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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- sodium dimethyldithiocarbamate
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Abstract
The invention relates to a method for preparing thiram by direct-electrochemical-oxidation. The method comprises the following steps: 1) adding a carbon disulfide aqueous solution drop by drop in a mixture of a sodium hydroxide aqueous solution and a dimethylamine aqueous solution, standing to prepare a sodium dimethyldithiocarbamate aqueous solution; 2) performing the direct-electrochemical-oxidation to the sodium dimethyldithiocarbamate aqueous solution by using an anode chamber of an electrolytic tank with diaphragm, namely injecting the prepared sodium dimethyldithiocarbamate aqueous solution into the anode chamber of the electrolytic tank with diaphragm, injecting a NaOH aqueous solution into a cathode chamber of the electrolytic tank with diaphragm to obtain an anode product; 3) filtering, washing and drying the anode product, crushing to obtain the thiram raw powder. The invention has the advantages of simple preparation technology, mild reaction condition and low energy consumption, and is suitable for large scale production; the product has high purity and no three wastes which uses a green synthetic technology; a cathode product is the sodium hydroxide aqueous solution and hydrogen, wherein the sodium hydroxide aqueous solution can be taken as a raw material for synthesizing the sodium dimethyldithiocarbamate, and the sodium dimethyldithiocarbamate can be circularly used in the whole production flow which reduces 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)
1. a Direct Electrochemistry oxidation prepares the method for thiram, it is characterized in that 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, 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.
2. said Direct Electrochemistry oxidation prepares the method for thiram according to claim 1, and it is characterized in that: 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%.
3. said Direct Electrochemistry oxidation prepares the method for thiram according to claim 1, and it is characterized in that: the mol ratio of said sodium hydroxide, n n dimetylaniline and dithiocarbonic anhydride is 1:1:1.
4. said Direct Electrochemistry oxidation prepares the method for thiram according to claim 1, and it is characterized in that: 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
5. said Direct Electrochemistry oxidation prepares the method for thiram according to claim 1, it is characterized in that: 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.
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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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Cited By (8)
| 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 |
| CN105566188A (en) * | 2014-01-21 | 2016-05-11 | 泰山医学院 | Solid SDD (Sodium Dimethyl Dithiocarbamate) synthetic technology with short drying time |
| CN105566189A (en) * | 2014-01-21 | 2016-05-11 | 泰山医学院 | Production process of low-impurity solid sodium dimethyldithiocarbamate |
| CN105693580A (en) * | 2014-01-21 | 2016-06-22 | 青岛中科荣达新材料有限公司 | Production method for solid sodium dimethyl dithiocarbamate with purity of 99% or higher |
| CN105566188B (en) * | 2014-01-21 | 2017-11-17 | 泰山医学院 | A kind of short solid Sodium Dimethyldithiocarbamate synthesis technique of drying time |
| CN105693580B (en) * | 2014-01-21 | 2018-01-30 | 青岛中科荣达新材料有限公司 | A kind of production method of the solid Sodium Dimethyldithiocarbamate of purity more than 99% |
| 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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