CN115232046A - Crystalline sodium methyldithiocarbamate and preparation method thereof - Google Patents
Crystalline sodium methyldithiocarbamate and preparation method thereof Download PDFInfo
- Publication number
- CN115232046A CN115232046A CN202210861271.0A CN202210861271A CN115232046A CN 115232046 A CN115232046 A CN 115232046A CN 202210861271 A CN202210861271 A CN 202210861271A CN 115232046 A CN115232046 A CN 115232046A
- Authority
- CN
- China
- Prior art keywords
- dropwise adding
- hours
- sodium methyldithiocarbamate
- monomethylamine
- methyldithiocarbamate
- 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.)
- Granted
Links
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical compound [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 title claims abstract description 46
- 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 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- UESSEMPSSAXQJC-UHFFFAOYSA-N ethanol;methanamine Chemical compound NC.CCO UESSEMPSSAXQJC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000001228 spectrum Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 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
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 19
- LGDSHSYDSCRFAB-UHFFFAOYSA-N Methyl isothiocyanate Chemical compound CN=C=S LGDSHSYDSCRFAB-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- HYVVJDQGXFXBRZ-UHFFFAOYSA-N metam Chemical compound CNC(S)=S HYVVJDQGXFXBRZ-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 239000002689 soil Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BIHPYCDDPGNWQO-UHFFFAOYSA-N 5-iai Chemical compound C1=C(I)C=C2CC(N)CC2=C1 BIHPYCDDPGNWQO-UHFFFAOYSA-N 0.000 description 5
- 239000012990 dithiocarbamate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002169 Metam Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000000575 pesticide 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 238000003958 fumigation Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing 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
- 241000607479 Yersinia pestis Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects 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
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000006283 soil fumigant Substances 0.000 description 2
- 238000012430 stability testing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 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
- 241000243785 Meloidogyne javanica Species 0.000 description 1
- 229920002472 Starch Polymers 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
- 239000002585 base Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 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
- 230000003472 neutralizing effect Effects 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
- 230000002265 prevention Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- -1 sodium (potassium) dithiocarbamate Chemical compound 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
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 a crystal sodium methyldithiocarbamate and a preparation method thereof. The XRD spectrum of the sodium methyldithiocarbamate has characteristic peaks at positions with diffraction angles 2 theta 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 and 43.842. The preparation method comprises the following steps: adding a catalyst which is 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, stirring for 2-10 hours at 10-30 ℃ after 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 dropwise adding, separating out crystals, filtering, and drying to obtain the 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, tradename metam. Metham sodium is a biocidal soil treatment agent, the chemical name of the metham sodium dithiocarbamate is sodium methyldithiocarbamate, the metham sodium dithiocarbamate is easily soluble in water and insoluble in most organic solvents, a concentrated solution is relatively stable, and the metham sodium dithiocarbamate is easily decomposed to release methyl isothiocyanate after being diluted to play a role in fumigation. At present, the application modes of metham are mainly injection, furrow application, irrigation, drip irrigation and the like. After entering soil, metham liquid medicine rapidly reacts with water to generate methyl isothiocyanate and hydrogen sulfide gas. (Zhao Wen et al, degradation characteristics of metham and methyl isothiocyanate in soil under laboratory conditions, proc. Agreement 2013, 15 (5): 567-573).
Metham has been used as a low-toxicity and high-efficiency soil fumigant for more than 50 years, klopping reports the bactericidal activity of metham in 1951, stauffer chemical company in the United states in 1955 firstly launches industrial products, and then metham is widely popularized and applied, the use amount of metham in the United states, western Europe and other countries with higher agricultural mechanization degree is continuously increased, and the use amount reaches 1.32 ten thousand tons per year in the United states only by 90 years in the 20 th century. For more than 50 years, metham sodium is widely applied due to wide prevention and control spectrum, good effect and low price, and is registered and used in nearly 20 countries in the world successively. In 2002, metham starts to be registered and used in China, but the metham is not widely popularized and applied due to the influence of low degree of agricultural mechanization in China. Metam is stable in concentrated aqueous solutions and unstable in dilute aqueous solutions. The metham liquor is chemically changed after contacting with water in soil, so that methyl isothiocyanate is decomposed, is an effective component which actually plays a role in fumigation, can effectively kill harmful microorganisms such as fungi and bacteria in the soil under a proper soil environment condition, has a good control effect on nematodes and underground pests, can kill field weed seeds, plays a role in weeding, is completely degraded, cannot generate adverse effects on crops, and does not have any residue in the crops and fruits.
CN1368005 discloses a pesticide of aminodithioformate and its preparation method, the effective component of said pesticide is up to general formula
In the formula: r is methylamine, dimethylamine, trimethylamine or ethylamine; m is metal K, na, zn, or Cu; the dithiocarbamate with n =1,2 is prepared by firstly reacting carbon disulfide with organic amine in a water medium, then adding sodium (potassium) alkali liquor to neutralize to generate sodium (potassium) dithiocarbamate, and reacting for 2-3 hours under heat preservation to prepare a liquid product; copper (zinc) salts can also be produced by metathesis reactions.
The patent CN102267931A discloses a metham production process, which is characterized in that 1-1.2 parts by weight of monomethylamine solution and 0.9-1.0 part by weight of carbon disulfide are mixed and react at 10-30 ℃ for 2-3 hours to obtain N-methyldithiocarbamic acid, then 2.0-2.2 parts by weight of sodium hydroxide solution is dripped to react at 35-60 ℃ for 2 hours, the pH value of the solution is 6-10, and after the reaction is finished, negative pressure dehydration, cooling, suction filtration and drying are carried out to obtain metham. The post-treatment of the method needs to be carried out by dehydration, cooling, suction filtration and drying to obtain metham, the dehydration energy consumption is large, and the gas volatilization and danger are large when the methylamine and the carbon disulfide are not completely reacted during vacuum dehydration.
The chemical reaction formula is as follows (two steps):
the metham synthesis process has long production time and low production efficiency, and the intermediate (n-methyldithiocarbamic acid) in the first step is easily decomposed into methyl isothiocyanate and hydrogen sulfide in the production process, so that the content of the product is reduced, and the storage stability of the product is influenced by the generation of byproducts. On the other hand, with the production of the reaction n-methyldithiocarbamic acid, the pH value of the reaction environment is gradually reduced, the reaction speed of the monomethylamine and the carbon disulfide is slowed down, excessive carbon disulfide begins to exist in the reaction system, and the carbon disulfide is easy to escape, so that the yield is reduced, the environment is polluted, and explosion or fire is possibly caused.
The patent CN 1118478A discloses a method for synthesizing a soil fumigant metam, which comprises the steps of stirring and mixing water, a monomethylamine aqueous solution and a sodium hydroxide aqueous solution, dropwise adding carbon disulfide, continuously stirring and reacting, and directly obtaining a metam finished product with yellow to reddish brown appearance 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 methyldithiocarbamate aqueous solution, and the sodium methyldithiocarbamate aqueous solution is widely applied in the field of pesticides. However, the aqueous solution of sodium methyldithiocarbamate had very poor storage stability (Wangshan, storage stability study of 4 dithiocarbamate fungicides in 6 fruit and vegetable samples, hunan agricultural university, master's academic thesis). The carbon disulfide is easy to decompose after being placed in a high-temperature environment for a long time or in the field, and the carbon disulfide is easy to escape, so that the environmental pollution is caused, and explosion or fire can be caused.
Disclosure of Invention
The invention aims to provide a crystal sodium methyldithiocarbamate, which has an XRD spectrum 2 theta with a series of characteristic peaks at 7.9, 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 and 43.842.
The preparation method comprises the following steps: adding a catalyst which is 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 dropwise adding;
controlling the reaction temperature to be minus 10-10 ℃, dropwise adding liquid caustic soda with the mass percentage concentration of 30-40%, stirring for 5-10 hours after dropwise adding is finished, separating out crystals, filtering and drying to obtain the crystal sodium methyldithiocarbamate.
As a preferred embodiment of the invention, the molar ratio of monomethylamine to carbon disulphide is from 1 to 1.05:1.
In a preferred embodiment of the invention, the molar ratio of monomethylamine to liquid base is 1:1 to 1.5.
As a preferable scheme of the invention, the catalyst is polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400 or polyethylene glycol 600.
The invention solves the defect that the sodium methyldithiocarbamate aqueous solution is unstable under the conditions of high temperature, high humidity and long-time storage, directly prepares the crystal sodium methyldithiocarbamate, 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 put forth so as to provide those of ordinary skill in the art with a view to making and evaluating the present invention, and are intended to be merely exemplary of the present disclosure and are not intended to limit the scope thereof. 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 degrees celsius or at ambient temperature and pressure is at or near atmospheric pressure. Detailed description of the preferred embodiment 1
Adding 1000 kg of 30% methylamine ethanol solution into a 5-cubic 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 dropwise adding, controlling the reaction temperature to be minus 10 ℃, dropwise adding 1290 kg of liquid alkali with the mass percentage concentration of 30%, stirring for 5 hours after 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 pattern is shown in figure 1, and the XRD pattern 2 theta thereof has a series of characteristic peaks at the positions 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, 3.340, 32.138,32.499,35.258,36.698,38.677,39.222,39.824,40.887,42.577 and 43.842. The infrared spectrum of the obtained crystalline sodium methyldithiocarbamate is shown in FIG. 2.
Weighing 0.3g of the prepared sample of the crystalline sodium methyldithiocarbamate (accurate to 0.0002 g) into a clean round-bottom flask, putting 50mL of zinc acetate solution with the mass percent concentration of 6% into a first absorption tube, adding 50mL of potassium hydroxide-methanol solution into a second absorption tube, connecting a decomposition absorption device, and checking the tightness of the device. The cooling water is opened, the air suction source is started, the air suction speed is controlled, and 2-6 bubbles per second uniformly and stably pass through the absorption tube. 50mL of 3% sulfuric acid solution was added to the round bottom flask via a long-necked funnel, and shaken well. And simultaneously, heating quickly, carefully controlling to prevent the reaction liquid from rushing out, keeping micro-boiling for 50min, disassembling the device, stopping heating, taking down a second absorption tube, washing the content into a 500mL triangular flask by using 200mL of water, checking the absorption tube by using phenolphthalein indicator liquid, washing until no residue is left in the tube, neutralizing by using 36% acetic acid solution until phenolphthalein fades, immediately titrating by using iodine standard titration solution, continuously shaking, adding 5mL of starch indicator liquid when the endpoint is reached, continuously titrating by using the iodine standard titration solution until light grey purple is the endpoint, simultaneously performing blank determination, and finally calculating to obtain the purity of 95.23%.
Specific example 2
Adding 1000 kg of 40% methylamine ethanol solution into a 5-cubic stainless steel reaction kettle, adding 3 kg of polyethylene glycol 300, controlling the reaction temperature to be 30 ℃, dropwise adding 934 kg of carbon disulfide within 24 hours, stirring at 30 ℃ for 10 hours after dropwise adding, controlling the reaction temperature to be 10 ℃, dropwise adding 1290 kg of liquid alkali with the mass percentage concentration of 40%, stirring for 10 hours after dropwise adding, separating out a large amount of light yellow crystals, filtering and drying to obtain 1100 kg of crystalline sodium methyldithiocarbamate with the purity of 96.89% (the test method is the same as that in example 1).
Specific example 3
Adding 1000 kg of 30% methylamine ethanol solution into a 5-cubic stainless steel reaction kettle, adding 1 kg of polyethylene glycol 400, controlling the reaction temperature to be 5 ℃, dropwise adding 735 kg of carbon disulfide within 12 hours, stirring at 20 ℃ for 2 hours after dropwise adding, controlling the reaction temperature to be 0 ℃, dropwise adding 1290 kg of liquid alkali with the mass percentage concentration of 30%, stirring for 8 hours after dropwise adding, precipitating a large amount of light yellow crystals, filtering and drying to obtain 1100 kg of crystalline sodium methyldithiocarbamate with the purity of 95.71% (the test method is the same as that in example 1).
Specific example 4
Adding 1000 kg of 40% methylamine ethanol solution into a 5-cubic stainless steel reaction kettle, adding 2 kg of polyethylene glycol 600, controlling the reaction temperature to be 0 ℃, dropwise adding 935 kg of carbon disulfide within 24 hours, stirring at 30 ℃ for 10 hours after dropwise adding, controlling the reaction temperature to be minus 10 ℃, dropwise adding 1200 kg of liquid alkali with the mass percentage concentration of 40%, stirring for 10 hours after dropwise adding, separating out a large amount of light yellow crystals, filtering, drying, and obtaining 1058 kg of crystalline sodium methyldithiocarbamate with the purity of 96.11% (the test method is the same as that in example 1).
Comparative example 1
100 g of 40 mass percent aqueous solution of monomethylamine and 100 g of carbon disulfide are added into a 500ml three-neck flask to be mixed and reacted to generate N-methyldithiocarbamic acid, the reaction temperature is 20 ℃, the reaction time is 3 hours, 210 g of 30 mass percent sodium hydroxide solution is dripped 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 crystal was precipitated.
Comparative example 2
100 g of 30% methylamine water solution is added into a 500ml three-neck flask, the reaction temperature is controlled to be 0 ℃, 73 g of carbon disulfide is dripped in 10 hours, the mixture is stirred for 2 hours at 10 ℃ after the dripping is finished, the reaction temperature is controlled to be minus 10 ℃, 129 g of liquid caustic soda with the mass percentage concentration of 30% is dripped, and the mixture is stirred for 5 hours after the dripping is finished, so that no crystal is separated out.
And (3) stability testing:
the crystalline sodium methyldithiocarbamate product obtained in example 2 was stored at room temperature, and samples were taken during storage to perform stability testing, the testing was performed according to the agricultural industry standard (NY/T1427-2016) of the people's republic of china, and samples were taken at 3 rd, 6 th, 12 th and 24 th months to test the purity (the testing method was the same as in example 1), and the results are shown in the following table.
| Storage time | Purity (%) |
| Initial storage | 96.89 |
| Month 3 | 96.88 |
| Month 6 | 96.88 |
| |
95.57 |
| Month 24 | 95.40 |
As can be seen from the table, crystalline sodium methyldithiocarbamate is stable under long-term storage conditions.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit of the invention, and these are within the scope of the invention.
Claims (5)
1. A sodium methyldithiocarbamate crystal characterized by an XRD spectrum having characteristic peaks at diffraction angles 2 theta 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.
2. A method for preparing sodium methyldithiocarbamate crystals as set forth in claim 1, which comprises the steps of:
adding a catalyst which accounts 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 dropwise adding;
controlling the reaction temperature to be minus 10-10 ℃, dropwise adding liquid caustic soda with the mass percentage concentration of 30-40%, stirring for 5-10 hours after dropwise adding is finished, separating out crystals, filtering and drying to obtain the crystal sodium methyldithiocarbamate.
3. The process for the preparation of sodium methyldithiocarbamate according to claim 2, wherein the molar ratio of monomethylamine to carbon disulfide is from 1 to 1.05.
4. The method for preparing sodium methyldithiocarbamate according to claim 2, wherein the catalyst is selected from the group consisting of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, and polyethylene glycol 600.
5. The process for the preparation of sodium methyldithiocarbamate according to claim 2, wherein the molar ratio of monomethylamine to liquid base is 1:1-1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210861271.0A CN115232046B (en) | 2022-07-20 | 2022-07-20 | Crystal sodium methyldithiocarbamic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210861271.0A CN115232046B (en) | 2022-07-20 | 2022-07-20 | Crystal sodium methyldithiocarbamic acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115232046A true CN115232046A (en) | 2022-10-25 |
| CN115232046B CN115232046B (en) | 2024-02-09 |
Family
ID=83674965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210861271.0A Active CN115232046B (en) | 2022-07-20 | 2022-07-20 | Crystal sodium methyldithiocarbamic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115232046B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2022
- 2022-07-20 CN CN202210861271.0A patent/CN115232046B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 胡元 等: "二硫代氨基甲酸盐(酯)的合成方法及应用进展", 应用化工, vol. 42, no. 2, pages 1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115232046B (en) | 2024-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Engst et al. | Residues of dithiocarbamate fungicides and their metabolites on plant foods | |
| DE2806097A1 (en) | AGROCHEMICAL AGENTS AND THEIR USE | |
| US2019121A (en) | Nitrogen insecticide and method of using same | |
| CN114853651B (en) | Method for synthesizing liquid sodium N-methyldithiocarbamate by micro-channel reactor | |
| CN115232046B (en) | Crystal sodium methyldithiocarbamic acid and preparation method thereof | |
| CN113200871B (en) | P-alkane-1-yl secondary amine compound, preparation method and weeding application thereof | |
| Goldsworthy et al. | FUNGICIDAL AND PHYTOCIDAL PROPERTIES OF SOME METAL DIALKYL DITHIOCARBAMATES ¹ | |
| CN112250478B (en) | Full-water-soluble titanium fertilizer and preparation method thereof | |
| CN106219613A (en) | The production technology of ferrous disulfide | |
| CN106518725B (en) | A kind of 1,8- is to two Schiff base derivatives of Meng's alkane and the preparation method and application thereof | |
| Ramos et al. | Preparation, characterization and thermal decomposition of sodium and potassium salts of dithiocarbamate | |
| CN108997181B (en) | Prosulfocarb and synthesis method thereof | |
| EP3358955A1 (en) | Managing ethylene in plants using a synergistic agricultural formula comprising diacyl or diary urea and at least one metal complex | |
| CN111848478A (en) | Method for synthesizing metham in one step | |
| CN113683529B (en) | Tetrahydrolinalyl Schiff base compound and preparation method and weeding application thereof | |
| CN105777647A (en) | Method for synthesizing 1-isopropyl benzamide-3-(3,5-dichlorophenyl)hydantoin | |
| CN1147233C (en) | Aminodithioformate-type agricultural chemicals and preparing process thereof | |
| CN106986673B (en) | Method for preparing ceramsite and nutrient solution for soilless culture by using livestock and poultry manure | |
| CN106070208B (en) | A kind of application of 3,5- dinitros guaiacol salt plant growth regulator | |
| CN100361575C (en) | Plant growth regulator and it preparing method | |
| CN103694129B (en) | Beet alkaline plant growth regulator containing cinnamamide groups | |
| CN115043737B (en) | Tetrahydrolinalool secondary amine compound, preparation method and weeding application thereof | |
| CN1253933A (en) | Plant exroot nutrition spray fertilizer and its application | |
| KR20170011771A (en) | Sulphur production process for an aqueous solution of potassium hydroxide component is mixed debugging | |
| Mangalagiu et al. | Effect of some new monoquaternary salts of pyridazine on germination and seedling growth of wheat |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |