CN101703069B - Chlorpyrifos water dispersible composition and preparation method thereof - Google Patents
Chlorpyrifos water dispersible composition and preparation method thereof Download PDFInfo
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- CN101703069B CN101703069B CN200910213020A CN200910213020A CN101703069B CN 101703069 B CN101703069 B CN 101703069B CN 200910213020 A CN200910213020 A CN 200910213020A CN 200910213020 A CN200910213020 A CN 200910213020A CN 101703069 B CN101703069 B CN 101703069B
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Abstract
The invention relates to a chlorpyrifos water dispersible composition and a preparation method thereof, in particular to a chlorpyrifos water dispersible composition with stable cold and hot storage, which comprises the following raw materials in percentage by weight: 2-40 percent of chlorpyrifos, 0.5-10 percent of solvent of carboxylic acid or carboxylic ether, 15-90 percent of porous carrier and the balance of other functional auxiliary agents. The preparation method comprises the following steps of: a. proportionally heating the chlorpyrifos into liquid chlorpyrifos, and adding the liquid chlorpyrifos into the solvent of the carboxylic acid or the carboxylic ether to obtain a solution; b. simultaneously heating the carrier to 65-71 DEG C, adding the solution obtained in the step a intothe porous carrier to obtain a dry powder intermediate, and fully adsorbing an active substance in a liquid state by the used carrier; c. cooling the dry powder intermediate obtained in the step b, and then adding other auxiliary agents to obtain a solid or liquid preparation; and d. pulverizing the solid or liquid composition obtained in the step c to the required grain diameter of 2-20 microns.
Description
Technical field
Chlorpyrifos water dispersible composition of the present invention and preparation method thereof relates to the composition of aqueous dispersion of a kind of chlopyrifos of cold and hot stable storage.The invention particularly relates to the preparation of compositions of the aqueous dispersion of chlopyrifos.The composition low temperature caking that The present invention be more particularly directed to suppress to contain the aqueous dispersion of chlopyrifos is separated out the method for crystallization with heat storage back active component.
Background technology
Chlopyrifos is a kind of broad-spectrum organic insecticide; Its mechanism of action is acetylcholine esterase inhibition; Have tag, stomach toxicity and stifling three kinds of modes of action; Insecticidal spectrum is wide, toxicity is lower, is one of main insecticide of control grain, fruit tree, vegetables and other economic crops insect pest, to user's safety.
Chlopyrifos (chlorpyrifos) chemical name: O, and O-diethyl-OO (3,5,6 ,-trichloro-2-pyridyl phosphorothionate.Belong to phosphorothionate class broad spectrum pesticide, have tag, stomach toxicity and fumigation action.Chlopyrifos can be widely used in preventing and treating various pests and mite classes such as snout moth's larva, tortrix moth, mythimna separata, scale insect, aphid, cotton bollworm on the crops such as paddy rice, cotton, fruit tree, tealeaves, wheat, sugarcane; Toxicity is relatively low; Insect had tag, stomach toxicity and effect such as stifling, the double again mite class of controlling.In recent years, country has accelerated the paces of superseded high-toxic pesticide, and chlopyrifos has become high malicious organic phosphorous insecticide and substituted one of kind.Mainly being processed into missible oil at present at home uses.Also there are some new formulations such as aqueous emulsion of chlorpyrifos, microemulsion to put on market in recent years.These formulations are used all has certain shortcoming, as: cream preparation uses a large amount of organic solvent such as toluene, xylol etc., not only wastes industrial resources, and serious environment pollution, and user's health is had harmful effect.Chlopyrifos also can be processed into solid pharmaceutical preparation and be used.The solid pharmaceutical preparation that is processed into has two kinds of powder and particles.Chlopyrifos can also be processed into environment amenable suspending agent and be used.
But in the preparation of aqueous dispersion, solid pharmaceutical preparation is wetting powder (WP) for example, water dispersible granules (WG), and liquid preparation such as suspending agent (SC), the particle diameter of micro-capsule suspension (CS) has very big influence to stability of formulation and suspensibility.In order to obtain very little particle diameter (2-20um), the pulverizing of variety of way is essential.But because low-melting active matter fusing point is low, be no more than 90 ℃, directly the low-melting insecticide of solid pulverized very difficulty, because in the process of pulverizing, active substance is easy to be melted or is softening.Perhaps, low-temperature grinding can address this problem; But this method that the production cost of extra increase makes can not be used widely; And because the particle diameter that the pulverizing of this method of use obtains has satisfied not demand, thereby brought the problem of bin stability and suspensibility aspect.
Organophosphorus insecticide is relative unstable compounds, particularly under too high or too low pH condition, is prone to decompose.And organic phosphorus compound is having facile hydrolysis under the condition of water.Can know that from known technology the inside the chemical stability of the solid composite of organic phosphor can be improved through adding some material, has reduced the chemical degradation of active substance.
US4,380,537,5,140,019,5,165,934 and 5,260,312 have all disclosed organic phosphor have been loaded on some solid carriers, for example the technology of clay.US4 particularly, 380,537 have disclosed a solid composite that contains organophosphorus insecticide, for example chlopyrifos are loaded on the clay, and for example montmorillonite or attapulgite add 0.5% to 10% lactone as stabilizing agent.Other materials as the organic phosphor stabilizing agent have polyethylene glycol and and polypropylene glycol.But with the clay is carrier, and the solid composite that has added stabilizing agent is also not always satisfactory.One 15% chlopyrifos solid composite for example as carrier, adds 4.5% dipropylene glycol as stabilizing agent with clay.After this solid composite was stored under the low relatively temperature, caking phenomenon appearred in preparation, had had a strong impact on agriculture use.So far, also there is not good method to solve the problem of the solid composite low temperature caking of chlopyrifos.
On the other hand, because the fusing point of chlopyrifos low (42 ℃-43.5 ℃), the solid composite of chlopyrifos exists the problem that heat storage back is prone to crystallization.Heat storage back active component is prone to from preparation crystallization to be separated out, and when pesticide spray was used, filter was separated out owing to the crystallization of active component with the nozzle meeting and blocked, to the agricultural use band inconvenience, and influenced drug effect.Because these technical barriers, the solid of chlopyrifos or the aqueous dispersion preparation of liquid are not widely used.Therefore solve these technical barriers and become pressing for that chlopyrifos can extensive use.
Summary of the invention
The present invention seeks to provides a kind of chlorpyrifos water dispersible composition and preparation method thereof to above-mentioned weak point, and the composition of the aqueous dispersion through a kind of chlopyrifos of having improved low temperature flow and heat storage stability is provided has satisfied above-mentioned demand.
Chlorpyrifos water dispersible composition and preparation method thereof is to take following method to realize:
Chlorpyrifos water dispersible composition; It is characterized in that comprising the solvent of chlopyrifos, carboxylic acid or carboxylate, porous carrier and other functional aids, wherein the raw material weight per distribution ratio is that the solvent 0.5-10% of chlopyrifos 2%-40%, carboxylic acid or carboxylate, porous carrier 15%-90%, auxiliary agent are surplus.
Said solvent carboxylic acid or carboxylate are selected one or more and the ester thereof in palmitic acid, stearic acid, arachidic acid, mountain Yu acid, the rosin acid for use.
The solvent of said carboxylic acid or carboxylate is selected the ester of rosin acid or rosin acid for use, like rosin triglyceride.
Said porous carrier is selected kaolin for use, is covered a kind of or its mixture that takes off in clay, attapulgite, white carbon black, vegetable fiber, the mineral fibre.
Said functional aid is selected one or more in water, emulsifying dispersant, viscosity-controlling agent, antifreeze, biocide, antifoaming agent, the cyst material for use; Emulsifying dispersant is selected one or more in alkylsulfonate, wooden sulfonated salts, naphthalene sulfonate, AEO, the NPE phosphate for use; Viscosity-controlling agent is selected one or more in xanthans, cellulose ether and derivative thereof, the polyvinyl alcohol for use; Antifreeze is selected ethylene glycol, propane diols, glycerine, isopropyl alcohol or urea for use; Biocide is selected potassium sorbate, Sodium Benzoate, formaldehyde or isothiazolinone for use; Antifoaming agent is selected for use silicone based or the low-carbon alcohols antifoaming agent; The carbamide resin that cyst material selects for use the isocyanates and the polyamine aqueous solution to make through interface polymerization reaction.
The preparation method of chlorpyrifos water dispersible composition may further comprise the steps;
A. by proportioning chlopyrifos heating is become in the solvent that joins a carboxylic acid or carboxylate after the liquid phase and obtain a solution; Said chlopyrifos heating-up temperature is 50-60 ℃;
B. simultaneously carrier is heated to 65-71 ℃, the solution that obtains in (a) is added to removes to obtain the powder intermediate done in the porous carrier, active matter is fully adsorbed by used carrier under liquid state;
C. behind the powder intermediate of doing that obtains in the cooling (b), add other functional auxiliary agent, obtain the preparation with nature of business of solid or liquid;
D. the composition of pulverizing solid that (c) obtain or liquid is to the particle diameter 2-20um that needs;
Wherein the raw material weight per distribution ratio is solvent 0.5-10%, the porous carrier 15-90% of chlopyrifos 2%-40%, carboxylic acid or carboxylate, and functional aid is a surplus.
Said composite preparation is wettable powder (WP), water-dispersible granule (WDG), suspending agent (SC) or microcapsule suspending agent (CS).
Carboxylic acid in the composition of the present invention or carboxylate solvent are water-insoluble or the acid of indissoluble or ester.Acid can be unit acid or polyacid, aliphatic or alicyclic.Only is fatty acid, and for example cerinic acids such as palmitic acid, stearic acid, arachidic acid, mountain Yu acid also comprise synthetic aliphatic-aromatic hydrocarbon carboxylic acid, and cyclic carboxylic acids is rosin acid for example.Ester can be unit acid or the corresponding ester of polyacid, for example ethyl palmitate, methyl stearate, rosin triglyceride etc.The ratio of the solvent of chlopyrifos and carboxylic acid or carboxylate is between 80: 1 and 3: 1.Preferably between 62: 38 and 80: 20.
Carrier described in the present invention is selected porous carrier for use, and the porous carrier of selection need have tangible liquid capacity.Preferred solid carrier comprises kaolin such as kaolinite, dickite, nacrite, anauxite, halloysite, endel etc.; Cover unsticking soil like beidellite, hectorite, saponite, bentonite; Attapulgite such as bleaching earth, sepiolite; Synthetic silicon such as white carbon; Vegetable fiber, mineral fibre etc.
Other various functional components comprise water; Emulsifying dispersant such as alkylsulfonate, wooden sulfonated salts, naphthalene sulfonate, AEO, one or more in the NPE phosphate etc.; Viscosity-controlling agent such as xanthans, cellulose ether and derivative thereof, polyvinyl alcohol etc.; Antifreeze such as ethylene glycol, propane diols, glycerine, isopropyl alcohol or urea; Biocide such as potassium sorbate, Sodium Benzoate, formaldehyde or isothiazolinone; Antifoaming agent such as silicone based or low-carbon alcohols antifoaming agent.Cyst material be isocyanates and the polyamine aqueous solution through interface polymerization reaction system carbamide resin.
The present invention also provides the composition low temperature caking of the aqueous dispersion that a kind of inhibition contains chlopyrifos and heat storage back active component to separate out the method for crystallization; This method is included in the chlorpyrifos water dispersible composition carboxylic acid that adds effective dose or carboxylate as solvent, and the solution of chlopyrifos/carboxylic acid or carboxylate adsorbs with the porous carrier of q.s.
The advantage of the composition of the aqueous dispersion that contains chlopyrifos through the present invention preparation is:
1. the composition low tempertaure storage of the aqueous dispersion that contains chlopyrifos through the present invention preparation does not lump good fluidity.
2. the composition heat storage stability of the aqueous dispersion that contains chlopyrifos through the present invention preparation is good, and heat storage back active component can not separated out from preparation in crystallization, and shower nozzle can be not blocked.
Embodiment
The invention provides a cold storage does not have caking, the composition of the aqueous dispersion of the stable chlopyrifos that the heat storage no crystallization in back is separated out.The present invention also provides the preparation of compositions method of the aqueous dispersion of a cold and hot stable storage that contains chlopyrifos.The composition that contains the aqueous dispersion of chlopyrifos of the present invention comprises and loads on chlopyrifos and the solution of carboxylic acid or carboxylate on the solid carrier.Further the invention provides the composition low temperature caking that a kind of inhibition contains the aqueous dispersion of chlopyrifos and separate out the method for crystallization with heat storage back active component.According to the present invention, the content of composition death by poisoning tick that contains the aqueous dispersion of chlopyrifos is 2%-40%.Preferred 20%-40%.The amount of carboxylic acid or carboxylate solvent is 0.5%-10%, preferred 2%-5%.Among the present invention, the ratio of general chlopyrifos and carboxylic acid or carboxylate is between 80: 1 and 3: 1.Between preferred 62: 38 and 80: 20.
The use of carboxylic acid or carboxylate has remarkable effect in the present invention.Employable carboxylic acid or carboxylate are the acid or the ester of water-insoluble or indissoluble among the present invention.Acid can be unit acid or polyacid, aliphatic or alicyclic.Only is fatty acid, and for example cerinic acids such as palmitic acid, stearic acid, arachidic acid, mountain Yu acid also comprise synthetic aliphatic-aromatic hydrocarbon carboxylic acid, and cyclic carboxylic acids is rosin acid for example.Ester can be unit acid or the corresponding ester of polyacid, for example ethyl palmitate, methyl stearate, rosin triglyceride etc.
Used solid carrier must have tangible liquid capacity among the present invention.The solid carrier that the present invention is fit to comprises kaolin such as kaolinite, dickite, nacrite, anauxite, halloysite, endel etc.; Cover unsticking soil like beidellite, hectorite, saponite, bentonite; Attapulgite such as bleaching earth, sepiolite; Synthetic silicon such as white carbon; Vegetable fiber, mineral fibre etc.It should be noted that such composition was too wet too sticking when the mass ratio of organic phosphor and solid carrier was too big.Beyond thoughtly be the liquid capacity that combines obviously to have increased solid carrier of chlopyrifos and carboxylic acid or carboxylate.
Can believe be solid carrier that enough big space, duct arranged with low-melting organic phosphorus compound to combine be that very important, such combination makes the liquid capacity of solid carrier that beyond thought increase arranged.When a liquid was loaded on the solid carrier, this liquid flowed in the inside and outside in the space, duct of solid carrier freely usually.When a low-melting compound is liquid state, believe this compound easy and crystalline inside the duct.If when in liquid, having comprised low-melting compound so, the amount of liquid that solid carrier can hold is many when not comprising low-melting compound in the liquid.
According to the present invention, find the low-temperature stability and the heat storage stability that combine to have improved the organic phosphor solid pharmaceutical preparation of carboxylic acid or carboxylate and solid carrier.
Solid intermediate powder of the present invention can obtain through organophosphorus insecticide and carboxylic acid or carboxylate solvent are loaded on the solid carrier.Can the solvent of organic phosphor and carboxylic acid or carboxylate be loaded to respectively separately on the solid carrier, also can the mixture of organic phosphor and carboxylic acid or carboxylate be loaded on the solid carrier.If load separately, the order of then adding is unrestricted, gets on but preferential selection loads to carrier earlier with solvent.Any way that the mixture of organic phosphor and solvent can be familiar with the technical staff in this field loads to solid carrier and gets on.
Some organophosphorus insecticides are solid states under room temperature or normal temperature, and it is the characteristic of a key of the present invention that SOLID ORGANIC phosphorus is loaded under liquid state that solid carrier gets on.So for being to want liquefy must be heated to fusing point the organic phosphor of solid so under room temperature or normal temperature.For example chlopyrifos at room temperature is a solid, and fusing point is about 42 ℃, and boiling point is 200 ℃.So chlopyrifos must be heated between 42-200 ℃.Preferred range is 50-60 ℃.To other is the organophosphorus insecticide of solid under room temperature or normal temperature, must be heated to it more than fusing point, below the boiling point, so just can make the evaporation of active component be controlled at minimum.
To those is that the SOLID ORGANIC phosphorus pesticide of liquid there is no need to heat before the solid carrier loading to again under room temperature or normal temperature.And near the SOLID ORGANIC phosphorus of those fusing points normal temperature or room temperature; These organic phosphors are the liquid of relative thickness; Slight heating can reduce the insecticide viscosity before loading to solid carrier, particularly insecticide and load on the solid carrier with the mode of spraying.
When SOLID ORGANIC phosphorus must heat, if SOLID ORGANIC phosphorus and solvent are when being loaded on the solid carrier together, carboxylic acid or carboxylate solvent also needed heating among the present invention.Preferably SOLID ORGANIC phosphorus pesticide and carboxylic acid or carboxylate are loaded on the solid carrier with the mode of mixture.So feasible method is first heat fused SOLID ORGANIC phosphorus pesticide, and holding temperature adds the solvent of carboxylic acid or carboxylate on the fusing point of organic phosphor.The temperature of the mixture of organic phosphor and solvent should be between SOLID ORGANIC phosphorus fusing point and boiling point.For example to chlopyrifos, mixture should remain between 42 ℃ and 200 ℃, preferred 50-60 ℃.The mixture of organic phosphor and carboxylic acid or carboxylate solvent should be stirred and mixed fully.The liquid phase mixture of organic phosphor and solvent is ready to load on the solid carrier.
When organic phosphor at room temperature is solid; If at room temperature organophosphorus insecticide is loaded on the solid carrier; Then except organophosphorus insecticide is heated; When being heated to solid carrier between organic phosphorous insecticide fusing point and the boiling point, can prevent the surface solidification of organophosphorus insecticide at solid carrier.Heating to solid carrier also makes the mixture of organic phosphor and carboxylic acid or carboxylate penetrate in the solid carrier more easily.For example to chlopyrifos, solid carrier should be heated to 42-200 ℃.Be preferably 65-71 ℃.Solid carrier can use any feasible mode to preheat the temperature of wanting.When SOLID ORGANIC phosphorus at room temperature is liquid, the heating of solid carrier is not then needed.
The meaning of low melting point one speech be fusing point between 30 ℃-130 ℃, preferred 30 ℃-90 ℃.
Other various functional components comprise water; In dispersant such as alkylsulfonate, wooden sulfonated salts, naphthalene sulfonate, AEO, the NPE phosphate etc. one or more; Viscosity-controlling agent such as xanthans, cellulose ether and derivative thereof, polyvinyl alcohol etc.; Antifreeze such as ethylene glycol, propane diols, glycerine, isopropyl alcohol or urea; Biocide such as potassium sorbate, Sodium Benzoate, formaldehyde or isothiazolinone; Antifoaming agent such as silicone based or low-carbon alcohols antifoaming agent.Cyst material is the carbamide resin that the isocyanates and the polyamine aqueous solution make through interface polymerization reaction.
Stablizing the speech meaning is at room temperature, and from the storage property of preparation, dispersed and sprayability reaches or surpassed the product of commercial criterion.
Following embodiment is used for explaining the present invention, but the spirit or scope of the present invention that aforementioned disclosure is set forth does not receive the restriction of these embodiment.All temperature units are degree centigrade that it all is quality percentage compositions that all percentage compositions do not specify.
Embodiment
Embodiment 1:10% chlopyrifos wetting powder WP
The percentage by weight of each component is:
| Component | Weight, Kg | Content, % |
| Chlopyrifos (technic) | 10 | 10 |
| Rosin acid | 5 | 5 |
| Sodium lignin sulfonate | 5 | 5 |
| White carbon black | 80 | 80 |
Process for preparation is following:
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then rosin acid is added in the tank diameter, stirs up to rosin acid and chlopyrifos and is mixed fully; Simultaneously the white carbon black of solid carrier is weighed by said ratio, be heated to 65-71 ℃ then, the solid carrier that heats is transferred in the preparation still; Then open the agitator of preparation still, the mixture of chlopyrifos and rosin acid is being sprayed on the surface of white carbon black under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and rosin acid.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The chlopyrifos of the top white carbon black load that obtains and the intermediate product of rosin acid are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.10% chlopyrifos wetting powder WP
Add sodium lignin sulfonate in the dry powder intermediate blend that obtains in the above.Then be crushed to the particle diameter (2-20um) that needs and just obtained solid powder preparation of the present invention.Then this solid powder preparation is transferred in the packing loading hopper, sealed mouth well, process 20% chlopyrifos wetting powder WP with packaging of aluminium foil bag.
Embodiment 2:20% chlopyrifos wetting powder WP
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (tech) | 20 | 20 |
| Rosin triglyceride | 8 | 8 |
| AEO | 8 | 8 |
| Kaolin | 64 | 64 |
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then rosin triglyceride is added in the tank diameter, stirs up to rosin triglyceride and chlopyrifos and is mixed fully.Simultaneously solid carrier kaolin is weighed, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, the mixture of chlopyrifos and rosin triglyceride is being sprayed on the kaolinic surface under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and rosin triglyceride.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The top kaoline loaded chlopyrifos that obtains and the intermediate product of rosin triglyceride are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.20% chlopyrifos wetting powder WP
Add AEO in the dry powder intermediate blend that obtains in the above.Then be crushed to the particle diameter (2-20um) that needs and just obtained solid powder preparation of the present invention.Then this solid powder preparation is transferred in the packing loading hopper, sealed mouth well, process 20% chlopyrifos wetting powder WP with packaging of aluminium foil bag.
The solid powder preparation for preparing is transferred in the packing loading hopper, seals mouth well with suitable packaging of aluminium foil bag.
Embodiment 3:30% chlopyrifos wetting powder WP
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (tech) | 30 | 30 |
| Stearic acid | 10 | 10 |
| Calcium dodecyl benzene sulfonate | 13 | 13 |
| White carbon black | 20 | 20 |
| Kaolin | 27 | 27 |
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then stearic acid is added in the tank diameter, stirs up to stearic acid and chlopyrifos and is mixed fully.Simultaneously white carbon black of solid carrier and kaolin are weighed, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, chlopyrifos and stearic mixture are being sprayed under the pressure of 30Pa on white carbon black and the kaolinic surface.Use two fan-shaped nozzles with chlopyrifos and the atomizing of stearic mixture.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.Top white carbon black that obtains and kaoline loaded chlopyrifos and stearic intermediate product are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.30% chlopyrifos wetting powder WP
Add AEO in the dry powder intermediate blend that obtains in the above.Then be crushed to the particle diameter (2-20um) that needs and just obtained solid powder preparation of the present invention.Then this solid powder preparation is transferred in the packing loading hopper, sealed mouth well, process 30% chlopyrifos wetting powder WP with packaging of aluminium foil bag.
The solid powder preparation for preparing is transferred in the packing loading hopper, seals mouth well with suitable packaging of aluminium foil bag.
The solid powder preparation for preparing is transferred in the packing loading hopper, seals mouth well with suitable packaging of aluminium foil bag.
Embodiment 4:40% chlopyrifos wetting powder WP
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (tech) | 40 | 40 |
| Methyl stearate | 12.7 | 12.7 |
| Calcium dodecyl benzene sulfonate | 9 | 9 |
| Vegetable fiber | 26.8 | 26.8 |
| Mineral fibre | 11.5 | 11.5 |
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then methyl stearate is added in the tank diameter, stirs up to methyl stearate and chlopyrifos and is mixed fully.Simultaneously solid carrier vegetable fiber and mineral fibre are weighed, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, the mixture of chlopyrifos and methyl stearate is being sprayed on the surface of vegetable fiber and mineral fibre under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and methyl stearate.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The chlopyrifos of top vegetable fiber that obtains and mineral fibre load and the intermediate product of methyl stearate are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.40% chlopyrifos wetting powder WP
Add calcium dodecyl benzene sulfonate in the dry powder intermediate blend that obtains in the above.Then be crushed to the particle diameter (2-20um) that needs and just obtained solid powder preparation of the present invention.Then this solid powder preparation is transferred in the packing loading hopper, sealed mouth well, process 40% chlopyrifos wetting powder WP with packaging of aluminium foil bag.
The solid powder preparation for preparing is transferred in the packing loading hopper, seals mouth well with suitable packaging of aluminium foil bag.
Embodiment 5:30% chlopyrifos water dispersible granules WG
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (tech) | 30 | 30 |
| Palmitic acid | 10 | 10 |
| Sodium lignin sulfonate | 8 | 8 |
| Kaolin | 52 | 52 |
Process for preparation is following:
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then palmitic acid is added in the tank diameter, stirs up to palmitic acid and chlopyrifos and is mixed fully.Simultaneously solid carrier kaolin is weighed, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, the mixture of chlopyrifos and palmitic acid is being sprayed on the kaolinic surface under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and palmitic acid.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The top kaoline loaded chlopyrifos that obtains and the intermediate product of palmitic acid are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.30% chlopyrifos water dispersible granules WG
Add sodium lignin sulfonate in the dry powder intermediate blend that in (1), obtains.Then be crushed to the particle diameter (2-20um) that needs.After adding an amount of water kneading then, the product that the process extruder grain is dried to the end.Through sieving, whole grain back is sealed mouth well with suitable packaging of aluminium foil bag.
Embodiment 6:40% chlopyrifos water dispersible granules WG
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (tech) | 40 | 40 |
| Arachidic acid | 10 | 10 |
| The NPE phosphate | 9 | 9 |
| Illiteracy is taken off clay | 41 | 41 |
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then arachidic acid is added in the tank diameter, stirs up to arachidic acid and chlopyrifos and is mixed fully.Simultaneously the solid carrier illiteracy is taken off clay and weigh, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, the mixture of chlopyrifos and arachidic acid takes off on the surface of clay being sprayed to illiteracy under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and arachidic acid.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The top illiteracy that obtains is taken off the chlopyrifos of clay load and the intermediate product of arachidic acid is cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.30% chlopyrifos water dispersible granules WG
Add the NPE phosphate in the dry powder intermediate blend that in (1), obtains.Then be crushed to the particle diameter (2-20um) that needs.After adding an amount of water kneading then, the product that the process extruder grain is dried to the end.Through sieving, whole grain back is sealed mouth well with suitable packaging of aluminium foil bag.
Embodiment 7:40% chlopyrifos aqueous suspension agent SC
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (98%) | 40 | 40 |
| Mountain Yu acid | 5 | 5 |
| Sodium naphthalene sulfonate | 5 | 5 |
| Attapulgite | 15 | 15 |
| Propane diols | 4 | 4 |
| Xanthans | 0.1 | 0.1 |
| Deionized water | 30.9 | 30.9 |
Process for preparation is following:
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then mountain Yu acid is added in the tank diameter, stirs Yu acid and the mixing fully of chlopyrifos quilt up to the mountain.Simultaneously the solid carrier attapulgite is weighed, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, the mixture of chlopyrifos and mountain Yu acid is being sprayed on the surface of attapulgite under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and mountain Yu acid.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The chlopyrifos of the top attapulgite load that obtains and the intermediate product of mountain Yu acid are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.40% chlopyrifos aqueous suspension agent SC
Add entry in the dry powder intermediate blend that in (1), obtains, propane diols, sodium naphthalene sulfonate, then sand milling is to the particle diameter (2-20um) that needs.Add the xanthans thickening then.The finished product that obtains is packed with the F-HDPE bottle.
Embodiment 8:40% chlopyrifos aqueous suspension agent SC
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (tech) | 40 | 40 |
| Isobutyl palmitate | 6 | 6 |
| The Nonyl pheno polyethers | 8 | 8 |
| Mineral fibre | 15 | 15 |
| Propane diols | 4 | 4 |
| Polyvinyl alcohol | 0.1 | 0.1 |
| Deionized water | 26.9 | 26.9 |
Process for preparation is following:
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then isobutyl palmitate is added in the tank diameter, stirs up to isobutyl palmitate and chlopyrifos and is mixed fully.Simultaneously the solid mineral fiber is weighed, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, the mixture of chlopyrifos and isobutyl palmitate is being sprayed on the surface of mineral fibre under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and isobutyl palmitate.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The chlopyrifos of the top mineral fibre load that obtains and the intermediate product of isobutyl palmitate are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.40% chlopyrifos aqueous suspension SC
Add entry in the dry powder intermediate blend that in (1), obtains, propane diols, the Nonyl pheno polyethers, then sand milling is to the particle diameter (2-20um) that needs.Add the polyvinyl alcohol thickening then.The finished product that obtains is packed with the F-HDPE bottle.
Embodiment 9:40% chlorpyrifos microcapsule suspension agent CS
The percentage by weight of each component is:
| Component | Weight, kg | Content, % |
| Chlopyrifos (tech) | 40 | 40 |
| Rosin acid | 6 | 6 |
| Polyphenyl polymethylene polyisocyanates PAPI | 4 | 4 |
| Toluene di-isocyanate(TDI) TDI | 0.9 | 0.9 |
| Diethylenetriamine | 0.6 | 0.6 |
| The Nonyl pheno polyethers | 8 | 8 |
| White carbon black | 15 | 15 |
| Propane diols | 3 | 3 |
| Xanthans | 2.5 | 2.5 |
| Glacial acetic acid | 0.15 | 0.15 |
| Deionized water | 19.85 | 19.85 |
Process for preparation is following:
1. the preparation of dry powder intermediate blend
The former medicine of chlopyrifos heat fused in 50-55 ℃ water-bath, heat fused are in former medicinal pump suction one tank diameter of the chlopyrifos of liquid, this tank diameter be furnished with agitator and hot water jacket with the temperature of keeping tank diameter at 50-55 ℃.Then rosin acid is added in the tank diameter, stirs up to rosin acid and chlopyrifos and is mixed fully.Simultaneously the white carbon black of carrier is weighed, be heated to 65-71 ℃ then.The solid carrier that heats is transferred in the preparation still.Then open the agitator of preparation still, the mixture of chlopyrifos and rosin acid is being sprayed on the surface of white carbon black under the pressure of 30Pa.Use of the mixture atomizing of two fan-shaped nozzles with chlopyrifos and rosin acid.Spray time is 8 minutes.Spraying was stirred 10 minutes after finishing again.The chlopyrifos of the top white carbon black load that obtains and the intermediate product of rosin acid are cooled to room temperature, obtain a dry powder intermediate blend.
The preparation of 2.40% chlorpyrifos microcapsule suspension agent CS
In the dry powder intermediate blend that in (1), obtains, join after the toluene di-isocyanate(TDI) TDI that adds polyphenyl polymethylene polyisocyanates PAPI and the 0.9g of 4g mixes in the mixture of xanthan gum solution and deionized water of Nonyl pheno polyethers, 5g of 8g and go to form emulsion.Then emulsion is heated to 50 ℃, slowly adds the diethylenetriamine of 0.6g simultaneously, kept stable cyst material solidification temperature 7 hours, add the propane diols of 3g then, the glacial acetic acid of 0.15g is transferred about pH to 7.Promptly obtain 40% chlopyrifos CS.The product that obtains is packed with the F-HDPE bottle, seals mouth.
Embodiment 10:
The sample that embodiment 1-9 prepares is with low-temperature stability to be tested and heat storage stability.The low-temperature stabilization property testing carries out in-5 ℃ low stabilization tester.Heat storage stability carries out in 54 ℃ baking oven.
Behind the low tempertaure storage, product is taken out from the low-temperature test appearance.When test article is poured out, through one 325 purpose sieve.When test article is poured out when sifting out, note observing the flowability of test article, and to stay block on the sieve be firmly or soft from bag.Soft block will be broken up when contacting with sieve or after shaking sieve gently.14 days cold storage result embodies in following table.
| Embodiment | Stored 2 days | Stored 7 days | Stored 14 days |
| 1 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 2 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 3 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 4 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 5 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 6 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 7 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 8 | Good fluidity, no hard caking | Good fluidity, no hard caking | Good fluidity, no hard caking |
| 9 | Good fluidity, the caking of no shadow | Good fluidity, no hard caking | Good fluidity, no hard caking |
Test result in the table shows that the composition low tempertaure storage of the aqueous dispersion of chlopyrifos prepared in accordance with the present invention does not lump good fluidity.
In 54 ℃ baking oven, after the heat storage, sample is taken out from baking oven.After being cooled to room temperature, test article is poured out.The test article of embodiment 1-4 and embodiment 7-9 is directly through one 325 purpose sieve.And the test article of embodiment 5 and 6 is earlier to after the water dilution, again with dilution through one 325 purpose sieve.Note observing and stay the particle on the sieve.If particle is hard, water flushing particle removes the particle surface covering, observes with the 10X magnifying glass, if can observe tangible crystalline form, then particle is the chlopyrifos crystal.56 days heat storage result embodies in following table.
| Embodiment | Stored 14 days | Stored 28 days | Stored 56 days |
| 1 | No crystallization | No crystallization | No crystallization |
| 2 | No crystallization | No crystallization | No crystallization |
| 3 | No crystallization | No crystallization | No crystallization |
| 4 | No crystallization | No crystallization | No crystallization |
| 5 | No crystallization | No crystallization | No crystallization |
| 6 | No crystallization | No crystallization | No crystallization |
| 7 | No crystallization | No crystallization | No crystallization |
| 8 | No crystallization | No crystallization | No crystallization |
| 9 | No crystallization | No crystallization | No crystallization |
Test result in the table shows that the no crystallization of water-dispersed composition heat storage of chlopyrifos prepared in accordance with the present invention is separated out.
Claims (3)
1. chlorpyrifos water dispersible composition; It is characterized in that comprising the solvent of chlopyrifos, carboxylic acid or carboxylate, porous carrier and other functional aids, wherein the raw material weight per distribution ratio is that the solvent 0.5-10% of chlopyrifos 2%-40%, carboxylic acid or carboxylate, porous carrier 15%-90%, other functional aids are surplus;
The solvent of said carboxylic acid or carboxylate is selected from one or more in rosin acid, rosin triglyceride, hard ester acid, palmitic acid, arachidic acid, the mountain Yu acid;
Said porous carrier is selected from kaolin, covers unsticking soil, attapulgite, a kind of in carbon black, vegetable fiber, the mineral fibre in vain;
Said other functional aids are selected from one or more in water, emulsifying dispersant, viscosity-controlling agent, antifreeze, biocide, antifoaming agent, the cyst material; Emulsifying dispersant is selected one or more in alkylsulfonate, wooden sulfonated salts, naphthalene sulfonate, AEO, the NPE phosphate for use; Viscosity-controlling agent is selected from one or more in xanthans, cellulose ether and derivative thereof, the polyvinyl alcohol; Antifreeze is selected ethylene glycol, propane diols, glycerine, isopropyl alcohol or urea for use; Biocide is selected potassium sorbate, Sodium Benzoate, formaldehyde or isothiazolinone for use; Antifoaming agent is selected silicone based antifoaming agent for use; The carbamide resin that cyst material selects for use the isocyanates and the polyamine aqueous solution to make through interface polymerization reaction.
2. chlorpyrifos water dispersible composition according to claim 1 is characterized in that said composite preparation is wettable powder agent, water-dispersible granules, suspending agent or microcapsule suspending agent.
3. the preparation method of a chlorpyrifos water dispersible composition is characterized in that may further comprise the steps;
A. by proportioning chlopyrifos heating is become in the solvent that joins a carboxylic acid or carboxylate after the liquid phase and obtain a solution; Said chlopyrifos heating-up temperature is 50-60 ℃;
B. simultaneously carrier is heated to 65-71 ℃, the solution that obtains in (a) is added to removes to obtain the powder intermediate done in the porous carrier, active matter is fully adsorbed by used carrier under liquid state;
C. behind the powder intermediate of doing that obtains in the cooling (b), add other functional aids, obtain the preparation with nature of business of solid or liquid;
D. the composition of pulverizing solid that (c) obtain or liquid is to the particle diameter 2-20um that needs;
Wherein the raw material weight per distribution ratio is solvent 0.5-10%, the porous carrier 15-90% of chlopyrifos 2%-40%, carboxylic acid or carboxylate, and other functional aids are surplus;
The solvent of said carboxylic acid or carboxylate is selected from one or more in rosin acid, rosin triglyceride, hard ester acid, palmitic acid, arachidic acid, the mountain Yu acid;
Said porous carrier is selected from kaolin, covers unsticking soil, attapulgite, a kind of in carbon black, vegetable fiber, the mineral fibre in vain;
Said other functional aids are selected from one or more in water, emulsifying dispersant, viscosity-controlling agent, antifreeze, biocide, antifoaming agent, the cyst material; Emulsifying dispersant is selected one or more in alkylsulfonate, wooden sulfonated salts, naphthalene sulfonate, AEO, the NPE phosphate for use; Viscosity-controlling agent is selected from one or more in xanthans, cellulose ether and derivative thereof, the polyvinyl alcohol; Antifreeze is selected ethylene glycol, propane diols, glycerine, isopropyl alcohol or urea for use; Biocide is selected potassium sorbate, Sodium Benzoate, formaldehyde or isothiazolinone for use; Antifoaming agent is selected silicone based antifoaming agent for use; The carbamide resin that cyst material selects for use the isocyanates and the polyamine aqueous solution to make through interface polymerization reaction.
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| CN105410015B (en) * | 2015-12-25 | 2018-08-21 | 山东潍坊润丰化工股份有限公司 | A kind of chlopyrifos water dispersible granules and preparation method thereof |
| CN108849952B (en) * | 2017-05-10 | 2020-11-17 | 江苏龙灯化学有限公司 | Pyraclostrobin water-dispersible solid composition and preparation method thereof |
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| CN101356918A (en) * | 2008-09-24 | 2009-02-04 | 中国农业科学院植物保护研究所 | Microcapsule suspension seed-coating agent |
| CN101427687A (en) * | 2007-11-08 | 2009-05-13 | 联合国南通农药剂型开发中心 | High-content chlorpyrifos microcapsule suspension agent and production method |
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| CN101427687A (en) * | 2007-11-08 | 2009-05-13 | 联合国南通农药剂型开发中心 | High-content chlorpyrifos microcapsule suspension agent and production method |
| CN101356918A (en) * | 2008-09-24 | 2009-02-04 | 中国农业科学院植物保护研究所 | Microcapsule suspension seed-coating agent |
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