CN108558772A - A kind of manufacturing technique method improving carbendazim quality - Google Patents
A kind of manufacturing technique method improving carbendazim quality Download PDFInfo
- Publication number
- CN108558772A CN108558772A CN201810614811.9A CN201810614811A CN108558772A CN 108558772 A CN108558772 A CN 108558772A CN 201810614811 A CN201810614811 A CN 201810614811A CN 108558772 A CN108558772 A CN 108558772A
- Authority
- CN
- China
- Prior art keywords
- reaction
- temperature
- added
- hydrochloric acid
- carbendazim
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/30—Nitrogen atoms not forming part of a nitro radical
- C07D235/32—Benzimidazole-2-carbamic acids, unsubstituted or substituted; Esters thereof; Thio-analogues thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of manufacturing technique method improving carbendazim quality, methanol and phosgene enter reaction tower by flowmeter, and temperature is controlled at 35~40 DEG C, and liquid flows in accumulator tank after synthesis, and gas is collected by condenser;Water is put into hydrolysis reaction device, start mixing plant and lime nitrogen is added, 1h is stirred at 35 DEG C and is centrifuged, centrifugate enters cyanamide reaction unit, methylchloroformate, which is added, makes reaction temperature control at 45 DEG C, and sustained response 3h is 6~8 up to pH value, is centrifuged;Salting liquid is added in reaction vessel, and o-phenylenediamine is added in stirring, and temperature is at 40 DEG C, it is initially added into hydrochloric acid, pH value is maintained at 5 hereinafter, when temperature reaches 98~100 DEG C, it keeps this temperature and pH value is maintained at 6, keep this temperature 1h, clean and dry with hot water after centrifugation;The stringent controlling reaction temperature of the present invention and PH actively add antioxidant and protective agent, and carbendazim product purity is made to improve, and quality improves.
Description
Technical field
The present invention relates to carbendazim synthesis technology fields, and in particular to a kind of production technology improving carbendazim quality
Method.
Background technology
Carbendazim is a kind of benzimidazole, and scientific name is the systemic fungicide of 2- benzimidazole ylcarbamic acid methyl esters,
Abbreviation MBC.Industrial products are white or grey-brown powder, and sterling fusing point is 330~335 DEG C, is dissolved in water and organic solvent
It is little, stablize at salt, property after dissolving in acid, but meet alkali and easily decompose.Its toxicity is low, acute toxicity half lethal dose, that is, LD50
Value:15g/kg is orally more than to big white mouse.Carbendazim can be absorbed by plants and be transferred to other positions through conduction, and interference germ is thin
The mitosis of born of the same parents inhibits growth.It is effective to Ascomycotina, Deuteromycotina disease fungus, to Mastigomycotina fungi
It is active with bacterium unrestraint, for preventing cereal crop, cotton, rape and other crop multiple diseases.Its fungicidal spectrum compared with
Extensively, pulvis, wettable powder and suspending agent are usually processed into.
Carbendazim original is the intermediate of DuPont Corporation's exploitation fungicide benomyl in 1967, G.P. grams of the U.S. in 1969
Lai Mengsi, C.A. Bi Desen and J.J. simms etc. report the bactericidal property of carbendazim, Shenyang China chemical industry in 1970 respectively
Research institute Zhang Shaoming etc. is also independently found that its bactericidal property.H. Han Peier and the F. Lao Qier of Britain in 1973 have delivered more
The report of bacterium spirit bactericidal activity, in the mid-1970s, China and Germany and the U.S. successively realize industrial production.To 80
Age, carbendazim have evolved into the maximum systemic fungicide kind of yield in China.
Invention content
To solve the above problems, the present invention is intended to provide a kind of conversion rate of products is high, product purity is high, economic benefit
Good, circular regeneration and environmental-friendly raising carbendazim quality manufacturing technique method.
Purpose to realize the present invention, the technical solution adopted is that:A kind of manufacturing technique method improving carbendazim quality, institute
Manufacturing technique method is stated to include the following steps:
1) synthesis of methylchloroformates:Methanol is added by flowmeter in reaction tower, and phosgene passes through buffer and flowmeter
Into reaction tower, phosgene remains 1.05~1.1 to the molar ratio of methanol:1, temperature is controlled at 35~40 DEG C, reacts 2~3h,
The content of methylchloroformate is more than 90% in Synthesis liquid at this time, and liquid flows in accumulator tank for use, after gas is collected by condenser
Tower is destroyed into tail gas, cooling methylchloroformate liquid instills accumulator tank;
The tail gas destroys the downstream connection hydrochloric acid absorption tower of tower, the downstream connection hydrochloric acid accumulator tank of the hydrochloric acid absorption tower
With tail gas liberation port;
The condenser is divided into condenser A and condenser B, wherein and sink temperature is set as 65~70 DEG C in condenser A,
The sink temperature of condenser B is set as 10~60 DEG C;
The tail gas, which destroys inside tower, phosgene decomposition catalyst;
2) synthesis of cyanamides base methyl formate salt:Water is put into hydrolysis reaction device and temperature control is at 35 DEG C or so,
Start mixing plant and lime nitrogen is added, in 35 DEG C of reaction 1h stirred below and be centrifuged, filtered solution enters
Cyanamide reaction unit, the methylchloroformate that addition step 1 slowly obtains make reaction temperature control at 45 DEG C, and temperature is by coolant liquid
Control, 1~3h of sustained response after methylchloroformate is added completely into until pH value 6~8 in the range of, by reaction solution carry out from
The heart detaches, and casts out the impurity solid of filtering, and it is for use to retain filtered fluid;
The coolant liquid is delivered to by insulating tube in the chuck outside cyanamide reaction unit by the uniform velocity program-controlled thermostat;
3) synthesis of carbendazim:The salting liquid that step 2 generates is added into reaction vessel, o-phenylenediamine is added in stirring,
Temperature starts that hydrochloric acid is added dropwise, pH value is maintained at 5 hereinafter, when temperature reaches 70 DEG C of progress initial reactions, continues to heat up at 40 DEG C
When to 98~100 DEG C, stop heating, constant temperature heat preservation and pH value be maintained at 6 or so, when o-phenylenediamine in mother liquor remaining weight
Less than 5g/L, 1~2h of this temperature is kept, reservation solid is centrifuged in obtained reaction mixture, centrifugation is obtained
Solid heating water clean and dry, obtain carbendazim;
Antioxidant is added before hydrochloric acid is added dropwise in the synthetic reaction;
Additive is added after hydrochloric acid is added dropwise in the synthetic reaction.
Preferably, in the manufacturing technique method step 2 molar ratio of lime nitrogen and methylchloroformate remain 1.2~
1.5:1。
Preferably, the molar ratio of salting liquid, o-phenylenediamine and hydrochloric acid remains 1.2 in the manufacturing technique method step 3
~1.5:1~1.05:0.8~1.
Preferably, antioxidant is specifically made of the raw material of following percentage in the manufacturing technique method step 3:Glycerine 30
~40%, rapeseed oil 10~15%, nano zine oxide 15~20%, zinc powder 3~6%, antifoaming agent 1~3% and polyethylene 20~
25%.
Preferably, additive is specifically made of the raw material of following percentage in the manufacturing technique method step 3:Glycerine 15
~25%, rapeseed oil 5~10% and paraformaldehyde 60~75%.
Preferably, the antifoaming agent is specifically made of the raw material of following percentage:Dimethyl silicone polymer 30~45%, beans
Oil 5~10%, tributyl phosphate 20~25%, white carbon 10~15%, dispersant 2~5% and stabilizer 1~3%.
Preferably, the preparation method of the antioxidant specifically includes following steps:Polyethylene heating is heated to 130~
Nano zine oxide is added thereto after 150 DEG C and is uniformly mixed, adds glycerine and rapeseed oil, hybrid reaction and stir 30~
Zinc powder and antifoaming agent is added in 45min after being cooled to 40~50 DEG C, stir 10~15min after mixing.
Preferably, in the manufacturing technique method step 3 molar ratio of antioxidant, hydrochloric acid and additive remain 0.3~
0.5:1~1.2:0.2~0.4.
Preferably, hydrochloric acid accumulator tank of the hydrochloric acid being added dropwise in the manufacturing technique method step 3 in step 1, wherein
Concentration of hydrochloric acid in hydrochloric acid accumulator tank is 30~40%.
The principle of the present invention is:Methanol generates methylchloroformate with phosgene reaction, and chemical equation is:
Lime nitrogen is reacted with water generates lime nitrogen hydrogen calcium and calcium hydroxide, lime nitrogen hydrogen calcium, calcium hydroxide and chloro-carbonic acid first
Ester reaction generates cyanamide base methyl formate calcium salt, and wherein side reaction is:Calcium hydroxide is reacted with hydrochloric acid generates calcium chloride and water, changes
Learning reaction equation is:
Cyanamide base methyl formate calcium salt, o-phenylenediamine are reacted with hydrochloric acid generates carbendazim, and chemical equation is:
Beneficial effects of the present invention are:The stringent controlling reaction temperature of carbendazim manufacturing technique method of the present invention and PH, science
Various raw materials are matched, antioxidant and protective agent are actively added, carbendazim product purity is made to improve, quality improves, and content is not less than
98%, DAP is suppressed, HAP impurity generates, and hot water is used in combination to be cleaned multiple times, and is further reduced o-phenylenediamine residual, makes in carbendazim
DAP, HAP, which are remained, to be controlled, and makes DAP, HAP residual less than 3.0pm, 0.5pm hereinafter, existing for residual inorganic salts to greatest extent
It is 0.14%, the quantity of chloride is no more than 0.0002%.
Description of the drawings
Fig. 1 is the flowage structure simplified schematic diagram for the manufacturing technique method that the present invention improves carbendazim quality.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Embodiment 1
As shown in Figure 1, the technical solution adopted by the present invention is:A kind of manufacturing technique method improving carbendazim quality, institute
Manufacturing technique method is stated to include the following steps:
1) synthesis of methylchloroformates:Methanol is added by flowmeter in reaction tower, and phosgene passes through buffer and flowmeter
Into reaction tower, phosgene remains 1.05~1.1 to the molar ratio of methanol:1, temperature is controlled at 35~40 DEG C, reacts 2~3h,
The content of methylchloroformate is more than 90% in Synthesis liquid at this time, and liquid flows in accumulator tank for use, after gas is collected by condenser
Tower is destroyed into tail gas, cooling methylchloroformate liquid instills accumulator tank;
2) synthesis of cyanamides base methyl formate salt:Water is put into hydrolysis reaction device and temperature control is at 35 DEG C or so,
Start mixing plant and lime nitrogen is added, in 35 DEG C of reaction 1h stirred below and be centrifuged, filtered solution enters
Cyanamide reaction unit, the methylchloroformate that addition step 1 slowly obtains make reaction temperature control at 45 DEG C, and temperature is by coolant liquid
Control, 1~3h of sustained response after methylchloroformate is added completely into until pH value 6~8 in the range of, by reaction solution carry out from
The heart detaches, and casts out the impurity solid of filtering, and it is for use to retain filtered fluid;
3) synthesis of carbendazim:The salting liquid that step 2 generates is added into reaction vessel, o-phenylenediamine is added in stirring,
Temperature starts that hydrochloric acid is added dropwise, pH value is maintained at 5 hereinafter, when temperature reaches 70 DEG C of progress initial reactions, continues to heat up at 40 DEG C
When to 98~100 DEG C, stop heating, constant temperature heat preservation and pH value be maintained at 6 or so, when o-phenylenediamine in mother liquor remaining weight
Less than 5g/L, 1~2h of this temperature is kept, reservation solid is centrifuged in obtained reaction mixture, centrifugation is obtained
Solid heating water clean and dry, obtain carbendazim.
Further, the tail gas destroys the downstream connection hydrochloric acid absorption tower of tower, the downstream connection of the hydrochloric acid absorption tower
Hydrochloric acid accumulator tank and tail gas liberation port.
Further, the condenser is divided into condenser A and condenser B, wherein sink temperature is set as in condenser A
65~70 DEG C, the sink temperature of condenser B is set as 10~60 DEG C.
Further, the tail gas, which destroys inside tower, phosgene decomposition catalyst.
Further, the coolant liquid is delivered to by insulating tube outside cyanamide reaction unit by the uniform velocity program-controlled thermostat
In chuck.
Further, antioxidant is added before hydrochloric acid is added dropwise in the synthetic reaction.
Further, additive is added after hydrochloric acid is added dropwise in the synthetic reaction.
Further, in the manufacturing technique method step 2 molar ratio of lime nitrogen and methylchloroformate remain 1.2~
1.5:1。
Further, the molar ratio of salting liquid, o-phenylenediamine and hydrochloric acid remains in the manufacturing technique method step 3
1.2~1.5:1~1.05:0.8~1.
Further, antioxidant is specifically made of the raw material of following percentage in the manufacturing technique method step 3:Glycerine
30~40%, rapeseed oil 10~15%, nano zine oxide 15~20%, zinc powder 3~6%, antifoaming agent 1~3% and polyethylene 20
~25%.
Further, additive is specifically made of the raw material of following percentage in the manufacturing technique method step 3:Glycerine
15~25%, rapeseed oil 5~10% and paraformaldehyde 60~75%.
Further, the antifoaming agent is specifically made of the raw material of following percentage:Dimethyl silicone polymer 30~45%,
Soya-bean oil 5~10%, tributyl phosphate 20~25%, white carbon 10~15%, dispersant 2~5% and stabilizer 1~3%.
Further, the preparation method of the antioxidant specifically includes following steps:Polyethylene heating is heated to 130~
Nano zine oxide is added thereto after 150 DEG C and is uniformly mixed, adds glycerine and rapeseed oil, hybrid reaction and stir 30~
Zinc powder and antifoaming agent is added in 45min after being cooled to 40~50 DEG C, stir 10~15min after mixing.
Further, the molar ratio of antioxidant, hydrochloric acid and additive remains 0.3 in the manufacturing technique method step 3
~0.5:1~1.2:0.2~0.4.
Further, hydrochloric acid accumulator tank of the hydrochloric acid being added dropwise in the manufacturing technique method step 3 in step 1,
In, the concentration of hydrochloric acid in hydrochloric acid accumulator tank is 30~40%.
Wherein, the purity of carbendazim product is not less than 98%;
Wherein, DAP, HAP residual are less than 3.0pm, 0.5pm or less;
Wherein, remain existing for inorganic salts is 0.14% to greatest extent;
Wherein, the quantity of chloride is no more than 0.0002%.
In the present invention, the stringent controlling reaction temperature of carbendazim manufacturing technique method of the present invention and PH, scientific matching are various
Raw material actively adds antioxidant and protective agent, and carbendazim product purity is made to improve, and suppresses DAP, and HAP impurity generates, and hot water is used in combination
It is cleaned multiple times, is further reduced o-phenylenediamine residual, so that DAP, HAP in carbendazim is remained and controlled.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of manufacturing technique method improving carbendazim quality, it is characterised in that:The manufacturing technique method includes following step
Suddenly:
1) synthesis of methylchloroformates:Methanol is added by flowmeter in reaction tower, and phosgene is entered by buffer and flowmeter
Reaction tower, phosgene remain 1.05~1.1 to the molar ratio of methanol:1, temperature is controlled at 35~40 DEG C, reacts 2~3h, at this time
The content of methylchloroformate is more than 90% in Synthesis liquid, and liquid flows in accumulator tank for use, and gas enters after being collected by condenser
Tail gas destroys tower, and cooling methylchloroformate liquid instills accumulator tank;
The tail gas destroys the downstream connection hydrochloric acid absorption tower of tower, the downstream connection hydrochloric acid accumulator tank and tail of the hydrochloric acid absorption tower
Gas liberation port;
The condenser is divided into condenser A and condenser B, wherein sink temperature is set as 65~70 DEG C in condenser A, condensation
The sink temperature of device B is set as 10~60 DEG C;
The tail gas, which destroys inside tower, phosgene decomposition catalyst;
2) synthesis of cyanamides base methyl formate salt:Water is put into hydrolysis reaction device and temperature control is at 35 DEG C or so, is started
Simultaneously lime nitrogen is added in mixing plant, in 35 DEG C of reaction 1h stirred below and is centrifuged, filtered solution enters cyanamide
Reaction unit, the methylchloroformate that addition step 1 slowly obtains make reaction temperature control at 45 DEG C, and temperature is by cooling down hydraulic control
System centrifuges reaction solution in 1~3h of sustained response after methylchloroformate is added completely into until in the range of pH value is 6~8
The impurity solid of filtering is cast out in separation, and it is for use to retain filtered fluid;
The coolant liquid is delivered to by insulating tube in the chuck outside cyanamide reaction unit by the uniform velocity program-controlled thermostat;
3) synthesis of carbendazim:The salting liquid that step 2 generates is added into reaction vessel, o-phenylenediamine, temperature is added in stirring
At 40 DEG C, start that hydrochloric acid is added dropwise, pH value is maintained at 5 hereinafter, when temperature reaches 70 DEG C of progress initial reactions, is continuously heating to 98
At~100 DEG C, stop heating, constant temperature is kept the temperature and pH value is maintained at 6 or so, when remaining weight is less than o-phenylenediamine in mother liquor
5g/L, keeps 1~2h of this temperature, and reservation solid is centrifuged in obtained reaction mixture, consolidates what centrifugation obtained
Body heating water is cleaned and is dried, and obtains carbendazim;
Antioxidant is added before hydrochloric acid is added dropwise in the synthetic reaction;
Additive is added after hydrochloric acid is added dropwise in the synthetic reaction.
2. a kind of manufacturing technique method improving carbendazim quality according to claim 1, it is characterised in that:The production
The molar ratio of lime nitrogen and methylchloroformate remains 1.2~1.5 in process step 2:1.
3. a kind of manufacturing technique method improving carbendazim quality according to claim 1, it is characterised in that:The production
The molar ratio of salting liquid, o-phenylenediamine and hydrochloric acid remains 1.2~1.5 in process step 3:1~1.05:0.8~1.
4. a kind of manufacturing technique method improving carbendazim quality according to claim 1, it is characterised in that:The production
Antioxidant is specifically made of the raw material of following percentage in process step 3:Glycerine 30~40%, rapeseed oil 10~15%,
Nano zine oxide 15~20%, zinc powder 3~6%, antifoaming agent 1~3% and polyethylene 20~25%.
5. a kind of manufacturing technique method improving carbendazim quality according to claim 1, it is characterised in that:The production
Additive is specifically made of the raw material of following percentage in process step 3:Glycerine 15~25%, 5~10% and of rapeseed oil
Paraformaldehyde 60~75%.
6. a kind of manufacturing technique method improving carbendazim quality according to claim 4, it is characterised in that:The defoaming
Agent is specifically made of the raw material of following percentage:Dimethyl silicone polymer 30~45%, soya-bean oil 5~10%, tributyl phosphate 20
~25%, white carbon 10~15%, dispersant 2~5% and stabilizer 1~3%.
7. a kind of manufacturing technique method improving carbendazim quality according to claim 4, it is characterised in that:The antioxygen
The preparation method of agent specifically includes following steps:It is heated to polyethylene heating that it is added in nano zine oxide after 130~150 DEG C
In be uniformly mixed, add glycerine and rapeseed oil, hybrid reaction simultaneously stirs 30~45min, after being cooled to 40~50 DEG C plus
Enter zinc powder and antifoaming agent, stirs 10~15min after mixing.
8. a kind of manufacturing technique method improving carbendazim quality according to claim 1, it is characterised in that:The production
The molar ratio of antioxidant, hydrochloric acid and additive remains 0.3~0.5 in process step 3:1~1.2:0.2~0.4.
9. a kind of manufacturing technique method improving carbendazim quality according to claim 1, it is characterised in that:The production
Hydrochloric acid accumulator tank of the hydrochloric acid being added dropwise in process step 3 in step 1, wherein the concentration of hydrochloric acid in hydrochloric acid accumulator tank
It is 30~40%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810614811.9A CN108558772A (en) | 2018-06-14 | 2018-06-14 | A kind of manufacturing technique method improving carbendazim quality |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810614811.9A CN108558772A (en) | 2018-06-14 | 2018-06-14 | A kind of manufacturing technique method improving carbendazim quality |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108558772A true CN108558772A (en) | 2018-09-21 |
Family
ID=63553965
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810614811.9A Pending CN108558772A (en) | 2018-06-14 | 2018-06-14 | A kind of manufacturing technique method improving carbendazim quality |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108558772A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104961685A (en) * | 2015-06-11 | 2015-10-07 | 安徽东至广信农化有限公司 | Method for reducing carbendazim impurity DAP in production process of carbendazim |
CN107188854A (en) * | 2017-07-12 | 2017-09-22 | 安徽广信农化股份有限公司 | A kind of synthesis technique for improving carbendazim quality |
CN107410294A (en) * | 2017-06-08 | 2017-12-01 | 合肥龙滨化工科技有限公司 | A kind of biological pesticide used additives |
-
2018
- 2018-06-14 CN CN201810614811.9A patent/CN108558772A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104961685A (en) * | 2015-06-11 | 2015-10-07 | 安徽东至广信农化有限公司 | Method for reducing carbendazim impurity DAP in production process of carbendazim |
CN107410294A (en) * | 2017-06-08 | 2017-12-01 | 合肥龙滨化工科技有限公司 | A kind of biological pesticide used additives |
CN107188854A (en) * | 2017-07-12 | 2017-09-22 | 安徽广信农化股份有限公司 | A kind of synthesis technique for improving carbendazim quality |
Non-Patent Citations (1)
Title |
---|
温变英: "《高分子材料加工》", 30 June 2016 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103626655B (en) | Preparation method of metal organic framework material with controllable exposed crystal face | |
WO2021179921A2 (en) | Method for using continuous tank reactor to prepare imidazole | |
CN106083651B (en) | The synthesis technique of salicylonitrile | |
CN112094200A (en) | Synthesis method of bromoxynil octanoate | |
CN101823704B (en) | Method for continuously synthesizing phosphorous acid | |
CN113860264A (en) | Method for continuously producing potassium hydrogen peroxymonosulfate composite salt | |
CN108558772A (en) | A kind of manufacturing technique method improving carbendazim quality | |
CN103333115B (en) | Production method of bromo-3-chloro-5,5-dimethylhydantoin (BCDMH) serving as chemical intermediate | |
CN109096206A (en) | A kind of method of acidity photocatalytic method synthesis carbendazim | |
CN103979600B (en) | A kind of preparation method of ultrafine copper oxide powder | |
CN105348323A (en) | Chlorpyrifos aqueous-phase synthesizing method with trichloro-acetic chloride as primary raw material | |
CN113061076B (en) | Preparation method of chloroterpentane | |
CN110256374B (en) | Preparation method of dimercaptothiadiazole dimer | |
CN112536014B (en) | Device and method for continuously preparing lithium bis (trifluoromethanesulfonyl) imide | |
CN106883103B (en) | Preparation method of 2, 4-dichlorophenol | |
CN108516946A (en) | A kind of synthetic method of new raising thiophanate-methyl quality | |
CN108164514A (en) | A kind of preparation method of epoxiconazole | |
CN114044747A (en) | Synthetic method of o-methylthiobenzonitrile | |
CN109293591A (en) | A kind of preparation method of triazinone | |
CN106748628B (en) | A kind of method that low temperature continuous chlorination prepares mixed-chlorotoluene | |
CN106278911A (en) | The production technology of 3,5 dichloro-4,4s (1,1,2,2 tetrafluoro ethyoxyl) aniline | |
US3980653A (en) | Process for the production of 3,6-bis-(2-methylmercaptoethyl)-2,5-piperazinedione | |
CN107986959A (en) | The preparation method and preparation system of ammonium adipate | |
CN110817821A (en) | Method for preparing food-grade dipotassium hydrogen phosphate by using industrial wet-process purified phosphoric acid | |
CN103552986B (en) | Semi continuous stabilizing chlorine dioxide disinfectant solution production method and production system thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180921 |