CN102898467A - One-pot synthesis method for glyphosate from chloroacetic acid - Google Patents
One-pot synthesis method for glyphosate from chloroacetic acid Download PDFInfo
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Abstract
The invention provides a one-pot synthesis method for glyphosate from chloroacetic acid. According to the method, chloroacetic acid is used as a starting material, triethylamine is used as a catalyst, and a synthesis crude drug is directly synthesized by subjecting chloroacetic acid, triethylamine, paraformaldehyde, ammonia, dimethylphosphite and the like to reactions like addition, condensation and hydrolysis in a methanol solution in a one-pot process; thus, the process of synthesis is substantially simplified, cost for the raw materials is reduced, and production of sewage is reduced.
Description
Technical field
The present invention relates to a kind of method of synthesizing glyphosate, further, be take Mono Chloro Acetic Acid as raw material, take triethylamine as catalyzer, one kettle way reacts the method for direct synthesizing glyphosate through addition, condensation, hydrolysis etc. with Paraformaldehyde 96, ammonia and dimethylphosphite in methanol solution.
Background technology
The weedicide that glyphosate is a kind of non-selective, efficient, low toxicity, interior absorption is wide, found and development and use in 1972 by About Monsanto Chemicals, because its herbicidal performance is remarkable, with low cost, and with after soil contacts, rapidly dissolving under the effect of soil and microorganism, therefore noresidue is promoted on market very soon.In addition, glyphosate is chosen as one of fitst water agricultural chemicals by United States Government, and application prospect is very wide.
Show according to Chinese glycine trade investment research report in 2010, China's glyphosate Industry Quick Development between 2006-2009 4 years, production capacity was by 180,000 tons of 600,000 tons of bringing up to 2009 in 2005, following along with developed country's environmental requirement increase and raw materials cost factor, domestic glyphosate production will occupy very large proportion in the world market.At present the industrial route of synthesizing glyphosate mainly contains two: one is iminodiethanoic acid (IDA) route take prussic acid or diethanolamine as starting raw material that U.S.'s About Monsanto Chemicals adopts; Another is the dimethylphosphite route take glycine as starting raw material that China generally adopts, this technique is because technique is simple, technology maturation, China has with the leading glycine production advantage of Mono Chloro Acetic Acid in addition, therefore, be widely used in China, 1 ton of glyphosate of general every production need consume about 0.96 ton of glycine.
Dialkyl phosphite process using Paraformaldehyde 96 obtains methylal〔Su〕 in the depolymerization of methyl alcohol triethylamine system, then obtain the complex compound of methylol glycine and triethylamine with the glycine condensation, with the dimethylphosphite condensation, obtain the former powder of glyphosate finally by acidifying, separating methanol, depickling, crystallization, filtration, oven dry again.Used main raw material glycine is synthetic with ammonia react under the katalysis of urotropine by Mono Chloro Acetic Acid in this technological process, because glycine is an independent process of producing, in product separation and purge process, produced a large amount of waste liquids, not only to environment, also affect simultaneously Mono Chloro Acetic Acid and utilization ratio, when the production line that makes Mono Chloro Acetic Acid to glyphosate lengthens, also improved production cost.
Summary of the invention
The technical problem to be solved in the present invention is how the synthetic glycine technology of Mono Chloro Acetic Acid and glycine synthesizing glyphosate technique organically to be coupled to a technique, and a kind of method of Mono Chloro Acetic Acid one kettle way synthesizing glyphosate is provided thus.
Based on the problems referred to above and purpose, the method for a kind of Mono Chloro Acetic Acid one kettle way synthesizing glyphosate provided by the present invention, its described method follows these steps to carry out:
(1) take Mono Chloro Acetic Acid as raw material, take methyl alcohol as solvent, 10 ~ 30 minutes salifies of reaction under 30 ~ 70 ℃ with Mono Chloro Acetic Acid and triethylamine obtain solution A;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: triethylamine: methyl alcohol=1:0.9 ~ 1.1:5 ~ 8;
(2) take methyl alcohol as solvent, add Paraformaldehyde 96 and logical ammonia and under 10 ~ 20 ℃, anyway generated hydramine in 30 ~ 50 minutes, obtain solution B;
Wherein, the molar mass of material ratio is: Paraformaldehyde 96: ammonia: methyl alcohol=1:1 ~ 2:2.5 ~ 4;
(3) the B solution with above-mentioned steps (2) joins in the A solution of above-mentioned steps (1), and under 0 ~ 10 ℃, reacts 10 ~ 30 minutes, analyzes the Mono Chloro Acetic Acid peak through high pressure liquid chromatography HPLC and disappears, and obtains solution C;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: Paraformaldehyde 96=1:1.2 ~ 2;
(4) maintain the temperature at 0 ~ 10 ℃ and in C solution, add into a certain amount of triethylamine, and add in batches Paraformaldehyde 96, until system is transparent, then be warming up to 38 ~ 42 ℃, reacted 80 ~ 100 minutes, obtain glycine formaldehyde condensation products solution D;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: triethylamine: Paraformaldehyde 96=1:0.6 ~ 1.2:0.5 ~ 3;
(5) in the D solution of above-mentioned steps (4), drip a certain amount of dialkyl phosphite, and under 48 ~ 55 ℃, reacted 120 ~ 150 minutes, obtain N-dialkyl (phosphonomethyl) glycine solution;
After be cooled to 0 ~ 10 ℃, separate out hydrochloric acid triethylammonium salts crystal, filter the salt separate out with a certain amount of methanol wash salt crystal 1 ~ 3 time, washings and filtrate merging acquisition solution E;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: dialkyl phosphite=1:1 ~ 1.5;
(6) under 10 ~ 25 ℃, E is added dropwise in a certain amount of concentrated hydrochloric acid, and be warming up under 110 ~ 120 ℃, backflow was carried out acidolysis 180 ~ 360 minutes, after acidolysis finishes, carry out air distillation and steam the low-boiling-point substance reuses such as methylal〔Su〕, methyl alcohol, triethylamine, in vacuum tightness be-0.085MPa under, underpressure distillation 60 ~ 120 minutes, slough unnecessary acid, temperature is controlled at 110 ~ 120 ℃, and underpressure distillation adds 30% sodium hydroxide solution after finishing, neutralization is also regulated pH value to 1 ~ 3, add a certain amount of water to concentrated solution, product is separated out in cooling again, and filtration drying makes glyphosate; Filtrate is made 30% gyphosate solution.
In above-mentioned, analyze through high pressure liquid chromatography HPLC, glyphosate is 50 ~ 80% to chloroacetic total mass percentage yield, and wherein the molar mass of material ratio is: Mono Chloro Acetic Acid: hydrochloric acid=1:3 ~ 6.
In technique scheme of the present invention, further technical characterictic is:
Material molar mass ratio in the building-up process is: Mono Chloro Acetic Acid: triethylamine: Paraformaldehyde 96: ammonia: dialkyl phosphite: hydrochloric acid: methyl alcohol=1:1.5 ~ 2.3:1.7 ~ 4:1 ~ 1.5:3 ~ 6:7.5 ~ 12.
Methanol wash hydrochloric acid triethylammonium salts crystal is to carry out at normal temperatures, with the methanol quality mole number is: methyl alcohol at every turn: salt triethylenetetraminehexaacetic acid ammonium=1 ~ 2:1.
Amount of water in concentrated solution is: Mono Chloro Acetic Acid: water=1:2.5 ~ 8.
The method of the above-mentioned a kind of Mono Chloro Acetic Acid one kettle way synthesizing glyphosate that provides of the present invention, the synthetic glycine technology of Mono Chloro Acetic Acid and glycine synthesizing glyphosate technique organically are coupled to a technique, make glycine directly carry out next step synthesizing glyphosate reaction without separating, simultaneously in the building-up process of glycine, do not use urotropine to be catalyzer, using triethylamine instead is catalyzer, and be solvent with methyl alcohol, unite with the building-up process of glyphosate, realized mutual supplement with each other's advantages, not only improved chloroacetic transformation efficiency, simplification and the high efficiency of Solvent and catalyst recovery have also been guaranteed, thereby simplified widely the processing step of Mono Chloro Acetic Acid to glycine, reduce production cost, also reduced the generation of sewage.
Embodiment
The below makes further instructions the specific embodiment of the present invention.
Embodiment 1
Mono Chloro Acetic Acid 9.6g (0.1mol) is dissolved in 20.3ml(0.5mol) in the methyl alcohol, add triethylamine 10.1g (0.1mol), thermopositive reaction slowly occurs, outlet temperature is remained on 30 ℃, keep naturally cooling to room temperature after the 30min, obtain solution A.
With Paraformaldehyde 96 4.0g(0.125mol) be suspended in 10.1ml (0.25mol) methyl alcohol and then import ammonia, temperature of reaction is remained on 20 ℃ stop logical ammonia during to bleach, obtain solution B, the logical 30 minutes ammonia time, the usage quantity of ammonia is 2.9g (0.172mol); Mentioned solution B is joined in the solution A, and temperature remains on 5 ℃, reacts namely to generate intermediate methylol glycine in 15 minutes, gets solution C; Replenish adding 8.6g (0.085mol) triethylamine in C, and add formaldehyde 2.0g (0.063mol), it is transparent to be stirred to solution becomes, then is warming up to 38 ℃, reacts 80 minutes, gets solution D; Solution D is warming up to 50 ℃, adds dimethylphosphite 14.6g(0.13 mol), 50 ℃ of lower insulation reaction 120 minutes.Then be refrigerated to 10 ℃, filter esterifying liquid, the Triethylammonium chloride that filtering is separated out, and the Triethylammonium chloride of separating out with the 15ml methanol wash, washing lotion and filtered liquid merged slowly to be added drop-wise in 9.9g (0.3mol) hydrochloric acid (38%) carry out acidifying, backflow was carried out acidolysis 180 minutes, after acidolysis finishes, air distillation steams methyl alcohol, triethylamine, the reuses such as methylal〔Su〕, when temperature rises to 115 ℃, be decompressed to vacuum tightness and be depickling under the-0.085MPa, underpressure distillation 60 minutes, when temperature reaches 115 ℃ again, stop underpressure distillation, add 10g water, the NaOH with 30% regulates PH=1.5, crystallisation by cooling, suction filtration, drying obtains the former powder of glyphosate, filtrate is made 30% gyphosate solution, analyzes through high pressure liquid chromatography HPLC, and overall yield is 67.8%.
Embodiment 2
Mono Chloro Acetic Acid 9.6g (0.1mol) is dissolved in 26.4ml(0.65mol) in the methyl alcohol, add triethylamine 10.6g (0.1mol), thermopositive reaction slowly occurs, outlet temperature is remained on 40 ℃, keep naturally cooling to room temperature after the 20min, obtain solution A.
With Paraformaldehyde 96 5.15g(0.163mol) be suspended in 13.2ml (0.33mol) methyl alcohol and then import ammonia, temperature of reaction is remained on 10 ℃ stop logical ammonia during to bleach, obtain solution B, the logical 40 minutes ammonia time, the usage quantity of ammonia is 3.15g (0.186mol); Mentioned solution B is joined in the solution A, and temperature remains on 10 ℃, reacts namely to generate intermediate methylol glycine in 10 minutes, gets solution C; Replenish adding 10.3g (0.103mol) triethylamine in C, and add formaldehyde 5.75g (0.182mol), it is transparent to be stirred to solution becomes, then is warming up to 40 ℃, reacts 90 minutes, gets solution D; Solution D is warming up to 50 ℃, adds dimethylphosphite 15.75g(0.14 mol), 50 ℃ of lower insulation reaction 150 minutes.Then be refrigerated to 5 ℃, filter esterifying liquid, the Triethylammonium chloride that filtering is separated out, and the Triethylammonium chloride of separating out with the 13ml methanol wash, washing lotion and filtered liquid merged slowly to be added drop-wise in 14.85g (0.45mol) hydrochloric acid (38%) carry out acidifying, backflow was carried out acidolysis 260 minutes, after acidolysis finishes, air distillation steams methyl alcohol, triethylamine, the reuses such as methylal〔Su〕, when temperature rises to 118 ℃, be decompressed to vacuum tightness and be depickling under the-0.085MPa, underpressure distillation 80 minutes, when temperature reaches 118 ℃ again, stop underpressure distillation, add 12g water, the NaOH with 30% regulates PH=1.5, crystallisation by cooling, suction filtration, drying obtains the former powder of glyphosate, filtrate is made 30% gyphosate solution, analyzes through high pressure liquid chromatography HPLC, and overall yield is 69.5%.
Embodiment 3
Mono Chloro Acetic Acid 9.6g (0.1mol) is dissolved in 32.5ml(0.8mol) in the methyl alcohol, add triethylamine 10.1g (0.1mol), thermopositive reaction slowly occurs, outlet temperature is remained on 60 ℃, keep naturally cooling to room temperature after the 25min, obtain solution A.
With Paraformaldehyde 96 6.3g(0.2mol) be suspended in 16.2ml (0.4mol) methyl alcohol and then import ammonia, temperature of reaction is remained on 20 ℃ stop logical ammonia during to bleach, obtain solution B, the logical 40 minutes ammonia time, the usage quantity of ammonia is 3.4g (0.20mol); Mentioned solution B is joined in the solution A, and temperature remains on 10 ℃, reacts namely to generate intermediate methylol glycine in 20 minutes, gets solution C; Replenish adding 12.2g (0.12mol) triethylamine in C, and add formaldehyde 9.5g (0.30mol), it is transparent to be stirred to solution becomes, then is warming up to 42 ℃, reacts 100 minutes, gets solution D; Solution D is warming up to 50 ℃, adds dimethylphosphite 16.9g(0.15 mol), 55 ℃ of lower insulation reaction 130 minutes.Then be refrigerated to 10 ℃, filter esterifying liquid, the Triethylammonium chloride that filtering is separated out, and the Triethylammonium chloride of separating out with the 12ml methanol wash, washing lotion and filtered liquid merged slowly to be added drop-wise in 19.8g (0.6mol) hydrochloric acid (38%) carry out acidifying, backflow was carried out acidolysis 300 minutes, after acidolysis finishes, air distillation steams methyl alcohol, triethylamine, the reuses such as methylal〔Su〕, when temperature rises to 120 ℃, be decompressed to vacuum tightness and be depickling under the-0.085MPa, underpressure distillation 100 minutes, when temperature reaches 120 ℃ again, stop underpressure distillation, add 14.4g water, the NaOH with 30% regulates PH=1.5, crystallisation by cooling, suction filtration, drying obtains the former powder of glyphosate, filtrate is made 30% gyphosate solution, analyzes through high pressure liquid chromatography HPLC, and overall yield is 58.6%.
Embodiment 4
Mono Chloro Acetic Acid 9.6g (0.1mol) is dissolved in 32.5ml(0.8mol) in the methyl alcohol, add triethylamine 10.1g (0.1mol), thermopositive reaction slowly occurs, outlet temperature is remained on 60 ℃, keep naturally cooling to room temperature after the 15min, obtain solution A.
With Paraformaldehyde 96 5.5g(0.113mol) be suspended in 14.6ml (0.36mol) methyl alcohol and then import ammonia, temperature of reaction is remained on 15 ℃ stop logical ammonia during to bleach, obtain solution B, the logical 35 minutes ammonia time, the usage quantity of ammonia is 2.7g (0.16mol); Mentioned solution B is joined in the solution A, and temperature remains on 0 ℃, reacts namely to generate intermediate methylol glycine in 30 minutes, gets solution C; Replenish adding 9.15g (0.09mol) triethylamine in C, and add formaldehyde 7.15g (0.225mol), it is transparent to be stirred to solution becomes, then is warming up to 38 ℃, reacts 100 minutes, gets solution D; Solution D is warming up to 48 ℃, adds dimethylphosphite 19.65g(0.153mol), 55 ℃ of lower insulation reaction 160 minutes.Then be refrigerated to 0 ℃, filter esterifying liquid, the Triethylammonium chloride that filtering is separated out, and the Triethylammonium chloride of separating out with the 14ml methanol wash, washing lotion and filtered liquid merged slowly to be added drop-wise in 18.2g (0.55mol) hydrochloric acid (38%) carry out acidifying, backflow was carried out acidolysis 360 minutes, after acidolysis finishes, air distillation steams methyl alcohol, triethylamine, the reuses such as methylal〔Su〕, when temperature rises to 116 ℃, be decompressed to vacuum tightness and be depickling under the-0.085MPa, underpressure distillation 120 minutes, when temperature reaches 116 ℃ again, stop underpressure distillation, add 8.5g water, the NaOH with 30% regulates PH=1.5, crystallisation by cooling, suction filtration, drying obtains the former powder of glyphosate, filtrate is made 30% gyphosate solution, analyzes through high pressure liquid chromatography HPLC, and overall yield is 79.6%.
Embodiment 5
Mono Chloro Acetic Acid 9.6g (0.1mol) is dissolved in 28.4ml(0.7mol) in the methyl alcohol, add triethylamine 10.1g (0.1mol), thermopositive reaction slowly occurs, outlet temperature is remained on 70 ℃, keep naturally cooling to room temperature after the 10min, obtain solution A.
With Paraformaldehyde 96 4.7g(0.125mol) be suspended in 13.0ml (0.32mol) methyl alcohol and then import ammonia, temperature of reaction is remained on 10 ℃ stop logical ammonia during to bleach, obtain solution B, the logical 50 minutes ammonia time, the usage quantity of ammonia is 2.0g (0.12mol); Mentioned solution B is joined in the solution A, and temperature remains on 0 ℃, reacts namely to generate intermediate methylol glycine in 25 minutes, gets solution C; Replenish adding 6.1g (0.060mol) triethylamine in C, and add formaldehyde 4.8g (0.15mol), it is transparent to be stirred to solution becomes, then is warming up to 42 ℃, reacts 80 minutes, gets solution D; Solution D is warming up to 48 ℃, adds dimethylphosphite 12.4g(0.11 mol), 48 ℃ of lower insulation reaction 180 minutes.Then be refrigerated to 0 ℃, filter esterifying liquid, the Triethylammonium chloride that filtering is separated out, and the Triethylammonium chloride of separating out with the 10ml methanol wash, washing lotion and filtered liquid merged slowly to be added drop-wise in 16.5g (0.5mol) hydrochloric acid (38%) carry out acidifying, backflow was carried out acidolysis 280 minutes, after acidolysis finishes, air distillation steams methyl alcohol, triethylamine, the reuses such as methylal〔Su〕, when temperature rises to 115 ℃, be decompressed to vacuum tightness and be depickling under the-0.085MPa, underpressure distillation 100 minutes, when temperature reaches 115 ℃ again, stop underpressure distillation, add 6.0g water, the NaOH with 30% regulates PH=1.5, crystallisation by cooling, suction filtration, drying obtains the former powder of glyphosate, filtrate is made 30% gyphosate solution, analyzes through high pressure liquid chromatography HPLC, and overall yield is 75.7%.
Claims (2)
1. the method for a Mono Chloro Acetic Acid one kettle way synthesizing glyphosate, its described method follows these steps to carry out:
(1) take Mono Chloro Acetic Acid as raw material, take methyl alcohol as solvent, 10 ~ 30 minutes salifies of reaction under 30 ~ 70 ℃ with Mono Chloro Acetic Acid and triethylamine obtain solution A;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: triethylamine: methyl alcohol=1:0.9 ~ 1.1:5 ~ 8;
(2) take methyl alcohol as solvent, add Paraformaldehyde 96, and pass into ammonia under 10 ~ 20 ℃, react 30 ~ 50 minutes generation hydramine, obtain solution B;
Wherein, the molar mass of material ratio is: Paraformaldehyde 96: ammonia: methyl alcohol=1:1 ~ 2:2.5 ~ 4;
(3) the B solution with above-mentioned steps (2) joins in the A solution of above-mentioned steps (1), and under 0 ~ 10 ℃, reacts 10 ~ 30 minutes, obtains solution C;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: Paraformaldehyde 96=1:1.2 ~ 2;
(4) maintain the temperature at 0 ~ 10 ℃ and in C solution, add into a certain amount of triethylamine, and add Paraformaldehyde 96, until system is transparent, then be warming up to 38 ~ 42 ℃, reacted 80 ~ 100 minutes, obtain glycine formaldehyde condensation products solution D;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: triethylamine: Paraformaldehyde 96=1:0.6 ~ 1.2:0.5 ~ 3;
(5) in the D solution of above-mentioned steps (4), drip a certain amount of dialkyl phosphite, and under 48 ~ 55 ℃, reacted 120 ~ 150 minutes, obtain N-dialkyl (phosphonomethyl) glycine solution;
After be cooled to 0 ~ 10 ℃, separate out hydrochloric acid triethylammonium salts crystal, filter the salt separate out with a certain amount of methanol wash 1 ~ 3 time, washings and filtrate merging acquisition solution E;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: dialkyl phosphite=1:1 ~ 1.5; Methanol wash hydrochloric acid triethylammonium salts crystal is to carry out at normal temperatures, with the methanol quality mole number is: methyl alcohol at every turn: salt triethylenetetraminehexaacetic acid ammonium=1 ~ 2:1;
(6) under 10 ~ 25 ℃, to drip in the E solution in a certain amount of concentrated hydrochloric acid, and be warming up under 110 ~ 120 ℃, after the backflow acidolysis 180 ~ 360 minutes, air distillation steams methylal〔Su〕, methyl alcohol and the reuse of triethylamine low-boiling-point substance, in vacuum tightness be-0.085MPa under, unnecessary acid is sloughed in underpressure distillation 60 ~ 120 minutes, and temperature is controlled at 110 ~ 120 ℃, after the underpressure distillation, add 30% sodium hydroxide solution, neutralization is also regulated pH value to 1 ~ 3, adds a certain amount of water to concentrated solution again, product is separated out in cooling, and filtration, drying make glyphosate; Filtrate is made 30% gyphosate solution;
Wherein, the molar mass of material ratio is: Mono Chloro Acetic Acid: hydrochloric acid=1:3 ~ 6; Amount of water in concentrated solution is: Mono Chloro Acetic Acid: water=1:2.5 ~ 8.
2. method according to claim 1, the total molar mass ratio of the material in its building-up process is: Mono Chloro Acetic Acid: triethylamine: Paraformaldehyde 96: ammonia: dialkyl phosphite: hydrochloric acid: methyl alcohol=1:1.5 ~ 2.3:1.7 ~ 4:1 ~ 1.5:3 ~ 6:7.5 ~ 12.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329350A (en) * | 2018-04-20 | 2018-07-27 | 湖北泰盛化工有限公司 | A kind of glyphosate synthesis device |
| CN108690071A (en) * | 2018-04-20 | 2018-10-23 | 湖北泰盛化工有限公司 | A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material |
| CN113402549A (en) * | 2021-07-14 | 2021-09-17 | 安徽东至广信农化有限公司 | Preparation method of glyphosate technical |
| CN113402549B (en) * | 2021-07-14 | 2024-05-31 | 安徽东至广信农化有限公司 | Preparation method of glyphosate raw medicine |
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2012
- 2012-09-14 CN CN2012103386391A patent/CN102898467A/en active Pending
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| 高立蕊: "氯乙酸—锅法合成草甘膦新工艺的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329350A (en) * | 2018-04-20 | 2018-07-27 | 湖北泰盛化工有限公司 | A kind of glyphosate synthesis device |
| CN108690071A (en) * | 2018-04-20 | 2018-10-23 | 湖北泰盛化工有限公司 | A kind of chloroacetic acid is the technique of the alkyl esterification method synthesizing glyphosate of raw material |
| CN113402549A (en) * | 2021-07-14 | 2021-09-17 | 安徽东至广信农化有限公司 | Preparation method of glyphosate technical |
| CN113402549B (en) * | 2021-07-14 | 2024-05-31 | 安徽东至广信农化有限公司 | Preparation method of glyphosate raw medicine |
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Application publication date: 20130130 |