CN102321890A - Method for preparing thiram by direct-electrochemical-oxidation - Google Patents
Method for preparing thiram by direct-electrochemical-oxidation Download PDFInfo
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- CN102321890A CN102321890A CN201110268550A CN201110268550A CN102321890A CN 102321890 A CN102321890 A CN 102321890A CN 201110268550 A CN201110268550 A CN 201110268550A CN 201110268550 A CN201110268550 A CN 201110268550A CN 102321890 A CN102321890 A CN 102321890A
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229960002447 thiram Drugs 0.000 title claims abstract description 39
- 239000005843 Thiram Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- 239000007864 aqueous solution Substances 0.000 claims abstract description 55
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract 6
- 239000011734 sodium Substances 0.000 claims abstract 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims 2
- 235000019254 sodium formate Nutrition 0.000 claims 2
- 229940008099 dimethicone Drugs 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- -1 dried and crushed Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910001948 sodium oxide Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 27
- 230000003647 oxidation Effects 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 22
- 230000005518 electrochemistry Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 238000010298 pulverizing process Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 208000031968 Cadaver Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
一种直接电化学氧化制备福美双的方法，步骤如下：1）在氢氧化钠水溶液和二甲胺水溶液混合液中，滴加二硫化碳水溶液，静置后制得福美钠水溶液；2）利用带有隔膜的电解槽阳极室对福美钠水溶液进行直接电化学氧化，即将上述制得的福美钠水溶液注入到隔膜电解槽阳极室，将NaOH水溶液注入到隔膜电解槽阴极室，获得阳极产物；3）将上述阳极产物过滤、水洗、烘干、粉碎后，即可制得福美双原粉。本发明的优点是：制备工艺简单、反应条件温和、能耗低、适合规模化生产；产品纯度高、基本无三废，是一种绿色合成工艺；阴极产物是氢氧化钠水溶液和氢气，其中氢氧化钠水溶液可做为原料用于福美钠的合成，在整个生产流程中循环使用，降低了成本。
A method for preparing thiram by direct electrochemical oxidation, the steps are as follows: 1) In the mixed solution of sodium hydroxide aqueous solution and dimethylamine aqueous solution, carbon disulfide aqueous solution is added dropwise, and after standing still, an aqueous solution of sodium thiram is obtained; The anode chamber of the electrolytic cell of the diaphragm directly electrochemically oxidizes the aqueous solution of sodium formamate, that is, injects the aqueous solution of sodium furbamate prepared above into the anode chamber of the diaphragm electrolyzer, and injects the NaOH aqueous solution into the cathode chamber of the diaphragm electrolyzer to obtain the anode product; 3) put After the above-mentioned anode product is filtered, washed with water, dried and crushed, thiram powder can be obtained. The invention has the advantages of simple preparation process, mild reaction conditions, low energy consumption, and is suitable for large-scale production; the product has high purity and basically no three wastes, and is a green synthesis process; the cathode product is sodium hydroxide aqueous solution and hydrogen gas, wherein hydrogen The aqueous solution of sodium oxide can be used as a raw material for the synthesis of sodium formex, and it can be recycled in the whole production process to reduce the cost.
Description
Technical field
The present invention relates to the technology of preparing of vulcanization accelerator and sterilant, particularly a kind of Direct Electrochemistry oxidation prepares the method for thiram.
Background technology
Thiram, chemical name are tetramethyl-thiuram disulfide, molecular formula C
6H
12N
2S
4Be widely used in the thiofide industry.In addition, it still is a kind of protective fungicide, as the control of corps diseases, seed treatment, fields such as soil treating.
At present, the compound method of thiram mainly adopts chemical method, promptly uses oxygenant, and like Sodium Nitrite, chlorine, ydrogen peroxide 50, oxygen etc., the oxidation Sodium Dimethyldithiocarbamate generates thiram.When adopting Sodium Nitrite and chlorine as oxygenant, these two kinds of oxygenants all are converted into other compound and get in waste water and the waste gas after accomplishing oxidation.Not only cause environmental pollution, increased the expense of handling the three wastes, also increased raw material consumption, also bigger to equipment corrosion.When adopting hydrogen peroxide oxidation method, production cost is high, and also higher to equipment requirements.Therefore, the domestic and international for a long time new green production process of active development thiram.Forefathers once adopted pure oxygen to replace chlorine as oxygenant, prepared in reaction thiram under the high pressure.Though this method is environmentally safe almost, need the mode of air separation equipment or employing oxygen bottle.Not only increased facility investment, and security reduces.A kind of preparation method was once disclosed in the patent of CN1370769A.This method still belongs to a kind of of traditional chemical method, is to replace above-mentioned pure oxygen with dry air.Though this method can realize green production, but still adopt catalyzer and organic solvent.Not only cost is higher, and product separating technique is complicated.
Organic electrosynthesis is compared with traditional chemical method, and its essence is to utilize electronics to replace the Oxidizing and Reducing Agents of the higher and easy contaminate environment of price.Electrode reaction is generally carried out under mild conditions, need not add catalyzer, and electrolytic solution can be recycled, thereby has practiced thrift raw material, has reduced cost.In addition, because reactant is single, so product is easy to separate and is refining, product purity is high, by product is few, do not have the three wastes basically, is green industry.
Summary of the invention
The objective of the invention is shortcoming to the traditional chemical oxidation style existence for preparing thiram at present; Provide a kind of Direct Electrochemistry oxidation to prepare the method for thiram; This preparing method's technology is simple, reaction conditions is gentle, cost is low, be fit to large-scale production, is kind of a green synthesis process.
Technical scheme of the present invention:
A kind of Direct Electrochemistry oxidation prepares the method for thiram, and step is following:
1) with after aqueous sodium hydroxide solution and the dimethylamine agueous solution mixing, the speed with 1/2 seconds under 10-20 ℃ of condition slowly drips the dithiocarbonic anhydride aqueous solution, and regulating the pH value is 8-10, and reaction is left standstill 12h after finishing, and makes the Sodium Dimethyldithiocarbamate aqueous solution;
2) utilize and to have membranous electrolyzer anode chamber the Sodium Dimethyldithiocarbamate aqueous solution is carried out the Direct Electrochemistry oxidation, be about to the above-mentioned Sodium Dimethyldithiocarbamate aqueous solution that makes and be injected into the diaphragm sell anolyte compartment, the NaOH aqueous solution is injected into the diaphragm sell cathode compartment, obtain anodic product;
3) above-mentioned anodic product is filtered, after the washing, 60 ℃ of oven dry, pulverizing, can make the former powder of thiram.
The weight percent concentration of said aqueous sodium hydroxide solution is 30%; The weight percent concentration of dimethylamine agueous solution is 40%; The weight percent concentration of the dithiocarbonic anhydride aqueous solution is 98%.
The mol ratio of said sodium hydroxide, n n dimetylaniline and dithiocarbonic anhydride is 1: 1: 1.
The weight percent concentration of the Sodium Dimethyldithiocarbamate aqueous solution of said injection anolyte compartment is 10%-40%; The concentration of injecting the NaOH aqueous solution of cathode compartment is 20g-60gL
-1
Saidly have a processing parameter that membranous electrolyzer carries out the Direct Electrochemistry oxidation: current density is 300-600mAcm
-2, electrolysis temperature is that 30-70 ℃, electrolysis time are 0.5-2 hour.
The present invention with the cleaning electronics as reagent, the anodic oxidation Sodium Dimethyldithiocarbamate obtains thiram.Cathode product is NaOH and H
2, do not pollute the environment, and the NaOH that generates can recycle as reactant.Need not any catalyzer and additive in the whole process of reaction.Its anodic reaction equation is:
Advantage of the present invention is: preparation technology is simple, reaction conditions is gentle, energy consumption is low, be fit to large-scale production; Product purity is high, by product is few, do not have the three wastes basically, is a kind of green synthesis process; Cathode product is the high-concentration sodium hydroxide aqueous solution and hydrogen, and the aqueous sodium hydroxide solution that negative electrode generates can be used for the synthetic of Sodium Dimethyldithiocarbamate as raw material, in the whole production flow process, can be recycled, and has reduced cost.
Description of drawings
Fig. 1 is the infrared FTIR spectrogram of thiram Fourier.
Fig. 2 is a thiram performance liquid HPLC color atlas.
Embodiment
Below in conjunction with specific examples the present invention is further specified.What following examples were used is that oneself makes simple and easy H type diaphragm sell.Anode adopts the Pt electrode, and negative electrode adopts stainless steel substrates, and barrier film adopts Nafion400.
Embodiment 1:
A kind of Direct Electrochemistry oxidation prepares the method for thiram, and step is following:
1) be that 30% aqueous sodium hydroxide solution and weight percent concentration are after 40% dimethylamine agueous solution mixes with weight percent concentration; Under 10 ℃ of conditions, slowly dripping weight percent concentration with 1/2 seconds speed is the 98% dithiocarbonic anhydride aqueous solution; The mol ratio of sodium hydroxide, n n dimetylaniline and dithiocarbonic anhydride is 1: 1: 1; Regulating the pH value is 8, fully leaves standstill 12h after the reaction, makes the Sodium Dimethyldithiocarbamate aqueous solution;
2) utilize H type diaphragm sell anolyte compartment that the Sodium Dimethyldithiocarbamate aqueous solution is carried out the Direct Electrochemistry oxidation; Be about to the above-mentioned Sodium Dimethyldithiocarbamate aqueous solution that makes and be injected into the diaphragm sell anolyte compartment; Add zero(ppm) water, the weight percent concentration that makes the Sodium Dimethyldithiocarbamate anolyte is 20%, is 30gL with concentration
-1The NaOH aqueous solution be injected into the diaphragm sell cathode compartment, the processing parameter that H type diaphragm sell carries out the Direct Electrochemistry oxidation: current density is 600mAcm
-2, electrolysis temperature is that 60 ℃, electrolysis time are 0.5 hour, groove is pressed and is substantially constant at 3.8V in electrolytic process, obtains anodic product;
3) above-mentioned anodic product is filtered, after the washing, 60 ℃ of oven dry, pulverizing, can make the former powder of thiram.
Fig. 1 and Fig. 2 are respectively the FTIR spectrogram and the HPLC spectrogram of purity 98% thiram standard specimen and this law synthetic thiram sample.Visible by two figure, the sample infrared spectrum of this law preparation conforms to standard sample spectrum, and the sample RT is consistent with standard specimen also, can assert that the synthetic product really is a thiram.Through measuring, this law synthetic product purity reaches 98.1%, 143.5 ℃ of fusing points, and current efficiency reaches 76%.
Embodiment 2:
1) be that 30% aqueous sodium hydroxide solution and weight percent concentration are after 40% dimethylamine agueous solution mixes with weight percent concentration; Under 20 ℃ of conditions, slowly dripping weight percent concentration with 1/2 seconds speed is the 98% dithiocarbonic anhydride aqueous solution; The mol ratio of sodium hydroxide, n n dimetylaniline and dithiocarbonic anhydride is 1: 1: 1; Regulating the pH value is 10, fully leaves standstill 12h after the reaction, makes the Sodium Dimethyldithiocarbamate aqueous solution;
2) utilize H type diaphragm sell anolyte compartment that the Sodium Dimethyldithiocarbamate aqueous solution is carried out the Direct Electrochemistry oxidation; Be about to the above-mentioned Sodium Dimethyldithiocarbamate aqueous solution that makes and be injected into the diaphragm sell anolyte compartment; Add zero(ppm) water, the weight percent concentration that makes the Sodium Dimethyldithiocarbamate anolyte is 40%, is 20gL with concentration
-1The NaOH aqueous solution be injected into the diaphragm sell cathode compartment, the processing parameter that H type diaphragm sell carries out the Direct Electrochemistry oxidation: current density is 400mAcm
-2, electrolysis temperature is that 50 ℃, electrolysis time are 1.5 hours, groove is pressed and is substantially constant at 3.6V in electrolytic process, obtains anodic product;
3) above-mentioned anodic product is filtered, after the washing, 60 ℃ of oven dry, pulverizing, can make the former powder of thiram.
The sample infrared spectrum of present embodiment preparation is identical with Fig. 1 and Fig. 2 respectively with RT, can assert that the synthetic product really is thiram.Through measuring, this law synthetic product purity reaches 99.2%, 144.5 ℃ of fusing points, and current efficiency reaches 78%.
Embodiment 3:
1) be that 30% aqueous sodium hydroxide solution and weight percent concentration are after 40% dimethylamine agueous solution mixes with weight percent concentration; Under 15 ℃ of conditions, slowly dripping weight percent concentration with 1/2 seconds speed is the 98% dithiocarbonic anhydride aqueous solution; The mol ratio of sodium hydroxide, n n dimetylaniline and dithiocarbonic anhydride is 1: 1: 1; Regulating the pH value is 9, fully leaves standstill 12h after the reaction, makes the Sodium Dimethyldithiocarbamate aqueous solution;
2) utilize H type diaphragm sell anolyte compartment that the Sodium Dimethyldithiocarbamate aqueous solution is carried out the Direct Electrochemistry oxidation; Be about to the above-mentioned Sodium Dimethyldithiocarbamate aqueous solution that makes and be injected into the diaphragm sell anolyte compartment; Add zero(ppm) water, the weight percent concentration that makes the Sodium Dimethyldithiocarbamate anolyte is 30%, is 60gL with concentration
-1The NaOH aqueous solution be injected into the diaphragm sell cathode compartment, the processing parameter that H type diaphragm sell carries out the Direct Electrochemistry oxidation: current density is 300mAcm
-2, electrolysis temperature is that 40 ℃, electrolysis time are 2 hours, groove is pressed and is substantially constant at 3.3V in electrolytic process, obtains anodic product;
3) above-mentioned anodic product is filtered, after the washing, 60 ℃ of oven dry, pulverizing, can make the former powder of thiram.
The sample infrared spectrum of present embodiment preparation is identical with Fig. 1 and Fig. 2 respectively with RT, can assert that the synthetic product really is thiram.Through measuring, this law synthetic product purity reaches 98.4%, 144.2 ℃ of fusing points, and current efficiency reaches 75%.
Embodiment 4:
1) be that 30% aqueous sodium hydroxide solution and weight percent concentration are after 40% dimethylamine agueous solution mixes with weight percent concentration; Under 18 ℃ of conditions, slowly dripping weight percent concentration with 1/2 seconds speed is the 98% dithiocarbonic anhydride aqueous solution; The mol ratio of sodium hydroxide, n n dimetylaniline and dithiocarbonic anhydride is 1: 1: 1; Regulating the pH value is 9, fully leaves standstill 12h after the reaction, makes the Sodium Dimethyldithiocarbamate aqueous solution;
2) utilize H type diaphragm sell anolyte compartment that the Sodium Dimethyldithiocarbamate aqueous solution is carried out the Direct Electrochemistry oxidation; Be about to the above-mentioned Sodium Dimethyldithiocarbamate aqueous solution that makes and be injected into the diaphragm sell anolyte compartment; Add zero(ppm) water, the weight percent concentration that makes the Sodium Dimethyldithiocarbamate anolyte is 10%, is 40gL with concentration
-1The NaOH aqueous solution be injected into the diaphragm sell cathode compartment, the processing parameter that H type diaphragm sell carries out the Direct Electrochemistry oxidation: current density is 500mAcm
-2, electrolysis temperature is that 70 ℃, electrolysis time are 1 hour, groove is pressed and is substantially constant at 3.7V in electrolytic process, obtains anodic product;
3) above-mentioned anodic product is filtered, after the washing, 60 ℃ of oven dry, pulverizing, can make the former powder of thiram.
The sample infrared spectrum of present embodiment preparation is identical with Fig. 1 and Fig. 2 respectively with RT, can assert that the synthetic product really is thiram.Through measuring, this law synthetic product purity reaches 98.8%, 143.2 ℃ of fusing points, and current efficiency reaches 76%.
Embodiment 5:
1) be that 30% aqueous sodium hydroxide solution and weight percent concentration are after 40% dimethylamine agueous solution mixes with weight percent concentration; Under 15 ℃ of conditions, slowly dripping weight percent concentration with 1/2 seconds speed is the 98% dithiocarbonic anhydride aqueous solution; The mol ratio of sodium hydroxide, n n dimetylaniline and dithiocarbonic anhydride is 1: 1: 1; Regulating the pH value is 10, fully leaves standstill 12h after the reaction, makes the Sodium Dimethyldithiocarbamate aqueous solution;
2) utilize H type diaphragm sell anolyte compartment that the Sodium Dimethyldithiocarbamate aqueous solution is carried out the Direct Electrochemistry oxidation; Be about to the above-mentioned Sodium Dimethyldithiocarbamate aqueous solution that makes and be injected into the diaphragm sell anolyte compartment; Add zero(ppm) water, the weight percent concentration that makes the Sodium Dimethyldithiocarbamate anolyte is 30%, is 50gL with concentration
-1The NaOH aqueous solution be injected into the diaphragm sell cathode compartment, the processing parameter that H type diaphragm sell carries out the Direct Electrochemistry oxidation: current density is 400mAcm
-2, electrolysis temperature is that 30 ℃, electrolysis time are 1.8 hours, groove is pressed and is substantially constant at 3.8V in electrolytic process, obtains anodic product;
3) above-mentioned anodic product is filtered, after the washing, 60 ℃ of oven dry, pulverizing, can make the former powder of thiram.
The sample infrared spectrum of present embodiment preparation is identical with Fig. 1 and Fig. 2 respectively with RT, can assert that the synthetic product really is thiram.Through measuring, this law synthetic product purity reaches 98.5%, 142.8 ℃ of fusing points, and current efficiency reaches 75%.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819375A (en) * | 2014-01-21 | 2014-05-28 | 青岛惠国新材料科技有限公司 | Synthetic method of high-purity solid sodium dimethyl dithiocarbamate |
| CN106139812A (en) * | 2015-04-20 | 2016-11-23 | 兰州信元新型材料有限责任公司 | Carbon disulfide Special desulfurizing agent and preparation method thereof |
| CN109518212A (en) * | 2018-11-21 | 2019-03-26 | 新乡市润宇新材料科技有限公司 | A kind of method of disulfide of the electrochemistry formated with S -- S |
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2011
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|---|---|---|---|---|
| US2385410A (en) * | 1941-07-21 | 1945-09-25 | Monsanto Chemicals | Production of organic disulphides |
| US4032416A (en) * | 1976-03-10 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Electrolytic oxidation process |
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| Title |
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