and super fine anion laminated material |
| CN1099999C (en) * | 1999-09-14 | 2003-01-29 | 北京化工大学 | Surface preparation of layered dihydroxy composite metal oxide powder |
| AUPQ533700A0 (en) * | 2000-01-28 | 2000-02-17 | Commonwealth Scientific And Industrial Research Organisation | Soil treatment method |
| GB0030460D0 (en) * | 2000-12-14 | 2001-01-24 | Isis Innovation | Drug delivery system |
-
2002
- 2002-12-13 CN CN 02155466 patent/CN1245079C/en not_active Expired - Fee Related
-
2003
- 2003-08-01 WO PCT/CN2003/000617 patent/WO2004054361A1/en not_active Application Discontinuation
- 2003-08-01 AU AU2003248230A patent/AU2003248230A1/en not_active Abandoned
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299616C (en) * | 2004-09-21 | 2007-02-14 | 北京化工大学 | Intercalator of slow-releasing food preservative substance, and its prepn. method |
| CN1293832C (en) * | 2005-07-06 | 2007-01-10 | 北京化工大学 | Magnetic sandwiching layer structure slow-releasing type sorbic acid, and its prepn. method |
| CN100383197C (en) * | 2006-06-09 | 2008-04-23 | 北京化工大学 | Sulfosalicylic with super molecular inserting layer structure, its preparation process and use |
| WO2010105454A1 (en) * | 2009-03-18 | 2010-09-23 | 北京化工大学 | Adenosine triphosphate intercalated hydrotalcite film and preparation method therefor |
| CN101773487B (en) * | 2010-01-15 | 2011-12-07 | 北京化工大学 | Exotic plant Flaveria bidentis active ingredient chlorogenic acid intercalation hydrotalcite and preparation method thereof |
| CN104823970A (en) * | 2014-04-15 | 2015-08-12 | 海南大学 | Preparation method of drug-loading Pickering emulsion |
| 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 |
| CN104509531A (en) * | 2014-11-17 | 2015-04-15 | 江苏隆昌化工有限公司 | One-step assembly synthesis method of pesticide calcium chloroaluminate sustained release agent |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003248230A1 (en) | 2004-07-09 |
| WO2004054361A1 (en) | 2004-07-01 |
| CN1245079C (en) | 2006-03-15 |
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