CN101538282A - Preparation method of imidan - Google Patents
Preparation method of imidan Download PDFInfo
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- CN101538282A CN101538282A CN200910061525A CN200910061525A CN101538282A CN 101538282 A CN101538282 A CN 101538282A CN 200910061525 A CN200910061525 A CN 200910061525A CN 200910061525 A CN200910061525 A CN 200910061525A CN 101538282 A CN101538282 A CN 101538282A
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- Prior art keywords
- reactor
- toluene
- phthalic imidine
- temperature
- imidine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 84
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 22
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 11
- 239000011592 zinc chloride Substances 0.000 claims abstract description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical group CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 abstract 2
- 238000005259 measurement Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- KOSLGDWRQDCASG-UHFFFAOYSA-N 4-(chloromethyl)isoindole-1,3-dione Chemical compound ClCC1=CC=CC2=C1C(=O)NC2=O KOSLGDWRQDCASG-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- QGGFJIALGORYME-UHFFFAOYSA-N 4-(hydroxymethyl)isoindole-1,3-dione Chemical compound OCC1=CC=CC2=C1C(=O)NC2=O QGGFJIALGORYME-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000035987 intoxication Effects 0.000 description 1
- 231100000566 intoxication Toxicity 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009156 water cure Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A preparation method of imidan comprises the following steps: adding phthalic anhydride and urea to a reaction kettle sequentially; reacting for 30min to obtain phthalic imidine for use; transferring formaldehyde and phthalic imidine into the reaction kettle for reacting for 2h to obtain N-hydroxymethylphthalic imidine for use; adding phosphorus pentasulfide and toluene to the reaction kettle, then slowly adding methanol dropwise to the reaction kettle; performing heat preservation for 1h after adding methanol dropwise to obtain 0.0-dimethylphosphonodithioate for use; and transferring the N-hydroxymethylphthalic imidine, zinc chloride and the toluene into the reaction kettle and mixing, then performing heat preservation for 2-5h to obtain bulk imidan crystal. The preparation method has the advantages of high reaction efficiency, short process cycle, high product yield up to 85% above and the like. Especially, the products prepared by the method have high purity; and measurement shows that purity of the products prepared by the method is above 98%.
Description
Technical field
The present invention relates to a kind of preparation method of agricultural chemicals, especially relate to the preparation method of the former medicine of a kind of R-1504.
Background technology
R-1504 is a broad-spectrum organic insecticide, and pure product are the colourless crystallization body, has and tags and stomach poison function.Its longevity of residure is long, and pesticide intoxication is lower, and is safe in utilization, and crop is had certain seepage force, can invade the blade face wax layer, is applicable to various crop insects such as fruits and vegetables, paddy rice, cotton, and doublely controls tetranychid.Be the improved seeds of control paddy rice, cotton, vegetables, fruit tree pest insect.
The preparation method of existing R-1504 is: phthalic acid is mixed slowly heating of back with 20% ammoniacal liquor, evaporation large quantity of moisture when temperature rises to 110-120 ℃, get the reactant hot-water cure then, get the white crystals phthalic imidine, with itself and 12% formalin heating reflux reaction 2-3 hour, cooling, filter, washing, dry, get the methylol Phthalimide, then with the 30-36% mixed in hydrochloric acid after chlorination in toluene, then in 60 ℃ of insulations 2 hours, get intermediate chloromethylbenzene dicarboximide, at last with chloromethylbenzene dicarboximide and O, the reaction of O-Methyl disulfide substituted phosphate makes R-1504.In the above-mentioned technology, because transportation, the carrying cost of ammoniacal liquor and hydrochloric acid are higher; Especially be difficult to control in reaction process, and above-mentioned process cycle is long, the products obtained therefrom yield is low, and purity is low.So extensive, the suitability for industrialized production of this method incompatibility R-1504.
Summary of the invention
The present invention solves the existing existing complex process of R-1504 preparation method, and product yield is limited, purity is low, production cost height, technical problems such as incompatibility is extensive, suitability for industrialized production.
The present invention is mainly solved the problems of the technologies described above by following technical proposals: the preparation method of described R-1504 may further comprise the steps:
A. 1.5-2.0 in molar ratio: 1 ratio drops into phthalic anhydride and urea in the reactor successively, temperature is controlled at 140-145 ℃, reacted 30 minutes, in reactor, add the deionized water equate with weight of urea then and preserved moisture 5-10 minute, then that reaction product is centrifugal, dry that to make phthalic imidine standby;
B. formaldehyde, phthalic imidine are conveyed in the reactor, described formaldehyde and phthalic imidine mol ratio are 1.1-1.6: 1, in reactor, add and the equiponderant water of formaldehyde then, temperature is controlled at 35-55 ℃, reacted 2 hours, temperature of reaction kettle is reduced to 5-15 ℃ then, after the reactant crystallization, take out that reactant is centrifugal, to dry, obtain N-methylol phthalic imidine standby;
C. thiophosphoric anhydride and toluene are sent in the reactor, wherein toluene by weight is thiophosphoric anhydride 70-90%, temperature of reactor is controlled at 50-70 ℃, slowly be added drop-wise to methyl alcohol in the reactor then, the mol ratio of described thiophosphoric anhydride and methyl alcohol is 1: 4.5-5.0, after dropwising, be incubated 1 hour again, make that O.0-the Methyl disulfide substituted phosphate is standby.
D. N-methylol phthalic imidine, zinc chloride, toluene are sent in the reactor and mixed, wherein toluene by weight be N-methylol phthalic imidine weight 1-1.1 doubly, normal temperature drips 0.0-Methyl disulfide substituted phosphate then, and the mol ratio of described N-methylol phthalic imidine, 0.0-Methyl disulfide phosphoric acid ester, zinc chloride is 1: (1.0-1.5): (0.6-1.0); After 0.0-the Methyl disulfide substituted phosphate dropwises, temperature is controlled at 40-65 °, is incubated 2-5 hour, feed deionized water at last reaction product is washed, toluene residual in the reaction product and water are removed in underpressure distillation again, obtain the former medicine crystal of R-1504.
The present invention has the reaction efficiency height, and process cycle is short, the product yield advantages of higher, and its yield reaches more than 85%.And, make production cost significantly reduce because raw materials cost is cheap.Especially adopt technology of the present invention, products obtained therefrom purity is very high, and after testing: the product purity of the inventive method preparation is more than 98%, and impurity is few, has reached international most advanced level.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: in phthalic anhydride and urea mol ratio is that 1.5: 1 ratio drops into phthalic anhydride and urea in the reactor respectively, temperature is controlled at 140 ℃, reacted 30 minutes, in reactor, add the deionized water equate with weight of urea then and preserved moisture 10 minutes, take out then that reaction product is centrifugal, to obtain phthalic imidine after drying standby; Be that 1.1: 1 ratio is conveyed into phthalic imidine, formaldehyde in the reactor respectively then in phthalic imidine and formaldehyde mole ratio, add and the equiponderant water of formaldehyde then, temperature is controlled at 35 ℃, reacted 2 hours, cool the temperature to 15 ℃ then, after the reaction product crystallization, take out centrifugal, the oven dry of reaction product, it is standby to obtain N-methylol phthalic imidine; In thiophosphoric anhydride and toluene by weight ratio is that 1: 0.7 ratio is sent into thiophosphoric anhydride, toluene in the reactor respectively, temperature of reactor is controlled at 70 ℃, slowly be added drop-wise to methyl alcohol in the reactor then, the mol ratio of described thiophosphoric anhydride and methyl alcohol is 1: 4.5, after dropwising, be incubated 1 hour again, it is standby to make 0.0-Methyl disulfide substituted phosphate;
Get N-methylol phthalic imidine respectively, zinc chloride, toluene is sent in the reactor and is mixed, normal temperature drips 0.0-Methyl disulfide substituted phosphate then, described N-methylol phthalic imidine, 0.0-Methyl disulfide phosphoric acid ester, the mol ratio of zinc chloride is 1: 1.0: 0.6, toluene by weight is 1.1 times of N-methylol phthalic imidine weight, after dropwising, temperature of reactor is controlled at 40 ℃, be incubated 2 hours, feeding deionized water at last washes reaction product, toluene residual in the reaction product and water are removed in underpressure distillation again, obtain the former medicine crystal of R-1504.After testing: the purity of this R-1504 finished product is 98.3%.
Embodiment 2: in phthalic anhydride and urea mol ratio is that 1.7: 1 ratio drops into phthalic anhydride and urea in the reactor respectively, temperature is controlled at 145 ℃, reacted 30 minutes, in reactor, add the deionized water equate with weight of urea then and preserved moisture 8 minutes, take out then that reaction product is centrifugal, to obtain phthalic imidine after drying standby; Be that 1.4: 1 ratio is conveyed into phthalic imidine, formaldehyde in the reactor respectively then in phthalic imidine and formaldehyde mole ratio, add and the equiponderant water of formaldehyde then, temperature is controlled at 55 ℃, reacted 2 hours, cool the temperature to 10 ℃ then, after the reaction product crystallization, take out centrifugal, the oven dry of reaction product, it is standby to obtain N-methylol phthalic imidine; In thiophosphoric anhydride and toluene by weight ratio is that 1: 0.8 ratio is sent into thiophosphoric anhydride, toluene in the reactor respectively, temperature of reactor is controlled at 50 ℃, slowly be added drop-wise to methyl alcohol in the reactor then, the mol ratio of described thiophosphoric anhydride and methyl alcohol is 1: 4.8, after dropwising, be incubated 1 hour again, it is standby to make 0.0-Methyl disulfide substituted phosphate;
Get N-methylol phthalic imidine respectively, zinc chloride, toluene is sent in the reactor and is mixed, normal temperature drips 0.0-Methyl disulfide substituted phosphate then, described N-methylol phthalic imidine, 0.0-Methyl disulfide phosphoric acid ester, the mol ratio of zinc chloride is 1: 1.3: 0.8, toluene by weight is 1 times of N-methylol phthalic imidine weight, after dropwising, temperature of reactor is controlled at 65 ℃, be incubated 4 hours, feeding deionized water at last washes reaction product, toluene residual in the reaction product and water are removed in underpressure distillation again, obtain the former medicine crystal of R-1504.After testing: the purity of this R-1504 finished product is 98.7%.
Embodiment 3: in phthalic anhydride and urea mol ratio is that 2.0: 1 ratio drops into phthalic anhydride and urea in the reactor respectively, temperature is controlled at 142 ℃, reacted 30 minutes, in reactor, add the deionized water equate with weight of urea then and preserved moisture 5 minutes, take out then that reaction product is centrifugal, to obtain phthalic imidine after drying standby; Be that 1.6: 1 ratio is conveyed into phthalic imidine, formaldehyde in the reactor respectively then in phthalic imidine and formaldehyde mole ratio, add and the equiponderant water of formaldehyde then, temperature is controlled at 45 ℃, reacted 2 hours, cool the temperature to 5 ℃ then, after the reaction product crystallization, take out centrifugal, the oven dry of reaction product, it is standby to obtain N-methylol phthalic imidine; In thiophosphoric anhydride and toluene by weight ratio is that 1: 0.9 ratio is sent into thiophosphoric anhydride, toluene in the reactor respectively, temperature of reactor is controlled at 65 ℃, slowly be added drop-wise to methyl alcohol in the reactor then, the mol ratio of described thiophosphoric anhydride and methyl alcohol is 1: 5.0, after dropwising, be incubated 1 hour again, it is standby to make 0.0-Methyl disulfide substituted phosphate;
Get N-methylol phthalic imidine respectively, zinc chloride, toluene is sent in the reactor and is mixed, normal temperature drips 0.0-Methyl disulfide substituted phosphate then, described N-methylol phthalic imidine, 0.0-Methyl disulfide phosphoric acid ester, the mol ratio of zinc chloride is 1: 1.5: 1.0, toluene by weight is 1 times of N-methylol phthalic imidine weight, after dropwising, temperature of reactor is controlled at 50 ℃, be incubated 5 hours, feeding deionized water at last washes reaction product, toluene residual in the reaction product and water are removed in underpressure distillation again, obtain the former medicine crystal of R-1504.After testing: the purity of this R-1504 finished product is 98.1%.
Claims (1)
1. the preparation method of a R-1504 is characterized in that this method may further comprise the steps:
A. 1.5-2.0 in molar ratio: 1 ratio drops into phthalic anhydride and urea in the reactor successively, temperature is controlled at 140-145 ℃, reacted 30 minutes, in reactor, add the deionized water equate with weight of urea then and preserved moisture 5-10 minute, then that reaction product is centrifugal, dry that to make phthalic imidine standby;
B. formaldehyde, phthalic imidine are conveyed in the reactor, described formaldehyde and phthalic imidine mol ratio are 1.1-1.6: 1, in reactor, add and the equiponderant water of formaldehyde then, temperature is controlled at 35-55 ℃, reacted 2 hours, temperature of reaction kettle is reduced to 5-15 ℃ then, after the reactant crystallization, take out that reactant is centrifugal, to dry, obtain N-methylol phthalic imidine standby;
C. thiophosphoric anhydride and toluene are sent in the reactor, wherein toluene by weight is thiophosphoric anhydride 70-90%, temperature of reactor is controlled at 50-70 ℃, slowly be added drop-wise to methyl alcohol in the reactor then, the mol ratio of described thiophosphoric anhydride and methyl alcohol is 1: 4.5-5.0, after dropwising, be incubated 1 hour again, it is standby to make 0.0-Methyl disulfide substituted phosphate.
D. N-methylol phthalic imidine, zinc chloride, toluene are sent in the reactor and mixed, wherein toluene by weight be N-methylol phthalic imidine weight 1-1.1 doubly, normal temperature drips 0.0-Methyl disulfide substituted phosphate then, and the mol ratio of described N-methylol phthalic imidine, 0.0-Methyl disulfide phosphoric acid ester, zinc chloride is 1: (1.0-1.5): (0.6-1.0); After 0.0-the Methyl disulfide substituted phosphate dropwises, temperature is controlled at 40-65 °, is incubated 2-5 hour, feed deionized water at last reaction product is washed, toluene residual in the reaction product and water are removed in underpressure distillation again, obtain the former medicine crystal of R-1504.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100615255A CN101538282B (en) | 2009-04-09 | 2009-04-09 | Preparation method of imidan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100615255A CN101538282B (en) | 2009-04-09 | 2009-04-09 | Preparation method of imidan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101538282A true CN101538282A (en) | 2009-09-23 |
| CN101538282B CN101538282B (en) | 2012-07-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100615255A Expired - Fee Related CN101538282B (en) | 2009-04-09 | 2009-04-09 | Preparation method of imidan |
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| Country | Link |
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| CN (1) | CN101538282B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951605A (en) * | 2014-05-04 | 2014-07-30 | 中国农业科学院植物保护研究所 | N-alkylated phthalimide propyl piperazine derivative and cooperative compositions thereof |
| CN105724424A (en) * | 2016-03-25 | 2016-07-06 | 江西正邦生物化工有限责任公司 | Pesticide composition containing tolfenpyrad and phosmet |
| CN108101800A (en) * | 2018-01-12 | 2018-06-01 | 山东聚强化学有限公司 | A kind of synthetic method of ortho-aminobenzoic acid |
| CN108864181A (en) * | 2018-07-26 | 2018-11-23 | 德州绿霸精细化工有限公司 | A kind of method of synthesis O, O- dimethyl disulfide substituted phosphate |
| CN113549001A (en) * | 2021-07-21 | 2021-10-26 | 华阳新材料科技集团有限公司 | A kind of preparation method of N-alkyl-4-nitrophthalimide |
-
2009
- 2009-04-09 CN CN2009100615255A patent/CN101538282B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951605A (en) * | 2014-05-04 | 2014-07-30 | 中国农业科学院植物保护研究所 | N-alkylated phthalimide propyl piperazine derivative and cooperative compositions thereof |
| CN105724424A (en) * | 2016-03-25 | 2016-07-06 | 江西正邦生物化工有限责任公司 | Pesticide composition containing tolfenpyrad and phosmet |
| CN105724424B (en) * | 2016-03-25 | 2018-06-26 | 江西正邦生物化工有限责任公司 | A kind of composition pesticide containing Tolfenpyrad and phosmet |
| CN108101800A (en) * | 2018-01-12 | 2018-06-01 | 山东聚强化学有限公司 | A kind of synthetic method of ortho-aminobenzoic acid |
| CN108101800B (en) * | 2018-01-12 | 2019-02-19 | 山东聚强化学有限公司 | A kind of synthetic method of ortho-aminobenzoic acid |
| CN108864181A (en) * | 2018-07-26 | 2018-11-23 | 德州绿霸精细化工有限公司 | A kind of method of synthesis O, O- dimethyl disulfide substituted phosphate |
| CN108864181B (en) * | 2018-07-26 | 2021-04-13 | 德州绿霸精细化工有限公司 | Method for synthesizing O, O-dimethyl phosphorodithioate |
| CN113549001A (en) * | 2021-07-21 | 2021-10-26 | 华阳新材料科技集团有限公司 | A kind of preparation method of N-alkyl-4-nitrophthalimide |
| CN113549001B (en) * | 2021-07-21 | 2024-03-22 | 华阳新材料科技集团有限公司 | A kind of preparation method of N-alkyl-4-nitrophthalimide |
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| Publication number | Publication date |
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| CN101538282B (en) | 2012-07-18 |
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