CN115232046B - Crystal sodium methyldithiocarbamic acid and preparation method thereof - Google Patents
Crystal sodium methyldithiocarbamic acid and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 30
- CJDORTNLPIVZKI-UHFFFAOYSA-N methylcarbamodithioic acid;sodium Chemical compound [Na].CNC(S)=S CJDORTNLPIVZKI-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 27
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical compound [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- UESSEMPSSAXQJC-UHFFFAOYSA-N ethanol;methanamine Chemical compound NC.CCO UESSEMPSSAXQJC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 6
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 229940068886 polyethylene glycol 300 Drugs 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 19
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- HYVVJDQGXFXBRZ-UHFFFAOYSA-N metam Chemical compound CNC(S)=S HYVVJDQGXFXBRZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003958 fumigation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000006283 soil fumigant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000243785 Meloidogyne javanica Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical class [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000835 effect on nematodes Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- -1 sodium (potassium) aminodithioformate Chemical compound 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses crystal sodium methyldithiocarbamate and a preparation method thereof. The crystal sodium methyldithiocarbamic acid provided by the invention has an XRD spectrum with characteristic peaks at the positions of diffraction angles 2 theta of 7.922 and 15.522,16.080,17.840,19.157,21.621,24.239,24.462,25.160,28.943,29.382,30.622,31.340,32.138,32.499,35.258,36.698,38.677,39.222,39.824,40.887,42.577,43.842. The preparation method comprises the following steps: adding a catalyst with the weight of 0.1-1% of that of monomethylamine into a monomethylamine ethanol solution with the mass percentage concentration of 30-40%, controlling the reaction temperature to be 0-30 ℃, dropwise adding carbon disulfide within 10-24 hours, stirring for 2-10 hours at 10-30 ℃ after the dropwise adding, controlling the reaction temperature to be-10-10 ℃, dropwise adding liquid alkali with the mass percentage concentration of 30-40%, stirring for 5-10 hours after the dropwise adding is finished, precipitating crystals, filtering and drying to obtain crystal sodium methyldithiocarbamate.
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to crystal sodium methyldithiocarbamate and a preparation method thereof.
Background
Sodium methyldithiocarbamate, CAS No.:137-42-8, trade name of weibaimu. The carb-acre belongs to a biocidal soil treatment agent, and the chemical name is sodium methyldithiocarbamic acid, which is easy to dissolve in water and most of organic solvents, and the concentrated solution is relatively stable, and is easy to decompose and release methyl isothiocyanate to play a role of fumigation after dilution. The current mode of administration for the wilfordii mainly comprises injection, ditch application, irrigation, drip irrigation and the like. After the carb-acre liquid medicine enters the soil, the carb-acre liquid medicine can react with water rapidly to generate methyl isothiocyanate and hydrogen sulfide gas. (Zhao Wen et al, pesticide science report 2013, 15 (5): 567-573) property of degradation of carb acre and methyl isothiocyanate in soil under laboratory conditions.
The use history of the wilfordii as a low-toxicity and high-efficiency soil fumigant is over 50 years, the bactericidal activity of the wilfordii is reported in Klopping 1951, the Stauffer chemical company in the United states in 1955 firstly pushes out industrialized products, the wilfordii is widely popularized and applied, the use amount of the wilfordii is continuously increased in countries with higher agricultural mechanization degrees such as the United states, western Europe and the like until the year of 20 century 90, and the use amount of the wilfordii only in the United states reaches 1.32 ten thousand tons per year. Over 50 years, the wilfordii is widely applied due to wide control spectrum, good effect and low price, and is registered and used in the near 20 countries in the world. The wilfordii in 2002 starts to register and use in China, but is not widely popularized and applied due to the influence of low agricultural mechanization degree in China. The carb acre is stable in a concentrated aqueous solution and unstable in a dilute aqueous solution. The chemical change occurs after the carb-acre liquid medicine contacts with the moisture in the soil, methyl isothiocyanate is decomposed, and is an effective component which actually plays a role in fumigation, and under proper soil environment conditions, harmful microorganisms such as fungi, bacteria and the like in the soil can be effectively killed, meanwhile, the chemical compound pesticide has a good control effect on nematodes and soil insects, can kill field weed seeds, has a weeding effect, and finally, the methyl isothiocyanate is completely degraded, does not have adverse effects on crops and has no residue in crops and fruits.
Patent CN1368005 discloses an aminodithioformate pesticide and its preparation method, and its effective component is a pesticide according with general formula
；
Wherein: r is methylamine, dimethylamine, trimethylamine or ethylamine; m is metal K, na, zn, or Cu; the preparation method of the n=1, 2 aminodithioformate comprises the steps of firstly, in an aqueous medium, reacting carbon disulfide with organic amine, then adding sodium (potassium) alkali liquor to neutralize to generate sodium (potassium) aminodithioformate, and carrying out heat preservation reaction for 2-3 hours to prepare a liquid product; copper (zinc) salts can also be produced by metathesis reactions.
Patent CN102267931A discloses a process for producing the carb acre, which comprises the steps of mixing 1-1.2 parts by weight of monomethylamine solution with 0.9-1.0 part by weight of carbon disulfide, reacting for 2-3 hours at 10-30 ℃ to obtain N-methyldithiocarbamic acid, then dropwise adding 2.0-2.2 parts by weight of sodium hydroxide solution, neutralizing for 2 hours at 35-60 ℃, enabling the pH value of the solution to be 6-10, and carrying out negative pressure dehydration, cooling, suction filtration and drying after the reaction is finished to obtain the carb acre. The post-treatment of the method needs to be dehydrated, cooled, filtered and dried to obtain the carb acre, the dehydration energy consumption is high, the unreacted complete methylamine and carbon disulfide exist, and the gas volatilizes and the danger is high during the vacuum dehydration.
The chemical reaction formula is as follows (two steps):
the process for synthesizing the carb acre has long production time and low production efficiency, and the intermediate (n-methyldithiocarbamic acid) in the first step is easy to decompose into methyl isothiocyanate and hydrogen sulfide in the production process, so that the content of a product is reduced, and the storage stability of the product is influenced by the generation of byproducts. On the other hand, along with the production of the reaction n-methyldithiocarbamic acid, the pH value of the reaction environment gradually decreases, the reaction speed of monomethylamine and carbon disulfide is reduced, excessive carbon disulfide exists in the reaction system, the carbon disulfide is easy to escape, the yield is reduced, the environment is polluted, and the explosion or the fire is possibly caused.
Patent CN 111848478A discloses a one-step method for synthesizing soil fumigant wilms, which is to stir and mix water, monomethylamine aqueous solution and sodium hydroxide aqueous solution, drop carbon disulfide, and after the continuous stirring reaction, directly obtain yellow to reddish brown wilms finished products, and the method is used for soil fumigation treatment, killing root-knot nematodes, harmful bacteria and underground pests, and removing weeds.
The chemical reaction formula is as follows:
the production process successfully prepares the sodium methyldithiocarbamic acid aqueous solution, is widely applied in the pesticide field, and has the advantage that the aqueous solution can be directly barreled for sale. However, aqueous sodium methyldithiocarbamate has very poor storage stability (Wang Han, storage stability study of 4 dithiocarbamate fungicides in 6 fruit and vegetable samples, hunan agricultural university, shuoshi treatises). Is placed in a long-time or high-temperature field environment, is easy to decompose, is easy to escape from carbon disulfide, causes environmental pollution, and can possibly cause explosion or fire.
Disclosure of Invention
The invention aims to provide a crystal sodium methyldithiocarbamic acid with XRD spectrum 2 theta of 7.9, 22, 15.522,16.080,17.840,19.157,21.621,24.239,24.462,25.160,28.943,29.382,30.622,31.340,32.138,32.499,35.258,36.698,38.677,39.222,39.824,40.887,42.577,43.842 and a series of characteristic peaks.
The preparation method comprises the following steps: adding a catalyst accounting for 0.1-1% of the weight of monomethylamine into a monomethylamine ethanol solution with the mass percentage concentration of 30-40%, controlling the reaction temperature to be 0-30 ℃, dropwise adding carbon disulfide within 10-24 hours, and stirring for 2-10 hours at 10-30 ℃ after the dropwise adding is finished;
controlling the reaction temperature to be-10-10 ℃, dropwise adding liquid alkali with the mass percent concentration of 30-40%, stirring for 5-10 hours after the completion of dropwise adding, precipitating crystals, filtering and drying to obtain the crystal sodium methyldithiocarbamic acid.
As a preferred embodiment of the invention, the molar ratio of monomethylamine to carbon disulphide is 1-1.05:1.
As a preferred embodiment of the invention, the molar ratio of monomethylamine to liquid base is 1:1-1.5.
As a preferable scheme of the invention, the catalyst is polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400 and polyethylene glycol 600.
The invention solves the defect that the aqueous solution of sodium methyldithiocarbamic acid is unstable under the conditions of high temperature, high humidity and long-time storage, and the crystal sodium methyldithiocarbamic acid is directly prepared, and is easy to transport and store.
Drawings
FIG. 1 is an X-ray diffraction pattern of sodium methyldithiocarbamate crystals;
FIG. 2 is an infrared spectrum of sodium methyldithiocarbamate crystals.
Detailed Description
The following examples are presented to those of ordinary skill in the art to make and evaluate the invention and are merely exemplary of the disclosure and are not intended to limit the scope. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise indicated, temperature is in units of degrees celsius or at ambient temperature and pressure is at or near atmospheric pressure. Example 1
Adding 1000 kg of 30% methylamine ethanol solution into a 5-cube stainless steel reaction kettle, adding 0.3 kg of polyethylene glycol 200, controlling the reaction temperature to be 0 ℃, dropwise adding 735 kg of carbon disulfide within 10 hours, stirring at 10 ℃ for 2 hours after the dropwise adding, controlling the reaction temperature to be-10 ℃, dropwise adding 1290 kg of 30% liquid alkali by mass percent, stirring for 5 hours after the dropwise adding is finished, precipitating a large amount of light yellow crystals, filtering and drying to obtain 1200 kg of crystal sodium methyldithiocarbamate. The X-ray diffraction diagram is shown in figure 1, and a series of characteristic peaks exist at the positions 7.922 and 15.522,16.080,17.840,19.157,21.621,24.239,24.462,25.160,28.943,29.382,30.622,31.340,32.138,32.499,35.258,36.698,38.677,39.222,39.824,40.887,42.577,43.842 of the XRD spectrum 2 theta. The infrared spectrum of the obtained crystalline sodium methyldithiocarbamate is shown in fig. 2.
0.3g of the prepared crystalline sodium methyldithiocarbamate sample (accurate to 0.0002 g) was weighed and placed in a clean round bottom flask, 50mL of a 6% strength by mass zinc acetate solution was placed in a first absorption tube, and 50mL of a potassium hydroxide-methanol solution was added to a second absorption tube, which was connected to a decomposition absorption device, and the tightness of the device was checked. The cooling water is opened, a pumping air source is opened, the pumping speed is controlled, and bubbles uniformly and stably pass through the absorption tube every second (2-6). 50mL of 3% sulfuric acid solution was added to the round bottom flask via a long neck funnel and shaken well. And simultaneously, immediately and rapidly heating, carefully controlling to prevent the reaction liquid from rushing out, keeping micro-boiling for 50min, disassembling the device, stopping heating, taking down the second absorption tube, washing the content into a 500mL triangular flask with 200mL of water, checking the absorption tube with phenolphthalein indicator liquid, washing until no residue exists in the tube, neutralizing with 36% acetic acid solution until the phenolphthalein is faded, excessively adding 3-4 drops, immediately titrating with iodine standard titration solution, continuously shaking, adding 5mL of starch indicator liquid when the end point is reached, continuously titrating with iodine standard titration solution until the light grey purple is reached as the end point, simultaneously performing blank measurement, and finally calculating to obtain the purity of 95.23%.
Example 2
In a stainless steel reaction kettle with 5 cubes, 1000 kg of 40% methylamine ethanol solution is added, 3 kg of polyethylene glycol 300 is added, the reaction temperature is controlled to be 30 ℃, 934 kg of carbon disulfide is dropwise added within 24 hours, the mixture is stirred at 30 ℃ for 10 hours after the dropwise addition, the reaction temperature is controlled to be 10 ℃, 1290 kg of 40% liquid alkali with the mass percent concentration is dropwise added, the stirring is completed for 10 hours, a large amount of light yellow crystals are separated out, and the crystals are filtered and dried to obtain 1100 kg of sodium methyldithiocarbamate with the purity of 96.89% (the testing method is the same as that of example 1).
Example 3
In a stainless steel reaction kettle with 5 cubes, 1000 kg of 30% methylamine ethanol solution is added, 1 kg of polyethylene glycol 400 is added, the reaction temperature is controlled to be 5 ℃, 735 kg of carbon disulfide is dropwise added within 12 hours, the reaction temperature is controlled to be 0 ℃ after the dropwise addition is finished, 1290 kg of 30% liquid alkali with the mass percent concentration is dropwise added, the dropwise addition is finished and the stirring is carried out for 8 hours, a large amount of light yellow crystals are separated out, and the crystals are filtered and dried to obtain 1100 kg of crystal sodium methyldithiocarbamate with the purity of 95.71% (the test method is the same as that of example 1).
Example 4
In a stainless steel reaction kettle with 5 cubes, 1000 kg of 40% methylamine ethanol solution is added, 2 kg of polyethylene glycol 600 is added, the reaction temperature is controlled to be 0 ℃, 935 kg of carbon disulfide is dropwise added within 24 hours, the reaction temperature is controlled to be-10 ℃ after the dropwise addition is finished, 1200 kg of liquid alkali with the mass percent concentration of 40% is dropwise added, the dropwise addition is finished and the stirring is carried out for 10 hours, a large amount of light yellow crystals are separated out, and the crystals are filtered and dried to obtain 1058 kg of sodium methyldithiocarbamate with the purity of 96.11% (the test method is the same as that of example 1).
Comparative example 1
100 g of monomethylamine aqueous solution with the mass percent concentration of 40% and 100 g of carbon disulfide are added into a 500ml three-neck flask to react in a mixed mode to generate N-methyldithiocarbamic acid, the reaction temperature is 20 ℃, the reaction time is 3 hours, 210 g of sodium hydroxide solution with the mass percent concentration of 30% is dropwise added into the prepared N-methyldithiocarbamic acid solution to react for 2 hours, the temperature is 60 ℃, and no crystal is separated out after the reaction is finished. The reaction solution was cooled to 0℃and no crystals were precipitated.
Comparative example 2
Into a 500ml three-neck flask, 100 g of 30% aqueous methylamine solution is added, the reaction temperature is controlled to be 0 ℃, 73 g of carbon disulfide is added dropwise within 10 hours, the mixture is stirred for 2 hours at 10 ℃ after the dropwise addition, the reaction temperature is controlled to be-10 ℃, 129 g of 30% liquid alkali in percentage by mass concentration is added dropwise, the mixture is stirred for 5 hours after the dropwise addition is completed, and no crystal is precipitated.
Stability test:
the crystalline sodium methyldithiocarbamate product obtained in example 2 was stored at room temperature, sampled during storage for stability testing, and tested according to the national agricultural industry standard for the people's republic of China (NY/T1427-2016), and sampled at 3, 6, 12 and 24 months for purity, respectively (test method is the same as in example 1), and the results are shown in the following table.
| Storage time | Purity (%) |
| Initial stage of storage | 96.89 |
| Month 3 | 96.88 |
| Month 6 | 96.88 |
| Month 12 | 95.57 |
| Month 24 | 95.40 |
As can be seen from the table, the crystalline sodium methyldithiocarbamate has good stability under long-term storage conditions.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (1)
1. A method for preparing sodium methyldithiocarbamate crystals, which is characterized in that the sodium methyldithiocarbamate crystals have characteristic peaks at diffraction angles 2θ of 7.922, 15.522,16.080,17.840,19.157,21.621,24.239,24.462,25.160,28.943,29.382,30.622,31.340,32.138,32.499,35.258,36.698,38.677,39.222,39.824,40.887,42.577, 43.842;
the preparation method of the sodium methyldithiocarbamic acid crystal comprises the following steps:
adding a catalyst accounting for 0.1-1% of the weight of monomethylamine into a monomethylamine ethanol solution with the mass percentage concentration of 30-40%, controlling the reaction temperature to be 0-30 ℃, dropwise adding carbon disulfide within 10-24 hours, and stirring for 2-10 hours at 10-30 ℃ after the dropwise adding is finished; wherein, the mol ratio of the monomethylamine to the carbon disulfide is 1-1.05:1; the catalyst is polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400 and polyethylene glycol 600;
controlling the reaction temperature to be-10-10 ℃, dropwise adding 30-40% liquid alkali in percentage by mass, wherein the molar ratio of monomethylamine to liquid alkali is 1:1 to 1.5; stirring for 5-10 hours after the dripping is completed, precipitating crystals, filtering and drying to obtain crystal sodium methyldithiocarbamic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210861271.0A CN115232046B (en) | 2022-07-20 | 2022-07-20 | Crystal sodium methyldithiocarbamic acid and preparation method thereof |
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| US3718467A (en) * | 1971-03-25 | 1973-02-27 | Canon Kk | Positive working photographic process for producing colored images of metal chelates of sulfur compounds |
| JPH0525122A (en) * | 1991-07-17 | 1993-02-02 | Nippon Hidorajin Kogyo Kk | Production of 4-alkyl-3-thiosemicarbazide |
| CN1368005A (en) * | 2002-03-04 | 2002-09-11 | 贾朝钧 | Aminodithioformate-type agricultural chemicals and preparing process thereof |
| CN102267931A (en) * | 2011-07-18 | 2011-12-07 | 利民化工股份有限公司 | Metham production process |
| CN114853651A (en) * | 2022-03-03 | 2022-08-05 | 烟台中科荣达新材料有限公司 | Method for synthesizing liquid sodium N-methyldithiocarbamate by microchannel reactor |
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| US3718467A (en) * | 1971-03-25 | 1973-02-27 | Canon Kk | Positive working photographic process for producing colored images of metal chelates of sulfur compounds |
| JPH0525122A (en) * | 1991-07-17 | 1993-02-02 | Nippon Hidorajin Kogyo Kk | Production of 4-alkyl-3-thiosemicarbazide |
| CN1368005A (en) * | 2002-03-04 | 2002-09-11 | 贾朝钧 | Aminodithioformate-type agricultural chemicals and preparing process thereof |
| CN102267931A (en) * | 2011-07-18 | 2011-12-07 | 利民化工股份有限公司 | Metham production process |
| CN114853651A (en) * | 2022-03-03 | 2022-08-05 | 烟台中科荣达新材料有限公司 | Method for synthesizing liquid sodium N-methyldithiocarbamate by microchannel reactor |
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| 二硫代氨基甲酸盐(酯)的合成方法及应用进展;胡元 等;应用化工;第42卷(第2期);1.1.1 二硫代氨基甲酸盐的合成 * |
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