CN101307030A - Preparation method of herbicide - Google Patents
Preparation method of herbicide Download PDFInfo
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- CN101307030A CN101307030A CNA2008100164839A CN200810016483A CN101307030A CN 101307030 A CN101307030 A CN 101307030A CN A2008100164839 A CNA2008100164839 A CN A2008100164839A CN 200810016483 A CN200810016483 A CN 200810016483A CN 101307030 A CN101307030 A CN 101307030A
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- Prior art keywords
- water
- ametryn
- preparation
- atrazine
- reaction
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- 230000002363 herbicidal effect Effects 0.000 title claims abstract description 7
- 239000004009 herbicide Substances 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- RQVYBGPQFYCBGX-UHFFFAOYSA-N ametryn Chemical compound CCNC1=NC(NC(C)C)=NC(SC)=N1 RQVYBGPQFYCBGX-UHFFFAOYSA-N 0.000 claims abstract description 33
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 23
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 19
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000005204 segregation Methods 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- RMBAVIFYHOYIFM-UHFFFAOYSA-M sodium methanethiolate Chemical compound [Na+].[S-]C RMBAVIFYHOYIFM-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing herbicide ametryn. The method adopts the following steps that: (1) after water, sodium hydroxide, sulfonic acid dimethyl ester are added to a reaction kettle and stirred to be dissolved, organic solvent, atrazine and trimethylamine are orderly added to the reaction kettle and heated, and then reflow; (2) after reaction is completed, heating and stirring are stopped; the reaction kettle is kept stand and has water segregated; water with a certain amount is added; the reaction kettle is started to stir and wash, and is kept stand to carry out secondary water segregation; (3) after secondary water segregation, the solution is heated, distilled, cooled, discharged and cooled so as to get ametryn lump material. The method has the advantages that: production raw materials are sufficient; toluene that can be recycled and used indiscriminately is used as the solvent, which reduces wastewater emission and causes little pollution; the method is short in reaction time, simple in post treatment, high in yield and capable of realizing industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of herbicide.
Background technology
Ametryn, chemical name N-2-ethylamino-N-4-isopropylamino-6-methylthio group-1,3,5-triazines.
Molecular formula: C
9H
17N
5S, molecular weight: 227.33
Chemical structural formula:
The physico-chemical property of ametryn: white powder, fusing point 84-85 ℃, vapour pressure 0.365mPa/25 ℃, relative density 1.18, solubleness is 200mg/L (25 ℃) in water, be soluble in organic solvent, nonflammable, do not explode non-corrosiveness, stable in neutral, little acid or slight alkalinity medium, and facile hydrolysis becomes the 6-hydroxy derivatives of no weeding activity in strong acid or strongly basic medium.
Ametryn is a triazines selectivity inner sucting conduction type weedicide, kills the grass effect rapidly, and medicament is absorbed the back by the root of weeds, leaf portion makes weeds withered and dead by suppressing photosynthesis.Its selectivity is relevant with the difference of plant ecological and biochemical reaction, and is best to the control of weeds of firm sprouting.Can form the medicine layer in the 0-5cm adsorption by soil, contact medicament when weed germination is unearthed, ametryn can promote plant-growth under lower concentration, both stimulated the growth of young shoot and root, promotes leaf area to increase, footpath overstriking etc.; Under high density, again plant is produced had strong inhibitory effects.Ametryn is applicable to that sugarcane, oranges and tangerines, corn, soybean, potato, Radix Dauci Sativae field prevent and kill off annual grassy weeds.High dosage can be prevented and kill off perennial weeds, can also aquatic weed control.
Ametryn is once reported weeding activity by H.Gysin and E.Kn ü sli (Adv.Pest Control Res., 1960,3,289) etc. in nineteen sixty, obtains patent GB814948 by the popularization of Switzerland J.R.Geigy S.A company in 1964; CH 337019; US 2909420 has introduced the preparation method, and at present domestic existing how tame producer gets permission registration.
The synthetic method major part of ametryn is that starting raw material forms through reaction with the atrazine both at home and abroad at present.Atrazine (2-chloro-4-ethylamino--6-isopropylamine base-sym-trinitrobenzene) the pure product of intermediate are the white crystals body, molecular formula: C
8H
14ClN
5, divide the amount of giving: 215.69, fusing point is 173--175 ℃, 200 ℃ of boiling points, vapour pressure 0.04MPa (20 ℃).Soluble in water in the time of 20--22 ℃, solubleness is 70ppm, is 1.8% in the methyl alcohol, and chloroform is 5.2%.Chemical structural formula is:
Atrazine also is a kind of weedicide, the existing maturation process of producing this product of China, and market has commodity to purchase.
The main synthetic method of ametryn has:
(1) thiomethyl alcohol method
This method advantage is simple to operate, the yield height, but thiomethyl alcohol market is in short supply, and boiling point is extremely low, bring difficulty to transportation, operate careless slightlyly simultaneously, easily cause thiomethyl alcohol loss, cause the imbalance of reaction mass ratio, and use solvent cost higher, the ametryn that obtains has niff.
(2) sodium methyl mercaptide method
This method advantage is simple to operate, and the reaction times is short, but because sodium methyl mercaptide market is in short supply, and stink is big, and environmental pollution is serious, and the atrazine that obtains has rank smell, " three wastes " intractability is big.This method of domestic main employing is at present produced ametryn.
(3) sodium disulfide method
The advantage of this method is that raw material is bought on market easily, and the smell of reaction is less, makees solvent with water and has reduced pollution and harm to environment.Patent CN1326931A is arranged, a kind of production method of ametryn, obligee Zhongshan Chemical Co., Ltd., Changxing County.Listing the ametryn content that obtains in this route patent only has 95%, because the condition harshness, long reaction time, product yield is low, content is low, impurity is many, and need be with phase-transfer catalyst.
(4) sulfonic acid dimethyl ester method
The molecular formula of this reaction main intermediate sulfonic acid dimethyl ester is: C
3H
6OS
2, structural formula is as follows:
People such as gondola Iacopo Degani and Rita Fochi introduced this route at chemistry and industry on the 6october1986, the exercise question of document is: a kind of new purposes of sulfonic acid dimethyl ester is used for synthesizing the S-triaizine compounds that contains methylthio group.Being to be solvent with 30% the KOH aqueous solution in the paper, is raw material with sulfonic acid dimethyl ester, atrazine, is phase-transfer catalyst with the quaternary ammonium salt of 16-30 straight chain carbon, at 80 ℃ of reaction 30-60min, does middle control with gas-chromatography, synthetic ametryn.The advantage of this law is that desired raw material is on the domestic goods produce market and is easy to get, reaction times is short, but finds the phase-transfer catalyst price height that this method is used in practical study, and consumption is big, this method has caused the cost of ametryn to rise, and the ametryn that this method is produced does not possess the market competitiveness.Can not carry out scale operation, when about 80 ℃, synthesizing ametryn in addition melting phenomenon can take place, after the ametryn fusion of generation atrazine be wrapped in the inside, cause reaction not exclusively, and the reunion balling-up, have influence on quality product.
Summary of the invention
The present invention provides a kind of preparation method of herbicide in order to overcome the deficiency of above-mentioned technical existence, has raw material and is easy to get, and cost is low, and reaction control is simple, helps environmental protection, the yield height, and gained ametryn product odour is little.
The present invention realizes by following measure:
The invention discloses a kind of preparation method of herbicide, it is characterized in that adopting following steps:
(1) water, sodium hydroxide, sulfonic acid dimethyl ester are added in the reactor, after the stirring and dissolving, add organic solvent, atrazine, Trimethylamine 99, temperature rising reflux more successively;
(2) after reaction is finished, stop heating and stirring, leave standstill, divide water, add a certain amount of water again, start to stir and wash, leave standstill, carry out secondary and divide water;
(3) after secondary divides water, the distillation that heats up, cooling, discharging, cooling obtains ametryn piece material.
Among the preparation method of the invention described above, described organic solvent is preferably toluene, and the add-on of toluene is 3～4g/1g atrazine.
Among the preparation method of the invention described above, the mol ratio of reactant is preferably: atrazine: sulfonic acid dimethyl ester: sodium hydroxide: Trimethylamine 99=1: 0.55～0.60: 3.76～3.92: 0.16～0.22.
Among the preparation method of the invention described above, be preferably: reflux temperature is 80-85 ℃, and the distillatory temperature is 105-130 ℃, and the temperature of discharging is 95-100 ℃.
Among the preparation method of the invention described above, be preferably: it is 4～5g water/1g atrazine that secondary divides the water requirement of water.
Among the preparation method of the invention described above, be preferably: described distillation is divided into air distillation and underpressure distillation, and the air distillation temperature is 105 ℃, and vacuum distillation temperature is 120-130 ℃.
The present invention is that to adopt sulfonic acid dimethyl ester, atrazine, sodium hydroxide solution be starting raw material, and employings toluene is solvent, and Trimethylamine 99 is that catalyzer synthesizes ametryn, has solved the defective of existing route existence.Concrete synthetic route is as follows:
Compared with prior art, the most significant advantage of the present invention has:
(1) various raw material used in the present invention all very easily buys in market at home.Suitability for industrialized production raw material abundance, and make solvent with toluene can recycled, has reduced discharged waste water.
(2) the present invention's reaction is made catalyzer with Trimethylamine 99, and consumption is few, and cost is low, and the reaction times is short.
(3) the present invention's reaction replaces sodium methyl mercaptide with sulfonic acid dimethyl ester, has reduced the pollution of sodium methyl mercaptide to environment, and the ametryn smell that obtains is little, and sulfonic acid dimethyl ester is that solid is convenient to transportation.
What (4) the present invention obtained is ametryn piece material, can carry out next step processing after the pulverizing, has saved drying course, has reduced energy consumption and artificial, and aftertreatment is simple.
(5) route of the present invention's employing has reduced cost, has improved the quality of ametryn, and having obtained yield is more than 90%, and interior mark content is the ametryn more than 97%, can realize suitability for industrialized production.
Embodiment
Embodiment 1
Molar ratio is an atrazine: sulfonic acid dimethyl ester: liquid caustic soda: Trimethylamine 99=1: 0.55: 3.76: 0.16.In the 1000ml four-hole boiling flask that has stirring and condenser, add 100g tap water, 150g liquid caustic soda (content 30%), 24.4g sulfonic acid dimethyl ester (content 91%), start stirring, add 66g atrazine (content 98%), add 180g toluene, add 10.2g Trimethylamine 99 (29%), temperature rising reflux reaction 3h, the GC detection reaction transforms situation.After reaction is finished, stop heating and stir, divide water after leaving standstill 5min, add again after 200ml water washes, leave standstill, carry out secondary and divide water.After secondary divided water, normal pressure heated up down and distills to 105 ℃, and underpressure distillation is to 120-130 ℃ then, and solvent-free steaming in 20min stops heating and cool to 95 ℃, and discharging, cooling obtain ametryn piece material 64.56 grams.Content is 97.32%, and yield is 92.26%.
Embodiment 2
Add sulfonic acid dimethyl ester 26.2g, the 156.3g liquid caustic soda, the 14g Trimethylamine 99, device and operation steps, unclassified stores proportioning get finished product ametryn 63.68g with embodiment 1, and content is 97.45%, and yield is 91.13%.
Embodiment 3
Molar ratio is with embodiment 1.In the i000L reactor that has stirring and condenser, thermometer, add 100kg tap water, 150kg liquid caustic soda (content 30%), 24.4kg sulfonic acid dimethyl ester (content 91%), start stirring, add 66kg atrazine (content 98%), add 180kg toluene, add 10.2kg Trimethylamine 99 (29%), temperature rising reflux reaction 3h, the GC detection reaction transforms situation.After reaction is finished, stop heating and stir, divide water after leaving standstill 5min, add again after 200kg water washes, leave standstill, carry out secondary and divide water.After secondary divided water, normal pressure heated up down and distills to 105 ℃, and underpressure distillation is to 120-130 ℃ then, and solvent-free steaming in 20min stops heating and cool to 95 ℃, discharging, and cooling obtains ametryn piece material 63.98kg.Content is 97.29%, and yield is 91.40%.
Embodiment 4
Molar ratio is with embodiment 1.To 3000L have stir and the enamel reaction still of reflux exchanger temperature regulator in adding 400kg tap water, 600kg liquid caustic soda (content 30%), 97.6kg sulfonic acid dimethyl ester (content 91%), start stirring, add 264kg atrazine (content 98%), add 720kg toluene, add 40.8kg Trimethylamine 99 (29%), temperature rising reflux reaction 4h, the GC detection reaction transforms situation.After reaction is finished, stop heating and stir, divide water after leaving standstill 5min, add again after 800kg water washes, leave standstill, carry out secondary and divide water.After secondary divided water, normal pressure heated up down and distills to 105 ℃, and underpressure distillation is to 120-130 ℃ then, and solvent-free steaming in 20min stops heating and cool to 95 ℃, discharging, and cooling obtains ametryn piece material 262.48kg.Content is 97.79%, and yield is 92.09%.
Embodiment 5
In having the enamel reaction still of stirring and reflux exchanger, temperature regulator, 3000L adds 400kg tap water, 480kg liquid caustic soda (content 30%), 107.5kg sulfonic acid dimethyl ester (content 91%), start stirring, add 264kg atrazine (content 98%), add 720kg toluene, add 45.9kg Trimethylamine 99 (29%), temperature rising reflux reaction 4h, the GC detection reaction transforms situation.After reaction is finished, stop heating and stir, divide water after leaving standstill 5min, add again after 800kg water washes, leave standstill, carry out secondary and divide water.After secondary divided water, normal pressure heated up down and distills to 105 ℃, and underpressure distillation is to 120-130 ℃ then, and solvent-free steaming in 20min stops heating and cool to 95 ℃, and discharging, cooling obtain ametryn piece material 268.48kg.Content is 92.56%, and yield is 89.17%.
Embodiment 6
In having the enamel reaction still of stirring and reflux exchanger, temperature regulator, 3000L adds 400kg tap water, 680kg liquid caustic soda (content 30%), 87.5kg sulfonic acid dimethyl ester (content 91%), start stirring, add 264kg atrazine (content 98%), add 720kg toluene, add 40.8kg Trimethylamine 99 (29%), temperature rising reflux reaction 4h, the GC detection reaction transforms situation.After reaction is finished, stop heating and stir, divide water after leaving standstill 5min, add again after 800kg water washes, leave standstill, carry out secondary and divide water.After secondary divided water, normal pressure heated up down and distills to 105 ℃, and underpressure distillation is to 120-130 ℃ then, and solvent-free steaming in 20min stops heating and cool to 95 ℃, discharging, and cooling obtains ametryn piece material 258.48kg.Content is 87.56%, and yield is 81.21%.
Claims (6)
1, a kind of preparation method of herbicide is characterized in that adopting following steps:
(1) water, sodium hydroxide, sulfonic acid dimethyl ester are added in the reactor, after the stirring and dissolving, add organic solvent, atrazine, Trimethylamine 99, temperature rising reflux more successively;
(2) after reaction is finished, stop heating and stirring, leave standstill, divide water, add a certain amount of water again, start to stir and wash, leave standstill, carry out secondary and divide water;
(3) after secondary divides water, the distillation that heats up, cooling, discharging, cooling obtains ametryn piece material.
2, preparation method as claimed in claim 1 is characterized in that: described organic solvent is a toluene, and the add-on of toluene is 3～4g/1g atrazine.
3, preparation method as claimed in claim 1 is characterized in that: the mol ratio of reactant is: atrazine: sulfonic acid dimethyl ester: sodium hydroxide: Trimethylamine 99=1: 0.55～0.60: 3.76～3.92: 0.16～0.22.
4, as claim 1,2 or 3 described preparation methods, it is characterized in that: reflux temperature is 80-85 ℃, and the distillatory temperature is 105-130 ℃, and the temperature of discharging is 95-100 ℃.
5, preparation method as claimed in claim 4 is characterized in that: it is 4～5g water/1g atrazine that secondary divides the water requirement of water.
6, preparation method as claimed in claim 4 is characterized in that: described distillation is divided into air distillation and underpressure distillation, and the air distillation temperature is 105 ℃, and vacuum distillation temperature is 120-130 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100164839A CN101307030A (en) | 2008-06-06 | 2008-06-06 | Preparation method of herbicide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100164839A CN101307030A (en) | 2008-06-06 | 2008-06-06 | Preparation method of herbicide |
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| Publication Number | Publication Date |
|---|---|
| CN101307030A true CN101307030A (en) | 2008-11-19 |
Family
ID=40123736
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|---|---|---|---|
| CNA2008100164839A Pending CN101307030A (en) | 2008-06-06 | 2008-06-06 | Preparation method of herbicide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700926B (en) * | 2009-11-20 | 2011-08-17 | 张运林 | Treatment method of waste liquid of imidazolone type herbicides |
| CN102960348A (en) * | 2012-12-11 | 2013-03-13 | 江苏龙灯化学有限公司 | Weeding combination containing ametryn and sulfentrazone and applications of weeding combination |
| CN103467401A (en) * | 2013-09-18 | 2013-12-25 | 山东潍坊润丰化工有限公司 | Production method and device for ametryn |
| CN108341787A (en) * | 2017-01-23 | 2018-07-31 | 浙江中山化工集团股份有限公司 | A kind of ametryn production method of no catalyst |
| CN108484515A (en) * | 2018-05-24 | 2018-09-04 | 宁夏格瑞精细化工有限公司 | A kind of preparation method of ametryn |
-
2008
- 2008-06-06 CN CNA2008100164839A patent/CN101307030A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700926B (en) * | 2009-11-20 | 2011-08-17 | 张运林 | Treatment method of waste liquid of imidazolone type herbicides |
| CN102960348A (en) * | 2012-12-11 | 2013-03-13 | 江苏龙灯化学有限公司 | Weeding combination containing ametryn and sulfentrazone and applications of weeding combination |
| CN102960348B (en) * | 2012-12-11 | 2014-07-30 | 江苏龙灯化学有限公司 | Weeding combination containing ametryn and sulfentrazone and applications of weeding combination |
| CN103467401A (en) * | 2013-09-18 | 2013-12-25 | 山东潍坊润丰化工有限公司 | Production method and device for ametryn |
| CN103467401B (en) * | 2013-09-18 | 2015-01-07 | 山东潍坊润丰化工股份有限公司 | Production method and device for ametryn |
| CN108341787A (en) * | 2017-01-23 | 2018-07-31 | 浙江中山化工集团股份有限公司 | A kind of ametryn production method of no catalyst |
| CN108484515A (en) * | 2018-05-24 | 2018-09-04 | 宁夏格瑞精细化工有限公司 | A kind of preparation method of ametryn |
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