CN100577012C - Water emulsion of hostathion and preparation method thereof - Google Patents
Water emulsion of hostathion and preparation method thereof Download PDFInfo
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- CN100577012C CN100577012C CN200510117621A CN200510117621A CN100577012C CN 100577012 C CN100577012 C CN 100577012C CN 200510117621 A CN200510117621 A CN 200510117621A CN 200510117621 A CN200510117621 A CN 200510117621A CN 100577012 C CN100577012 C CN 100577012C
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Abstract
The invention discloses a triazophos aqueous emulsion and its preparing process, wherein the aqueous emulsion comprises 25-50% of triazophos, 5-15% of emulsifying agent, 1-4% of stabilizer, 0-10% of auxiliary solvent, 0-2% of dispersing agent, 0-3% of thickening agent, 0-4% of anti-freeze agent, and balancing water as dispersive medium. The emulsion is prepared through shearing emulsification or high-pressure homogeneity process and homogeneous decentralizing.
Description
Technical field:
The present invention relates to a kind of insecticidal/acaricidal agent, particularly a kind of aqueous emulsion that contains Hostathion and preparation method thereof.
Background technology:
Organic solvent in the emulsifiable concentrates for agricultural chemicals has not only caused the waste of petroleum resources, increased the weight of production cost, and environment there is pollution, operator there is harm, the missible oil that contains aromatic hydrocarbon solvent in some countries is limited the use of or is forbidden, thereby impel the formulations of pesticide to bring in constant renewal in and development, wherein Water-borne modification is exactly one of dominant direction of formulations of pesticide development.
Pesticide emulsion in water (emulsion oil in water, EW) be that water-fast original liquid body or former medicine are dissolved in the liquid of water-fast organic solvent gained as disperse phase, by auxiliary agents such as emulsifier, utilize the input energy to be scattered in a kind of pesticidal preparations that forms in the water, it substitute with water section or replacing whole missible oil in organic solvent, so aqueous emulsion can reduce petroleum resources and wastes, reduces production costs, alleviates environmental pollution.
Hostathion (Triazophos) has another name called triazophos, is broad spectrum insecticide, miticide, also has nematocidal effect.Have stomach toxicity and action of contace poison, plant tissue is had permeability.Can be used for preventing and treating lepidoptera pest and aphid on fruit tree, vegetables, the cereal crop.Hostathion at present at home, the main preparation variety that circulates on the international market still is cream preparation, and content is mainly 20%, and the aromatic hydrocarbon solvent consumption is very big, and preparation is prone to crystalline polamer, shelf life is short, has had a strong impact on the quality of product, very easily brings heavy economic losses to production firm.Formulation content low (≤20%), packing cost and the just increase of storing cost simultaneously.
Hostathion will be developed into aqueous emulsion, must solve the physical stability difference of preparation and the problem of poor chemical stability, activity substance content is high more, is mixed with O/W type aqueous emulsion with regard to difficult more, and phase inversion easily takes place.Simultaneously, Hostathion is met water and is easily decomposed, and therefore, Hostathion is mixed with water is the aqueous emulsion of solvent, and guarantee its 54 ℃ store down 14 days resolution ratios less than 5%, 2 years resolution ratios of storage at normal temperature are not more than 5%0 fen difficulty.
Summary of the invention:
The present invention is intended to solve above-mentioned technical problem, provide a kind of can reduce aromatic hydrocarbon organic solvent to the pollution of environment, reduce production costs, avoid the triazophos emulsifiable solution crystallization, and all preferable aqueous emulsion of triazophos of physical stability, chemical property stability and preparation method thereof.
Above-mentioned purpose of the present invention is to realize by following technological means.
Aqueous emulsion of triazophos provided by the present invention, adopt following prescription:
Weight percentages of components
Hostathion 25-50%
Emulsifier 5-15%
Stabilizing agent 1-4%
Cosolvent 0-10%
Dispersant 0-2%
Thickener 0-3%
Antifreezing agent 0-4%
Water surplus,
And the content of cosolvent, dispersant, thickener and antifreezing agent can not be 0 simultaneously.
Described emulsifier is selected from castor oil polyoxyethylene ether, styryl phenyl APEO, styrene phenol formaldehyde resin APEO, polyoxyethylene nonylphenol ether, styrene phenol formaldehyde resin polyoxyethylene polyoxypropylene block co-polyether, styrene phenol formaldehyde resin oxirane propylene oxide block copolyether, ethylene glycol glucoside stearate, the methyl glucoside stearate, polyoxyethylene (20) sorbitan mono-laurate, calcium dodecyl benzene sulfonate and EO/PO block polyether.
Our Pluronic RPE2520, Pluronic PE 10500, Pluronic PE6200 of having selected for use German BAST company to produce of wherein said EO/PO block polyether.
Described stabilizing agent is selected from epoxidized soybean oil, epoxychloropropane, methyl propanediol, butyl glycidyl ether, phenyl glycidyl ether.
Used cosolvent is selected from n-butanol, isobutanol, n-octyl alcohol, n-amyl alcohol, toluene, dimethylbenzene.
Described dispersant is selected from naphthalene sulfonic acid condensate sodium salt, polymeric polycarboxylic acid derivative, sodium lignin sulfonate, maleic acid-acrylic acid copolymer sodium salt.
Described thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose, polyvinyl alcohol.
Described antifreezing agent is selected from ethylene glycol, PEG400, propane diols, glycerine, urea.
Described water is deionized water or distilled water, replaces organic solvent in the missible oil as dispersion medium, thereby reduces the pollution to environment.
The preparation method of aqueous emulsion of triazophos provided by the present invention adopts following processing step:
A. take by weighing raw material according to aforementioned proportion;
B. water, antifreezing agent, dispersant and thickener are mixed, obtain water;
C. Hostathion, emulsifier, cosolvent and stabilizing agent are mixed and obtain oil phase;
D. with mix under water, the oil phase high speed shearing condition the aqueous emulsion of triazophos finished product.
Aqueous emulsion of triazophos preparation method provided by the present invention, can also adopt following processing step:
A. take by weighing raw material according to aforementioned proportion;
B. water, antifreezing agent, dispersant and thickener are mixed in stirred tank, obtain water;
C. Hostathion, emulsifier, cosolvent and stabilizing agent are mixed in stirred tank, obtain oil phase;
D. under stirring condition, water is added in the oil phase or with oil phase gradually and adds to aqueous phase gradually, make two-phase be mixed into thick emulsion;
E. thick emulsion is input in the high pressure homogenizer, after high-pressure homogeneous, promptly obtains the aqueous emulsion of triazophos finished product.
Generally about 80%, former medicine density is about 1.3g/ml for the former medicine effective content of the domestic Hostathion commonly used of China at present, and the density of water has only 1.0g/ml.According to the Stokes theory, if Hostathion is made O/W type aqueous emulsion, the rate of settling of disperse phase in storage process---Hostathion---can be bigger so, and preparation is prone to layering, and physical stability is poor.And, along with the rising of the former medicine content of Hostathion in the aqueous emulsion, keep the physical stability of preparation can become more difficult.Simultaneously, the effective content of aqueous emulsion of triazophos is 25% o'clock, and the content of the former medicine of Hostathion is added some oily components such as cosolvent, stabilizing agent more than 31.3% in the aqueous emulsion, oily matter content total in the preparation equates with the content of water substantially at 40%-45%.Along with the further rising of Hostathion content in the aqueous emulsion, oily matter content is also high more in the preparation, is mixed with O/W type aqueous emulsion with regard to difficult more, and phase inversion easily takes place.
Aqueous emulsion of triazophos provided by the present invention has overcome above-mentioned technical barrier, and the outward appearance homogeneous is creamy white or little yellow, good fluidity, and stability of emulsion is qualified, and cold and hot storage physical stability is good.
Discovering that according to Zhao Hua etc. under 25 ℃, Hostathion is that hydrolysising half-life is 49.4 days in 5 the water in the pH value, is that hydrolysising half-life is 38.5 days in 7 the water in the pH value, is that hydrolysising half-life then only is 9.5 days in 9 the water in the pH value; And under 50 ℃, the hydrolysis rate of Hostathion is faster, is that hydrolysising half-life is 5.7 days in 5 the water in the pH value, is that hydrolysising half-life is 5.4 days (pesticide science and management, 2004,25 (10): 7～10) in 7 the water in the pH value.
According to aqueous emulsion of triazophos heat two weeks of storage under 54 ± 1 ℃ condition of method preparation provided by the present invention, the Hostathion resolution ratio is less than 5%, and storage back preparation outward appearance still keeps the homogeneous shape.
The aqueous emulsion of triazophos and preparation method thereof that provides provided by the present invention, compare with prior art and also to have following advantage:
1. be dispersion medium with water, reduced the toxicity of pesticidal preparations, to human and environment safety, environmental pollution is little;
2. drug effect height, to insect good drug efficacy such as control rice-stem borer, paddy stem borer, pink rice borer, aphid, cotton red spiders, and residual low on the crops;
3. storage at normal temperature did not have precipitation and crystalline polamer in 2 years, and shelf life is long;
4. suitable in used emulsification dosage and the missible oil, but saved a large amount of organic solvents, the cost of preparation descends significantly;
5. the flash-point height is nonflammable, storing safety.
Embodiment:
Describe aqueous emulsion of triazophos provided by the present invention and preparation method thereof in detail below in conjunction with specific embodiment; described embodiment is in order to explain the present invention better; rather than to the restriction of claim protection domain of the present invention; all all belong to the scope that the present invention asks for protection based on the modification and the change of basic thought of the present invention.
Example 1
Hostathion 25.0%, castor oil polyoxyethylene ether 4.0%, polyoxyethylene (20) sorbitan mono-laurate 1.0%, epoxidized soybean oil 1.0%, n-butanol 4.0%, dimethylbenzene 6% are put in the high shearing mixing emulsor, be oil phase after mixing.In stirred tank, add ethylene glycol 2.0%, urea 2.0%,, xanthans 0.5%, sodium carboxymethylcellulose 2.5%, deionized water adds to 100%, is water after stirring.Water is pumped in the head tank, under the condition of high speed shear, water is added in the oil phase gradually, finish the back and continued high speed shear 10-60 minute, get final product 25% aqueous emulsion of triazophos.
Example 2
Hostathion 25.0%, castor oil polyoxyethylene (40) ether 1.0%, styryl phenyl APEO 4.0%, calcium dodecyl benzene sulfonate 1.0%, epoxychloropropane 2.0%, isobutanol 4.0%, dimethylbenzene 5.0% are put in the stirred tank, promptly got oil phase after stirring.Naphthalene sulfonic acid condensate sodium salt 1.0%, Magnesiumaluminumsilicate 2.0%, PEG400 3.0% are dropped in the high shearing mixing emulsor, after shearing evenly, promptly get water.Oil phase is pumped into head tank, under the condition of high speed shear, oil phase is added to aqueous phase gradually, finish the back and continue to shear 10-60 minute, get final product 25% aqueous emulsion of triazophos.
Example 3
Hostathion 25.0%, styrene phenol formaldehyde resin APEO 3.0%, polyoxyethylene nonylphenol ether 4.0%, methyl propanediol 1.0%, phenyl glycidyl ether 2.0% are put in the stirred tank, after stirring, promptly got oil phase.Input polymeric polycarboxylic acid derivative 1%, polyvinyl alcohol 1.5%, propane diols 2.0%, deionized water are mended to 100% in another stirred tank, after stirring, promptly get water, water is squeezed into head tank, and under stirring condition, water is added in the oil phase gradually, finishes the back and continue to stir 10 minutes, obtain thick emulsion, thick emulsion is transported in the high pressure homogenizer, after high-pressure homogeneous, promptly got 25% aqueous emulsion of triazophos.
Example 4
Hostathion 30.0%, styrene phenol formaldehyde resin APEO 2.0%, styrene phenol formaldehyde resin polyoxyethylene polyoxypropylene block co-polyether 5.0%, polyoxyethylene (20) sorbitan mono-laurate 1.0%, epoxidized soybean oil 1.0%, epoxychloropropane 2.0%, butyl glycidyl ether 1.0%, isobutanol 3.0%, toluene 2.0% are put in the stirred tank, after mechanical agitation is even, promptly got oil phase.Drop into polymeric polycarboxylic acid derivative 2.0%, xanthans 0.5%, Magnesiumaluminumsilicate 1.5% in another stirred tank, distilled water is mended to 100%, promptly gets water after mechanical agitation is even.Oil phase is pumped into head tank, under stirring condition, oil phase is added to aqueous phase gradually, finish back continuation stirring and obtained thick emulsion in 10 minutes, thick emulsion is transported in the high pressure homogenizer, after high-pressure homogeneous, promptly get 30% aqueous emulsion of triazophos.
Example 5
Hostathion 35.0%, ethylene glycol glucoside stearate 4.0%, methyl glucoside stearate 3.0%, styrene phenol formaldehyde resin oxirane propylene oxide block copolyether 2.0%, epoxidized soybean oil 2.0%, methyl propanediol 1.0%, isobutanol 3.0%, dimethylbenzene 3.0% are dropped in the reactor, after mechanical agitation is even, promptly get oil phase.Maleic acid-acrylic acid copolymer sodium salt 1.0%, Magnesiumaluminumsilicate 1.0%, sodium carboxymethylcellulose 1.0% are put in the high shearing mixing emulsor, and deionized water is mended to 100%, promptly gets water after shearing evenly.Oil phase is pumped into head tank, under the condition of high speed shear, oil phase is added to aqueous phase gradually, finish the back and continued high speed shear 10-60 minute, can obtain 35% aqueous emulsion of triazophos.
Example 6
Hostathion 40.0%, castor oil polyoxyethylene (60) ether 7.0%, polyoxyethylene nonylphenol ether 2.0%, calcium dodecyl benzene sulfonate 1.0%, epoxychloropropane 1.0%, methyl propanediol 1.0%, n-octyl alcohol 1.0%, toluene 7.0% are put in the high shearing mixing emulsor, after shearing evenly, be oil phase.Add naphthalene sulfonic acid condensate sodium salt 1.0%, xanthans 0.1%, Magnesiumaluminumsilicate 1.9% in stirred tank, deionized water is added to 100%, is water after stirring.Water is pumped in the head tank, under the condition of high speed shear, water is added in the oil phase gradually, finish the back and continued high speed shear 10-60 minute, get final product 40% aqueous emulsion of triazophos.
Example 7
Hostathion 45.0%, styrene phenol formaldehyde resin polyoxyethylene polyoxypropylene block co-polyether 6.0%, styrene phenol formaldehyde resin oxirane propylene oxide block copolyether 4.0%, polyoxyethylene (20) sorbitan mono-laurate 2.0%, epoxychloropropane 3.0%, n-octyl alcohol 3.0%, toluene 3.0% are put in the stirred tank, after mechanical agitation is even, promptly got oil phase.Drop into polymeric polycarboxylic acid derivative 1.0% in another stirred tank, distilled water is added to 100%, promptly gets water after mechanical agitation is even.Under stirring condition, water is added in the oil phase gradually, finish back continuation stirring and obtained thick emulsion in 10 minutes, thick emulsion is transported in the high pressure homogenizer, after high-pressure homogeneous, promptly get 45% aqueous emulsion of triazophos.
Example 8
Hostathion 50.0%, castor oil polyoxyethylene (80) ether 7.0%, polyoxyethylene nonylphenol ether 5.0%, methyl glucoside stearate 2.0%, calcium dodecyl benzene sulfonate 1.0%, methyl propanediol 2.0%, n-butanol 2.0%, toluene 7.0% are put in the high shearing mixing emulsor, after shearing evenly, be oil phase.Add maleic acid-acrylic acid copolymer sodium salt 1.0% in stirred tank, deionized water is added to 100%, is water after stirring.Water is pumped in the head tank, under the condition of high speed shear, water is added in the oil phase gradually, finish the back and continued high speed shear 10-60 minute, get final product 50% aqueous emulsion of triazophos.
Aqueous emulsion of triazophos provided by the present invention has good adhesive force, sprawls and infiltration capacity plant and polypide surface.
Through Zhejiang University's agricultural chemicals and environment toxicological study the indoor biological activity determination of aqueous emulsion of triazophos is shown, aqueous emulsion of triazophos provided by the present invention has biologically active preferably to striped rice borer, rice leaf roller, diamond-back moth, Tetranychus cinnabarinus, and biologically active is higher than 20% Hostathion EC.
Indoor bioassay result of the test of the present invention sees Table 1, table 2, table 3, table 4 (EW represents aqueous emulsion in the table, and EC represents missible oil).
Each medicament of table 1. is to the biologically active (24h) of striped rice borer 3 instar larvaes
Each medicament of table 2. is to the biologically active (48h) of rice leaf roller 3 instar larvaes
Each medicament of table 3. is to the biologically active (48h) of diamond-back moth 2 instar larvaes
Each medicament of table 4. becomes the biologically active (48h) of mite to Tetranychus cinnabarinus
Through field control effectiveness test, aqueous emulsion of triazophos provided by the present invention has good control efficiency to insects such as cotton red spiders.
Field control effectiveness test result of the present invention is as follows:
Through Zhejiang Province's agriculture chemical examination administrative institute the field medicine effect test in 2 years of 40% aqueous emulsion of triazophos is found that aqueous emulsion of triazophos has higher control efficiency to cotton red spider, and the lasting period reaches more than 20 days, to cotton safety.See table 5, table 6 (EW represents aqueous emulsion in the table, and EC represents missible oil) for details.
Table 5.40% aqueous emulsion of triazophos is to the field control effectiveness test of cotton red spider Lanxi, Zhejiang as a result, 2004.6-7
Table 6.40% aqueous emulsion of triazophos is to the field control effectiveness test of cotton red spider Yuyao, Zhejiang as a result, 2005.6-7
Claims (3)
1. aqueous emulsion of triazophos, it is characterized in that ingredient and percentage by weight thereof are: Hostathion 25-50%, emulsifier 5-15%, stabilizing agent 1-4%, cosolvent 0-10%, dispersant 0-2%, thickener 0-3%, antifreezing agent 0-4% and water surplus, and the content of cosolvent, dispersant, thickener and antifreezing agent can not be 0 simultaneously
Wherein, described emulsifier is selected from castor oil polyoxyethylene ether, styryl phenyl APEO, styrene phenol formaldehyde resin APEO, polyoxyethylene nonylphenol ether, styrene phenol formaldehyde resin polyoxyethylene polyoxypropylene block co-polyether, styrene phenol formaldehyde resin oxirane propylene oxide block copolyether, ethylene glycol glucoside stearate, methyl glucoside stearate, polyoxyethylene (20) sorbitan mono-laurate, calcium dodecyl benzene sulfonate and EO/PO block polyether;
Described stabilizing agent is selected from epoxidized soybean oil, epoxychloropropane, methyl propanediol, butyl glycidyl ether and phenyl glycidyl ether;
Described cosolvent is selected from n-butanol, isobutanol, n-octyl alcohol, n-amyl alcohol, toluene and dimethylbenzene;
Described dispersant is selected from naphthalene sulfonic acid condensate sodium salt, polymeric polycarboxylic acid derivative, sodium lignin sulfonate and maleic acid-acrylic acid copolymer sodium salt;
Described thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose and polyvinyl alcohol;
Described antifreezing agent is selected from ethylene glycol, PEG400, propane diols, glycerine and urea.
2. the preparation method of aqueous emulsion of triazophos as claimed in claim 1 is characterized in that adopting following processing step:
A. according to Hostathion 25-50%, emulsifier 5-15%, stabilizing agent 1-3%, cosolvent 0-10%, dispersant 0-2%, thickener 0-3%, antifreezing agent 0-4% and water surplus and cosolvent, dispersant, the content of thickener and antifreezing agent can not be that 0 weight percent takes by weighing raw material simultaneously, and wherein said emulsifier is selected from castor oil polyoxyethylene ether, styryl phenyl APEO, styrene phenol formaldehyde resin APEO, polyoxyethylene nonylphenol ether, styrene phenol formaldehyde resin polyoxyethylene polyoxypropylene block co-polyether, styrene phenol formaldehyde resin oxirane propylene oxide block copolyether, ethylene glycol glucoside stearate, the methyl glucoside stearate, polyoxyethylene (20) sorbitan mono-laurate, calcium dodecyl benzene sulfonate and EO/PO block polyether; Described stabilizing agent is selected from epoxidized soybean oil, epoxychloropropane, methyl propanediol, butyl glycidyl ether and phenyl glycidyl ether; Used cosolvent is selected from n-butanol, isobutanol, n-octyl alcohol, n-amyl alcohol, toluene and dimethylbenzene; Described dispersant is selected from naphthalene sulfonic acid condensate sodium salt, polymeric polycarboxylic acid derivative, sodium lignin sulfonate and maleic acid-acrylic acid copolymer sodium salt; Described thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose and polyvinyl alcohol; Described antifreezing agent is selected from ethylene glycol, PEG400, propane diols, glycerine and urea;
B. water, antifreezing agent, dispersant and thickener are mixed, obtain water;
C. Hostathion, emulsifier, cosolvent and stabilizing agent are mixed and obtain oil phase;
D. water, oil phase high speed shear are mixed and to obtain the aqueous emulsion of triazophos finished product.
3. the preparation method of aqueous emulsion of triazophos as claimed in claim 1 is characterized in that adopting following processing step:
A. according to Hostathion 25-50%, emulsifier 5-15%, stabilizing agent 1-3%, cosolvent 0-10%, dispersant 0-2%, thickener 0-3%, antifreezing agent 0-4% and water surplus and cosolvent, dispersant, the content of thickener and antifreezing agent can not be that 0 weight percent takes by weighing raw material simultaneously, and wherein said emulsifier is selected from castor oil polyoxyethylene ether, styryl phenyl APEO, styrene phenol formaldehyde resin APEO, polyoxyethylene nonylphenol ether, styrene phenol formaldehyde resin polyoxyethylene polyoxypropylene block co-polyether, styrene phenol formaldehyde resin oxirane propylene oxide block copolyether, ethylene glycol glucoside stearate, the methyl glucoside stearate, polyoxyethylene (20) sorbitan mono-laurate, calcium dodecyl benzene sulfonate and EO/PO block polyether; Described stabilizing agent is selected from epoxidized soybean oil, epoxychloropropane, methyl propanediol, butyl glycidyl ether and phenyl glycidyl ether; Used cosolvent is selected from n-butanol, isobutanol, n-octyl alcohol, n-amyl alcohol, toluene and dimethylbenzene; Described dispersant is selected from naphthalene sulfonic acid condensate sodium salt, polymeric polycarboxylic acid derivative, sodium lignin sulfonate and maleic acid-acrylic acid copolymer sodium salt; Described thickener is selected from xanthans, Magnesiumaluminumsilicate, sodium carboxymethylcellulose and polyvinyl alcohol; Described antifreezing agent is selected from ethylene glycol, PEG400, propane diols, glycerine and urea;
B. water, antifreezing agent, dispersant and thickener are mixed in stirred tank, obtain water;
C. Hostathion, emulsifier, cosolvent and stabilizing agent are mixed in stirred tank, obtain oil phase;
D. under stirring condition, water is added in the oil phase or with oil phase gradually and adds to aqueous phase gradually, make two-phase be mixed into thick emulsion;
E. thick emulsion is input in the high pressure homogenizer, after high-pressure homogeneous, promptly obtains the aqueous emulsion of triazophos finished product.
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| ES2536648T3 (en) * | 2008-12-23 | 2015-05-27 | Cognis Ip Management Gmbh | Compositions of agrochemical auxiliary agents |
| CN102177889A (en) * | 2011-03-15 | 2011-09-14 | 广东中迅农科股份有限公司 | Difenoconazole water emulsion and preparation method thereof |
| CN102204531A (en) * | 2011-04-07 | 2011-10-05 | 中国地质大学（武汉） | Triazophos emulsion in water without organic solvent and preparation method thereof |
| CN102258015B (en) * | 2011-08-11 | 2013-04-10 | 中化化工科学技术研究总院 | Triazophos film spreading oiling agent and preparation method thereof |
| CN103081894A (en) * | 2013-01-25 | 2013-05-08 | 江苏省苏科农化有限责任公司 | Novel preparation method of pesticide emulsion in water |
| CN103893992A (en) * | 2014-03-19 | 2014-07-02 | 安徽生力农化有限公司 | Technical triazophos floating stabilizing bag taking silicon gel as adsorbent |
| CN103893994A (en) * | 2014-03-19 | 2014-07-02 | 安徽生力农化有限公司 | Triazophos technical toxicant floatation stabilizing pocket using inorganic salt drying agent as adsorbent |
| CN106614550A (en) * | 2016-12-28 | 2017-05-10 | 江苏钟山化工有限公司 | Additive used for producing pesticide emulsion in water and preparation and application thereof |
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Address after: 317300. Three Li River, Chengdong, Xianju County, Zhejiang Province Patentee after: Zhejiang Xinnong Chemical Co., Ltd. Address before: 317300 three Li River, Chengdong, Zhejiang, Xianju Patentee before: Xinnong Chemical Co., Ltd., Zhejiang Prov. |
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| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 317300 three Li River, Yang Fu, Xianju County, Zhejiang Patentee after: Zhejiang Xinnong Chemical Co., Ltd. Address before: 317300. Three Li River, Chengdong, Xianju County, Zhejiang Province Patentee before: Zhejiang Xinnong Chemical Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100106 Termination date: 20161107 |