CN113264860A - Synthesis and purification method of O-isopropyl-N, N' -di-N-propyl thiocarbamate - Google Patents
Synthesis and purification method of O-isopropyl-N, N' -di-N-propyl thiocarbamate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims description 21
- 238000003786 synthesis reaction Methods 0.000 title claims description 21
- 238000000746 purification Methods 0.000 title description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical compound [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 claims abstract description 35
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000005481 NMR spectroscopy Methods 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 238000004817 gas chromatography Methods 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 15
- 238000005188 flotation Methods 0.000 abstract description 8
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052951 chalcopyrite Inorganic materials 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 54
- 230000035484 reaction time Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GFJMOZYIDADKLJ-UHFFFAOYSA-N 5-bromo-2-chloro-3-methoxypyridine Chemical compound COC1=CC(Br)=CN=C1Cl GFJMOZYIDADKLJ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012991 xanthate 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
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
- C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/12—Dithiocarbonic acids; Derivatives thereof
- C07C329/14—Esters of dithiocarbonic acids
- C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
Abstract
The invention relates to a synthesis method of O-isopropyl-N, N' -di-N-propyl thiocarbamate, which comprises the following steps: step 1, adding sodium chloroacetate as a raw material into sodium isopropyl xanthate to perform a reduction reaction to generate an intermediate sodium isopropyl xanthate; step 2, di-N-propylamine is added into the reactant in the step 1, and ammonolysis reaction is carried out on the di-N-propylamine and the intermediate sodium isopropyl xanthate generated by the reaction in the step 1, so that the target product O-isopropyl-N, N' -di-N-propyl thiocarbamate is synthesized by using an acetate chlorination method. And simultaneously, acidifying and purifying the synthesized product by adopting an acid solution to obtain a product with higher purity. The invention provides a method for synthesizing and purifying a novel thiourethane collecting agent, and also provides a novel collecting agent, which greatly improves the collecting capacity on the basis of ensuring excellent selectivity, and has excellent flotation separation efficiency on chalcopyrite.
Description
Technical Field
The invention relates to the field of collectors in the field of mineral separation, in particular to a synthetic method and a purification method of O-isopropyl-N, N' -di-N-propyl thiocarbamate in the collectors.
Background
Along with the continuous exploitation of mineral products, the quantity of refractory copper sulfide ores is increased gradually. In order to improve the copper-sulfur flotation separation efficiency, the research and development of the high-efficiency copper-sulfur separation collecting agent is an important research direction.
Currently, collectors in this field have the following problems: the most common collecting agents are xanthates which are generally ethyl xanthate, butyl xanthate, amyl xanthate and the like, and the collecting agents are strong in collecting capacity and poor in selectivity. The currently used thiourethane collector Z-200 (O-isopropyl-N-ethyl thiourethane) has better selectivity, but relatively weaker collecting capability. Therefore, on the basis of ensuring the excellent selectivity of the collecting agent, the problem of improving the collecting capacity of the thiourethane collecting agent to the chalcopyrite is brought forward, and the problem becomes a hotspot of research.
Researches find that the collecting capacity of thiourethane is enhanced by increasing the number of hydrocarbon groups connected with N atoms in thiourethane molecules or increasing the length of carbon chains. The thiourethane molecules with long carbon chains are difficult to synthesize and have low purity. If a simple and effective method can be utilized to synthesize the thiourethane molecules with long carbon chains and improve the purity of the thiourethane product, the method has great practical significance for mineral flotation production practice.
Disclosure of Invention
The invention designs a method for synthesizing and purifying O-isopropyl-N, N' -di-N-propyl thiocarbamate, which solves the technical problems that: (1) a method for the synthesis and purification of a novel thiourethane collector is provided. (2) The novel collector is provided, the collecting capacity of the novel collector is greatly improved on the basis of ensuring excellent selectivity, and the novel collector has excellent flotation separation efficiency on chalcopyrite.
In order to solve the technical problems, the invention adopts the following scheme:
a method for synthesizing O-isopropyl-N, N' -di-N-propylthiocarbamate, comprising the steps of:
step 1, sodium chloroacetate reduction reaction: sodium chloroacetate is taken as a raw material, sodium isopropyl xanthate is added, and reduction reaction is carried out to generate an intermediate sodium isopropyl xanthate;
step 2, synthesizing a target product through ammonolysis reaction: adding di-N-propylamine into the reactant in the step 1, and carrying out ammonolysis reaction with the intermediate sodium isopropyl xanthate generated by the reaction in the step 1 to synthesize a target product O-isopropyl-N, N' -di-N-propyl thiocarbamate by using an acetate chlorination method;
the reaction equations of step 1 and step 2 are as follows:
further, the specific operation steps of step 1 and step 2 are as follows:
(1) taking a 100ml three-neck flask, adding 0.05-0.075mol of sodium isopropyl xanthate and 0.025ml-0.05mol of sodium chloroacetate, adding 30ml-60ml of tap water for dissolving, installing a stirring device, and inserting a thermometer into the flask;
(2) adjusting the pH value of the reaction system obtained in the step (1), starting a stirring device, starting a water bath heating device, controlling the temperature of the reaction system to be 35-55 ℃, and stirring for 2 hours;
(3) stopping heating after the stirring time is up, reducing the temperature of the reaction system to 25 ℃, adding 0.025mol-0.05mol of di-n-propylamine into the three-neck flask by using a constant-pressure dropping funnel, continuing heating in a water bath for reaction, keeping the temperature of the reaction system at 30-80 ℃, and stirring for 2-7 h;
(4) after the reaction in the step (3) is finished, pouring a product obtained by the reaction into a separating funnel, standing the mixture in the separating funnel, separating the mixture, collecting the product, weighing the product, and calculating the yield;
(5) and (4) measuring the content of the product obtained in the step (4) by using a gas chromatograph, and determining the structure of the product by using Nuclear Magnetic Resonance (NMR).
Further, the molar ratio of the raw materials sodium chloroacetate, sodium isopropyl xanthate and di-n-propylamine in the step (1) and the step (3) is 0.5-1:1-1.5: 0.5-1.
Further, in the step (2), the pH value of the reaction system is adjusted to 8, and a reagent for adjusting the pH value is 0.1mol/L sodium hydroxide solution or 0.1mol/L hydrochloric acid solution.
Further, in the step (3), the dropping time of adding the di-n-propylamine into the three-neck flask by using a constant pressure dropping funnel is 25-30 min.
Further, the time for standing in the separating funnel in the step (4) is 30 min.
Further preferably, the specific operation steps of step 1 and step 2 are as follows:
(1) taking a 100ml three-neck flask, adding 0.05mol of sodium isopropyl xanthate and 0.05mol of sodium chloroacetate, adding 40ml of water for dissolving, installing a stirring device, and inserting a thermometer into the flask;
(2) adjusting the pH value of the reaction system obtained in the step (1) to be pH =8, starting a stirring device, starting a water bath heating device, controlling the temperature of the reaction system to be 35 ℃, and stirring for 2 h;
(3) stopping heating after the stirring time is up, reducing the temperature of the reaction system to 25 ℃, adding 0.03mol of di-n-propylamine into the three-neck flask by using a constant-pressure dropping funnel, maintaining the dropping time to be 25-30min, continuing heating in a water bath for reaction, keeping the temperature of the reaction system at 50 ℃, and stirring for 6 h;
(4) after the reaction in the step (3) is finished, pouring a product obtained by the reaction into a separating funnel, standing the mixture in the separating funnel for 30min, separating the mixture, collecting the product, weighing the product, and calculating the yield;
(5) and (4) measuring the content of the product obtained in the step (4) by using a gas chromatograph, and determining the structure of the product by using Nuclear Magnetic Resonance (NMR).
A method for purifying O-isopropyl-N, N' -di-N-propylthiocarbamate, characterized by comprising the steps of:
step 1, placing 5ml of synthesized O-isopropyl-N, N' -di-N-propyl thiocarbamate into a 100ml small beaker, adding 10ml of 1mol/L acid solution, and performing primary stirring by using a glass rod;
step 2, after the primary stirring is finished, adding 40ml of deionized water into the beaker, and stirring for the second time; after the secondary stirring is finished, transferring the mixed solution to a 250ml separating funnel, standing and layering, wherein an upper organic phase is the purified O-isopropyl-N, N' -di-N-propyl thiocarbamate;
and 3, after standing and layering are finished, taking a small amount of organic samples on the upper layer by using a disposable dropper, dripping 2-3 drops of organic samples into a 1.5ml sample tube, adding dichloromethane serving as a solvent for dilution, then injecting samples, taking 2 mu ml of organic samples for gas chromatography determination, and determining the content of the purified O-isopropyl-N, N' -di-N-propylthiocarbamate.
Further, the acid solution in step 1 is a hydrochloric acid solution or a glacial acetic acid solution.
Further, the primary stirring time in the step 1 is 10 min; the secondary stirring time in the step 2 is 5min-10 min; the standing and layering time in the step 2 is 15 min.
The amount of sodium chloroacetate used in the reaction is strictly controlled and should not be excessive, and if excessive, the sodium chloroacetate will react with HSCH generated in the reaction2COONa reaction to give S (CH2COONa)2Also, also can be combined with (C)3H7)2Reaction of NH to (C)3H7)2NCH2COONa, the resulting impurities affect not only product recovery but also product purity. Therefore, the optimal reaction dosage and proportion are obtained by continuously adjusting the reaction conditions and the dosage of the raw materials through repeated experiments.
Compared with the synthesis of Z-200 thiourethane, the synthesis difficulty of O-isopropyl-N, N' -di-N-propyl thiocarbamate is higher, and the amines added in the second step of reaction are different. The alkylamine added in the second step of the Z-200 type thiourethane is ethylamine which is easily soluble in water and reacts with sodium isopropyl xanthate which is a product of the first step in a homogeneous phase, and the alkylamine added in the synthesis of O-isopropyl-N, N' -di-N-propyl thiocarbamate is di-N-propylamine which is slightly soluble in water and is subjected to multiphase reaction with the sodium isopropyl xanthate which is a product of the first step in a heterogeneous phase, and the di-N-propylamine has large steric hindrance, so that the synthesis difficulty is increased. Thus, by continuously optimizing the reaction conditions, an optimal synthesis scheme is found.
The synthesis and purification method of O-isopropyl-N, N' -di-N-propylthiocarbamate of the present invention has the following beneficial effects:
(1) the invention provides a method for synthesizing and purifying a novel thiourethane collecting agent, and relates to a method for synthesizing and purifying O-isopropyl-N, N' -di-N-propyl thiocarbamate.
(2) The synthesis method of the O-isopropyl-N, N' -di-N-propyl thiocarbamate and the purification method is simple to operate and high in product yield.
(3) The synthesis and purification method of O-isopropyl-N, N' -di-N-propyl thiocarbamate provides a novel collecting agent, which greatly improves the collecting capacity of the collecting agent on the basis of ensuring excellent selectivity, and the collecting agent has excellent flotation separation efficiency on chalcopyrite. Compared with the existing z-200 collecting agent, the separation and recovery efficiency of S can be improved to 21% from 10% under the conditions of the same use amount and pH value, and the separation and recovery efficiency of S is improved by more than one time; the separation and recovery efficiency of Cu can be improved to 89% from the original 68%, and the overall flotation separation efficiency is greatly improved.
Drawings
FIG. 1: the invention synthesizes O-isopropyl-N, N' -di-N-propyl thiocarbamate under the best reaction condition;
FIG. 2: the gas chromatography spectrogram of O-isopropyl-N, N' -di-N-propyl thiocarbamate is synthesized under the optimal reaction condition;
FIG. 3: a gas chromatography spectrogram obtained by acidifying O-isopropyl-N, N' -di-N-propyl thiocarbamate synthesized under the optimal reaction condition in the invention;
FIG. 4: the nuclear magnetic resonance H spectrum of O-isopropyl-N, N' -di-N-propyl thiocarbamate is synthesized under the optimal reaction condition;
FIG. 5: the nuclear magnetic resonance spectrum C of the O-isopropyl-N, N' -di-N-propyl thiocarbamate is synthesized under the optimal reaction condition.
Detailed Description
The invention is further illustrated below with reference to fig. 1 to 5:
first part, assay reagents and instruments
The main test reagents used in the present invention are shown in Table 1-1. Wherein isopropanol, carbon disulfide and sodium hydroxide are used to synthesize sodium isopropyl xanthate.
TABLE 1-1 Main reagents for the experiment
| Name (R) | Chemical formula (II) | Molecular weight | Specification of | Manufacturer of the product |
| Isopropanol (I-propanol) | C3H7OH | 60.06 | Analytical purity | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
| Carbon disulfide | CS2 | 76.14 | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Sodium hydroxide | NaOH | 40.00 | Analytical purity | Xilong Chemical Co., Ltd. |
| Chloroacetic acid sodium salt | ClCH2COONa | 116.50 | Analytical purity | TIANJIN KWANGFU FINE CHEMICAL INDUSTRY Research Institute |
| Di-n-propylamine | (C3H7)2NH | 101.19 | Analytical purity | Shanghai Hansi chemical Co Ltd |
| Anhydrous ethanol | C2H5OH | 46.07 | Analytical purity | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
| Glacial acetic acid | CH3COOH | 60.05 | Analytical purity | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
Under the actual condition, the factors such as operating conditions, experiment cost, medicine sources, safety and the like are considered, and the chloroacetic acid esterification method is adopted in the experiment to prepare the product.
The experiment is the synthesis of O-isopropyl-N, N' -di-N-propylthiocarbamate and the optimization of the synthesis process, and the main experimental instruments used are shown in tables 1-2:
TABLE 1-2 main instruments of experiment
The specific experimental steps for synthesizing O-isopropyl-N, N' -di-N-propylthiocarbamate in the invention are as follows:
(1) taking a 100ml three-neck flask, adding 0.05-0.075mol of sodium isopropyl xanthate and 0.025-0.05mol of sodium chloroacetate, adding water for dissolving, installing a stirring device, and inserting a thermometer into the flask;
(2) adjusting the pH value of the reaction system obtained in the step (1) to be pH =8, starting a stirring device, starting a water bath heating device, and controlling the temperature T1 of the reaction system for 2 h;
(3) stopping heating after the stirring time is up, reducing the temperature of the reaction system to 25 ℃, adding 0.025-0.05mol of di-n-propylamine into the three-neck flask by using a constant-pressure dropping funnel, maintaining the dropping time to be 25min-30min, continuing the water bath heating reaction to keep the temperature of the reaction system at T2, and stirring for T2(ii) a Wherein the molar ratio of the raw materials of sodium chloroacetate, sodium isopropyl xanthate and di-n-propylamine is 0.5-1:1-1.5:0.5-1 respectively;
(4) after the reaction in the step (3) is finished, pouring a product obtained by the reaction into a separating funnel, standing the mixture in the separating funnel for 30min, separating the mixture, collecting the product, weighing the product, and calculating the yield;
(5) and (4) measuring the content of the product obtained in the step (4) by using a gas chromatograph, and determining the structure of the product by using Nuclear Magnetic Resonance (NMR).
In the second part, the invention determines the influence of each factor on the yield of O-isopropyl-N, N' -di-N-propyl thiocarbamate through a plurality of groups of experiments, thereby selecting an optimal experimental scheme.
The material ratios mentioned in the following reactions are all sodium chloroacetate: sodium isopropyl xanthate: the molar ratio of di-n-propylamine.
Effect of reaction time on yield
1) Reaction time t in step 22Influence on the yield
In order to explore the second step ammonolysis reaction time t2The yield of O-isopropyl-N, N' -di-N-propyl thiocarbamate is influenced, and the reaction material ratio, the temperature and pH of the reaction system and the reaction time t are controlled1The time t is changed without change22h, 3h, 4h, 5h, 6h and 7h, and the experimental result is shown in the table 2-1.
TABLE 2-1 reaction time t in step 22Influence on the yield
As can be seen from Table 2-1, when the pH was 8, the reaction temperature T in the first step was set to be 81At 35 ℃ and a second-step reaction temperature T2Setting the material ratio at 1:1:1 when the temperature is 40 ℃ and keeping the reaction time t1Is 2 hours, when t is2At 6h, the yield reaches the maximum, the reaction time is prolonged, the yield is not obviously increased and is even slightly reduced, so when the reaction time t is longer2The yield is up to 29.157% when the yield is 6 h.
Effect of reaction temperature on yield
1) Step 1 reaction temperature T1
In order to explore the temperature T of the first step reduction reaction1The yield of O-isopropyl-N, N' -di-N-propyl thiocarbamate is influenced, and the reaction material ratio, the reaction time, the pH of the reaction system and the reaction temperature T of the step 2 are controlled2Constant, varying the temperature T1The temperature was 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ and 55 ℃, and the experimental results are shown in Table 2-2.
TABLE 2-2 step 1 reaction temperature T1Influence on the yield
As can be seen from Table 2-2, when the pH was 8, the reaction temperature T in step 1 was set to 82At 40 ℃, the material ratio is set to be 1:1:1, and the reaction time t is kept1Is 2 hours, when t is2At 6h, with the reaction temperature T1The yield of O-isopropyl-N, N' -di-N-propylthiocarbamate starts to increase when the reaction temperature T of step 1 is increased1At 35 ℃ the yield reaches a maximum of 29.157%, after which the temperature continues to rise, with a tendency for the yield to drop significantly, so that when step 1 the reaction temperature T is such that1The yield was maximal at 35 ℃.
2) Step 2 reaction temperature T2
In order to explore the ammonolysis reaction temperature T in step 22The yield of O-isopropyl-N, N' -di-N-propyl thiocarbamate is influenced, and the reaction material ratio, the reaction time, the pH of the reaction system and the reaction temperature T in the step 1 are controlled1Changing the temperature T in step 2 without changing2The temperature was 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃, and the experimental results are shown in tables 2-3.
TABLE 2-3 step 2 reaction temperature T2Influence on the yield
As can be seen from tables 2-3, when the pH was 8, the reaction temperature T in step 1 was set to 81At 35 ℃, the material ratio is set to be 1:1:1, and the reaction time t is kept1Is 2 hours, when t is2At 6h, the reaction temperature T is increased along with the step 22The yield of O-isopropyl-N, N' -di-N-propylthiocarbamate starts to increase when the reaction temperature T is reached2At 50 ℃ the yield reaches a maximum of 36.721%, after which the temperature continues to rise, with a tendency for the yield and the content to drop significantly, so that when step 2 the reaction temperature T is such that2The yield was maximal at 50 ℃.
Effect of the reaction Material ratio (sodium chloroacetate: sodium isopropyl xanthate: di-n-propylamine) on the yield
1) Effect of the amount of Di-n-propylamine on the reaction yield
In order to investigate the influence of the reaction material ratio on the yield of O-isopropyl-N, N' -di-N-propylthiocarbamate, the reaction temperature, the reaction time and the pH of the reaction system were controlled, the amounts of sodium chloroacetate and sodium isopropyl xanthate were kept constant, and the amounts of di-N-propylamine were varied so that the material ratios (sodium chloroacetate: sodium isopropyl xanthate: di-N-propylamine) were 1:1:1, 1:1:0.9, 1:1:0.8, 1:1:0.7, 1:1:0.6, 1:1:0.5, and the experimental results were as shown in tables 2 to 4.
TABLE 2-4 Effect of Di-n-propylamine amount on yield
As can be seen from tables 2-4, when the pH was 8, the reaction time t in step 1 was1Is 2h, step 2 reaction time t2When the time is 6 hours, and the reaction temperature T of the step 1 is kept1At 35 ℃ and a reaction temperature T in step 22The reaction mass ratio was varied at 50 ℃ and the amount of di-n-propylamine used was varied, and when the mass ratio was 1:1:0.6, the yield reached a maximum of 50.450%, after which the amount of di-n-propylamine used was increased and the yield was reduced.
2) Effect of the amount of sodium Isopropylxanthate on the reaction yield
In order to investigate the influence of the reaction material ratio on the yield of O-isopropyl-N, N' -di-N-propylthiocarbamate, the reaction temperature, the reaction time and the pH of the reaction system were controlled, the amounts of sodium chloroacetate and di-N-propylamine were kept constant, and the amounts of sodium isopropylxanthate were changed so that the material ratios (sodium chloroacetate: sodium isopropylxanthate: di-N-propylamine) were 1:1:0.6, 1:1.1:0.6, 1:1.2:0.6, 1:1.3:0.6, 1:1.4:0.6, 1:1.5:0.6, and the experimental results were as shown in tables 2 to 5.
Tables 2-5 Effect of the amount of sodium Isopropylxanthate on the yield
As can be seen from tables 2-5, when the pH was 8, the reaction time t in step 1 was1Is 2h, step 2t2When the time is 6 hours, and the reaction temperature T of the step 1 is kept1At 35 ℃ and a reaction temperature T in step 22The reaction mass ratio was changed at 50 ℃, and the amount of sodium isopropyl xanthate used was increased, so that the yield and the content of O-isopropyl-N, N' -di-N-propylthiocarbamate were all decreased with the increase in the amount of sodium isopropyl xanthate, and therefore, when the mass ratio was 1:1:0.6, the yield was the highest, 50.450%.
3) Effect of the amount of sodium chloroacetate on the reaction yield
In order to investigate the influence of the reaction material ratio on the yield of O-isopropyl-N, N' -di-N-propylthiocarbamate, the reaction temperature, the reaction time and the pH of the reaction system were controlled, the amounts of sodium isopropyl xanthate and di-N-propylamine were kept constant, and the amounts of sodium chloroacetate were changed so that the material ratios (sodium chloroacetate: sodium isopropyl xanthate: di-N-propylamine) were 1:1:0.6, 0.9:1:0.6, 0.8:1:0.6, 0.7:1:0.6, 0.6:1:0.6, 0.5:1:0.6, and the experimental results were as shown in tables 2 to 6.
TABLE 2-6 Effect of the amount of sodium chloroacetate on the yield
As can be seen from tables 2-6, when the pH was 8, the reaction time t in step 1 was1Is 2h, step 2 reaction time t2When the time is 6 hours, and the reaction temperature T of the step 1 is kept1At 35 ℃ and a reaction temperature T in step 22The reaction mass ratio was varied at 50 ℃. When the amount of sodium chloroacetate is changed, the yield and the content of O-isopropyl-N, N' -di-N-propylthiocarbamate are both increased with the increase of the amount of sodium chloroacetate, and thus, when the material ratio is 1:1:0.6, the yield is the highest, 50.450%.
Through the determination of the above experiment, the optimal experimental conditions of the invention are as follows:
when the pH value of the reaction system is 8, the reaction time t of the step 11Is 2h, step 2 reaction time t2When the reaction time is 6 hours, and the reaction temperature T of the step 1 is controlled1At 35 ℃ and the reaction temperature T of step 22At 50 ℃, sodium chloroacetate: sodium isopropyl xanthate: di-n-propylamineWhen the material ratio of (1: 1: 0.6), the yield of the invention is highest, and the purity of the obtained thiourethane product is higher and reaches 80.22%. FIG. 1 is a flow chart of the synthesis process under the optimal reaction conditions.
Third section on purification treatment
The experimental procedure for the purification of O-isopropyl-N, N' -di-N-propylthiocarbamate according to the invention is as follows:
step 1, placing 5ml of synthesized O-isopropyl-N, N' -di-N-propyl thiocarbamate into a 100ml small beaker, adding 10ml of 1mol/L acid solution, and performing primary stirring by using a glass rod;
step 2, after the primary stirring is finished, adding 40ml of deionized water into the beaker, and stirring for the second time; after the secondary stirring is finished, transferring the mixed solution to a 250ml separating funnel, standing and layering, wherein an upper organic phase is the purified O-isopropyl-N, N' -di-N-propyl thiocarbamate;
and 3, after standing and layering are finished, taking a small amount of organic samples on the upper layer by using a disposable dropper, dripping 2-3 drops of organic samples into a 1.5ml sample tube, adding dichloromethane serving as a solvent for dilution, then injecting samples, taking 2 mu ml of organic samples for gas chromatography determination, and determining the content of the purified O-isopropyl-N, N' -di-N-propylthiocarbamate.
The acid solution in the step 1 is a hydrochloric acid solution or a glacial acetic acid solution.
The primary stirring time in the step 1 is 10 min; the secondary stirring time in the step 2 is 5min-10 min; the standing and layering time in the step 2 is 15 min.
The material ratio of sodium chloroacetate to sodium isopropyl xanthate to amine was varied to obtain synthetic products, which were then acidified separately, and the results are shown in the following table:
tables 2-7 results of acidification of the product with varying amounts of di-n-propylamine
Tables 2-8 results of acidification treatment of the product with varying amounts of sodium isopropyl xanthogenate
Tables 2-9 results of acidification treatment of the product with varying amounts of sodium chloroacetate
The test results of the invention are detected and analyzed.
The gas chromatography spectrum of O-isopropyl-N, N '-di-N-propyl thiocarbamate synthesized under the optimal reaction conditions of the present invention and the gas chromatography spectrum of O-isopropyl-N, N' -di-N-propyl thiocarbamate acidified synthesized under the optimal reaction conditions of the present invention were analyzed with reference to fig. 2 and 3. The gas chromatography data analysis data are shown in tables 2-10 and tables 2-11 below.
TABLE 2-10 gas chromatography data analysis of the products synthesized under the optimal reaction conditions
| Peak sequence | Retention time (min) | Peak height (mV) | Peak area (mV. s) | Peak area (%) | Content% |
| 1 | 3.147 | 176.265 | 436.2807 | 13.7826 | 13.7826 |
| 2 | 7.661 | 39.582 | 85.4971 | 2.7009 | 2.7009 |
| 3 | 7.841 | 29.988 | 61.1755 | 1.9326 | 1.9326 |
| 4 | 8.513 | 23.182 | 43.1185 | 1.3622 | 1.3622 |
| 5 | 10.139 | 949.509 | 2539.3743 | 80.2217 | 80.2217 |
Tables 2-11 gas chromatography data analysis tables for the acidification of the synthesis product under optimum reaction conditions
| Peak sequence | Retention time (min) | Peak height (mV) | Peak area (mV. s) | Peak area (%) | Content% |
| 1 | 7.534 | 24.282 | 29.4230 | 1.1613 | 1.1613 |
| 2 | 7.710 | 20.321 | 24.8573 | 0.9795 | 0.9795 |
| 3 | 8.408 | 19.346 | 15.9797 | 0.6328 | 0.6328 |
| 4 | 9.927 | 913.375 | 2466.1125 | 97.2264 | 97.2264 |
In the gas chromatograms 2 and 3, peak (1) is dichloromethane, which acts as a solvent, diluting the sample before injection. The values shown in tables 2-10 and tables 2-11 are raw data on gas chromatograph for each material in the product, excluding solvent dichloromethane.
In fig. 2, peak (2) is di-N-propylamine, peaks (3), (4), (5) are peaks corresponding to the by-products, and peak (6) is a peak exhibited by the experimental product O-isopropyl-N, N' -di-N-propylthiocarbamate, and these 5 peaks are corresponding to the peak sequences in tables 2 to 10.
In fig. 3, peaks (2), (3), and 4) are peaks corresponding to the by-product, and peak (5) is a peak indicated by the product O-isopropyl-N, N' -di-N-propylthiocarbamate of this experiment, and these 4 peaks are corresponded to the peak order in tables 2 to 11.
As can be seen from FIG. 2 and tables 2-10, the majority of the effect on product content is its excess unreacted reactant, di-n-propylamine. Comparing fig. 2 and fig. 3, it is evident that after purification with glacial acetic acid, the excess di-n-propylamine in the product is mainly separated, so that the content of the product is increased. And the contents of the products are further compared, and the data in tables 2-10 and tables 2-11 are analyzed, so that glacial acetic acid not only separates the di-n-propylamine from the products, but also separates a very small amount of byproducts, and the degree of purification of the final products reaches a certain threshold value.
Because di-n-propylamine is slightly soluble in water and the steric hindrance of the material structure is large, the ammonolysis reaction is difficult, so that the excessive unreacted di-n-propylamine mainly influencing the product content is obtained by theory. It was found through several experiments that the level of product was indeed affected by the excess unreacted di-n-propylamine in the product, the two oils being miscible. Thus removing excess unreacted di-n-propylamine therefrom to increase the product content. The alkyl number of the di-n-propylamine is more than that of ethylamine which is a raw material for synthesizing Z-200 type thiourethane, so that the basicity of the di-n-propylamine is stronger in a pure substance liquid state, and the organic acid glacial acetic acid is added into the obtained product according to the characteristics of the substance and the oily substance of the product.
After the glacial acetic acid is added, all the organic matters are mutually soluble, so that a proper amount of water is added into the organic matters, and the water phase and the oil phase are separated. And separating the upper layer organic matter, and measuring the content of the matter, wherein after the synthetic product is purified by adding glacial acetic acid, the effect is obvious, and the content of the obtained product can reach 97.23%.
Similarly, the product synthesized by the invention is purified by using hydrochloric acid solution, namely, the acid solution in the step 1 is replaced by hydrochloric acid solution, and the content of the obtained product can also reach 93.16%. According to experimental results, the synthetic O-isopropyl-N, N' -di-N-propyl thiocarbamate has very obvious purification effect after being acidified and purified by hydrochloric acid solution or glacial acetic acid.
Nuclear Magnetic Resonance (NMR) spectrum of the synthetic product of the invention:
the O-isopropyl-N, N' -di-N-propyl thiocarbamate molecule produced by the present invention was subjected to nuclear magnetic resonance spectroscopy, and an H spectrum and a C spectrum were obtained, as shown in fig. 4 and 5. The detection result shows that the synthesized compound has a consistent structure with a target product, and the related nuclear magnetic data are as follows:
1H NMR (400 MHz, CDCl3 δ ppm): δ: 5.46 (m, 1H, OCH), 3.57 (m, 2H, NCH2), 3.24 (m, 2H, NCH2), 1.58 (m, 2H, CH2CH3), 1.46 (m, 2H, CH2CH3), 1.19(d, J = 6.3 Hz, 6H, CH2CH3), 0.78 (m, 6H, CH2CH3)； 13C NMR (100 MHz, CDCl3) δ: 186.8, 74.1, 54.5, 50.4, 21.7, 21.3, 20.0, 11.3, 11.1 ppm。
the synthesis and purification method of O-isopropyl-N, N' -di-N-propylthiocarbamate of the present invention has the following beneficial effects:
(1) the invention provides a method for synthesizing and purifying a novel thiourethane collecting agent, and relates to a method for synthesizing and purifying O-isopropyl-N, N' -di-N-propyl thiocarbamate.
(2) The synthesis method of the O-isopropyl-N, N' -di-N-propyl thiocarbamate and the purification method is simple to operate and high in product yield.
(3) The synthesis and purification method of O-isopropyl-N, N' -di-N-propyl thiocarbamate provides a novel collecting agent, which greatly improves the collecting capacity of the collecting agent on the basis of ensuring excellent selectivity, and the collecting agent has excellent flotation separation efficiency on chalcopyrite. Compared with the existing z-200 collecting agent, the separation and recovery efficiency of S can be improved to 21% from 10% under the conditions of the same use amount and pH value, and the separation and recovery efficiency of S is improved by more than one time; the separation and recovery efficiency of Cu can be improved to 89% from the original 68%, and the overall flotation separation efficiency is greatly improved.
The invention is described above by way of example with reference to the accompanying drawings and embodiments, it is to be understood that the invention is not limited to the embodiments described above, but is intended to cover various modifications made by the method and technical solution of the invention, or to be applied to other fields without modification.
Claims (10)
1. A method for synthesizing O-isopropyl-N, N' -di-N-propylthiocarbamate, characterized by comprising the steps of:
step 1, sodium chloroacetate reduction reaction: sodium chloroacetate is taken as a raw material, sodium isopropyl xanthate is added, and reduction reaction is carried out to generate an intermediate sodium isopropyl xanthate;
step 2, synthesizing a target product through ammonolysis reaction: adding di-N-propylamine into the reactant in the step 1, and carrying out ammonolysis reaction with the intermediate sodium isopropyl xanthate generated by the reaction in the step 1 to synthesize a target product O-isopropyl-N, N' -di-N-propyl thiocarbamate by using an acetate chlorination method;
the reaction equations of step 1 and step 2 are as follows:
2. the method of synthesis of O-isopropyl-N, N' -di-N-propylthiocarbamate according to claim 1, characterized in that: the specific operation steps of the step 1 and the step 2 are as follows:
(1) taking a 100ml three-neck flask, adding 0.05-0.075mol of sodium isopropyl xanthate and 0.025ml-0.05mol of sodium chloroacetate, adding 30ml-60ml of tap water for dissolving, installing a stirring device, and inserting a thermometer into the flask;
(2) adjusting the pH value of the reaction system obtained in the step (1), starting a stirring device, starting a water bath heating device, controlling the temperature of the reaction system to be 35-55 ℃, and stirring for 2 hours;
(3) stopping heating after the stirring time is up, reducing the temperature of the reaction system to 25 ℃, adding 0.025mol-0.05mol of di-n-propylamine into the three-neck flask by using a constant-pressure dropping funnel, continuing heating in a water bath for reaction, keeping the temperature of the reaction system at 30-80 ℃, and stirring for 2-7 h;
(4) after the reaction in the step (3) is finished, pouring a product obtained by the reaction into a separating funnel, standing the mixture in the separating funnel, separating the mixture, collecting the product, weighing the product, and calculating the yield;
(5) and (4) measuring the content of the product obtained in the step (4) by using a gas chromatograph, and determining the structure of the product by using Nuclear Magnetic Resonance (NMR).
3. The method of synthesis of O-isopropyl-N, N' -di-N-propylthiocarbamate according to claim 2, characterized in that: the molar ratio of the raw materials sodium chloroacetate, sodium isopropyl xanthate and di-n-propylamine in the step (1) and the step (3) is 0.5-1:1-1.5: 0.5-1.
4. The method of synthesis of O-isopropyl-N, N' -di-N-propylthiocarbamate according to claim 2, characterized in that: in the step (2), the pH value of the reaction system is adjusted to be 8, and a reagent for adjusting the pH value is 0.1mol/L sodium hydroxide solution or 0.1mol/L hydrochloric acid solution.
5. The method of synthesis of O-isopropyl-N, N' -di-N-propylthiocarbamate according to claim 2, characterized in that: and (3) adding di-n-propylamine into the three-neck flask by using a constant-pressure dropping funnel within 25-30 min.
6. The method of synthesis of O-isopropyl-N, N' -di-N-propylthiocarbamate according to claim 2, characterized in that: and (4) standing in a separating funnel for 30 min.
7. The O-isopropyl-N, N' -di-N-propyl thiocarbamate synthesis method according to claim 1 or 2, characterized in that: the specific operation steps of the step 1 and the step 2 are as follows:
(1) taking a 100ml three-neck flask, adding 0.05mol of sodium isopropyl xanthate and 0.05mol of sodium chloroacetate, adding 40ml of water for dissolving, installing a stirring device, and inserting a thermometer into the flask;
(2) adjusting the pH value of the reaction system obtained in the step (1) to be pH =8, starting a stirring device, starting a water bath heating device, controlling the temperature of the reaction system to be 35 ℃, and stirring for 2 h;
(3) stopping heating after the stirring time is up, reducing the temperature of the reaction system to 25 ℃, adding 0.03mol of di-n-propylamine into the three-neck flask by using a constant-pressure dropping funnel, maintaining the dropping time to be 25-30min, continuing heating in a water bath for reaction, keeping the temperature of the reaction system at 50 ℃, and stirring for 6 h;
(4) after the reaction in the step (3) is finished, pouring a product obtained by the reaction into a separating funnel, standing the mixture in the separating funnel for 30min, separating the mixture, collecting the product, weighing the product, and calculating the yield;
(5) and (4) measuring the content of the product obtained in the step (4) by using a gas chromatograph, and determining the structure of the product by using Nuclear Magnetic Resonance (NMR).
8. A method for purifying O-isopropyl-N, N' -di-N-propyl thiocarbamate synthesized by the method of claims 1-7, characterized by comprising the following steps:
step 1, placing 5ml of synthesized O-isopropyl-N, N' -di-N-propyl thiocarbamate into a 100ml small beaker, adding 10ml of 1mol/L acid solution, and performing primary stirring by using a glass rod;
step 2, after the primary stirring is finished, adding 40ml of deionized water into the beaker, and stirring for the second time; after the secondary stirring is finished, transferring the mixed solution to a 250ml separating funnel, standing and layering, wherein an upper organic phase is the purified O-isopropyl-N, N' -di-N-propyl thiocarbamate;
and 3, after standing and layering are finished, taking a small amount of organic samples on the upper layer by using a disposable dropper, dripping 2-3 drops of organic samples into a 1.5ml sample tube, adding dichloromethane serving as a solvent for dilution, then injecting samples, taking 2 mu ml of organic samples for gas chromatography determination, and determining the content of the purified O-isopropyl-N, N' -di-N-propylthiocarbamate.
9. The method of purifying O-isopropyl-N, N' -di-N-propylthiocarbamate according to claim 8, characterized in that: the acid solution in the step 1 is a hydrochloric acid solution or a glacial acetic acid solution.
10. The method of purifying O-isopropyl-N, N' -di-N-propylthiocarbamate according to claim 8, characterized in that: the primary stirring time in the step 1 is 10 min; the secondary stirring time in the step 2 is 5min-10 min; the standing and layering time in the step 2 is 15 min.
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