CN105859597A - Synthesis method of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester - Google Patents
Synthesis method of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester Download PDFInfo
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- CN105859597A CN105859597A CN201610252637.9A CN201610252637A CN105859597A CN 105859597 A CN105859597 A CN 105859597A CN 201610252637 A CN201610252637 A CN 201610252637A CN 105859597 A CN105859597 A CN 105859597A
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- methyl acrylate
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- dibutyl dithio
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/18—Esters of dithiocarbamic acids
- C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
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Abstract
The invention relates to the technical field of flotation reagent synthesis, and discloses a method for synthesizing N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester, wherein 26-32 parts of carbon disulfide and 20-32 parts of methyl acrylate are mixed and added into a reaction container; then slowly dripping 40-52 parts of di-n-butylamine into a reaction container, controlling the dripping speed at 0.5-1 mL/min, cooling and stirring, and controlling the reaction temperature to be not more than 20 ℃; after the dropwise adding and the exothermic reaction are finished, preserving heat at the temperature of 30-50 ℃ and stirring for 1-2 hours to obtain a crude product; and (3) distilling the excessive carbon disulfide in the crude product under reduced pressure to obtain a qualified N, N-dibutyl dithio methyl acrylate azothionate product. According to the invention, carbon disulfide, methyl acrylate and di-N-butylamine are used as raw materials to synthesize N, N-dibutyl dithio methyl acrylate sulfur nitrogen ester in one step, and di-N-butylamine and carbon disulfide directly act without intermediate products, so that the synthesis process is simple, high in efficiency, low in cost and environment-friendly.
Description
Technical field
The present invention relates to floating agent synthesis technical field, the synthetic method of a kind of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester.
Background technology
Dibutyl dithio methyl acrylate sulphur nitrogen ester is a kind of new and effective sulfide mineral collector, and complicated and severe cold areas sulphide ore is had the feature that collecting ability is strong and the best.The main method producing this medicament at present mainly has:
(1) xanthate ammonolysis process, the method is mainly by being reacted xanthates processed by alcohol and carbon disulfide, then xanthates reacts with halogenated alkane, prepare raw material xanthate, then adding aminated compounds and xanthate generation aminolysis reaction, final production target product, the synthesis of this technique is divided into two-step reaction to carry out, complex synthetic route, seldom uses.
(2) tertiary amine method, raw material tertiary amine is expensive, and is difficult to obtain, and products therefrom separates difficulty.There is the shortcoming that accessory substance alkyl hydrosulfide separates with target product difficulty when using alkyl halide method to prepare in technique, and association contains industrial waste gas and the waste water of mercaptan in a large number, environmental pollution is bigger.
(3) Changsha Mining & Metallurgy Inst's acrylonitrile, dimethylamine, carbon disulfide single step reaction, has synthesized a kind of Novel vulcanization ore deposit collecting agent: dimethyl dithiocarbamic acid acrylonitrile ester (CH3)2NC-SCNH2CH2CN.Though this reaction uses one-step synthesis method, but the grade and rate of recovery raising degree to copper is inconspicuous；And raw material propylene nitrile is inflammable, its steam and air can form explosive mixture.Saidi is with water as solvent and catalyst, another be Ranu ionic liquid be solvent and catalyst, the most successfully synthesize dithiocarbamate derivative, and solvent used has been all green solvent, be the preferable example of environment-friendly organic synthesis.But we have found that when using water as solvent, the reaction time is longer, the substantial amounts of solvent extraction of product；When being solvent with ionic liquid, though the reaction time is shorter, but the separation of product is also required to substantial amounts of solvent and extracts, and is not substantially the green syt in complete meaning.
, all there is technique process loaded down with trivial details in the preparation method of above-described several dibutyl dithio methyl acrylate sulphur nitrogen ester, operating environment is poor, and production cost is high, the problems such as waste water is difficult, environmental pollution.
Summary of the invention
It is an object of the invention to provide a kind of N, the synthetic method of N-dibutyl dithio methyl acrylate sulphur nitrogen ester, under condition of no solvent, use " one-step method " synthesis N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester, loaded down with trivial details to solve technique in prior art, production cost is high, the problem easily causing environmental pollution.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of N, the synthetic method of N-dibutyl dithio methyl acrylate sulphur nitrogen ester, N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is mining floating agent, it is prepared from by the raw material of following parts by weight: di-n-butylamine 40～52 parts, methyl acrylate 20～32 parts, carbon disulfide 26～32 parts, its preparation method comprises the following steps:
Step one, equipped with in the there-necked flask of condensation reflux unit, add 26～32 parts of carbon disulfide, 20～32 parts of methyl acrylates mix；
Step 2, being slowly added dropwise in there-necked flask by 40～52 parts of di-n-butylamines, rate of addition controls 0.5～1mL/min again, just the stirring of dropping limit, uses ice-water bath to cool down, control dropping temperature less than 20 DEG C in whipping process；
Step 3, treat step 2 dropping and after exothermic reaction terminates, be incubated under the conditions of 30～50 DEG C and stir 1～2h, preparing N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product；
Step 4, decompression distill out the carbon disulfide of excess in the N prepared by step 3, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product, i.e. obtain qualified N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester product.
Preferably, the distillation condition that reduces pressure in described step 4 is 0.06Mpa～-0.1Mpa, and 60 DEG C of hot water heat up.
Preferably, described di-n-butylamine, carbon disulfide and methyl acrylate raw material are AR.
The equation that chemical reaction occurs under the conditions of di-n-butylamine, carbon disulfide and methyl acrylate are above-mentioned is as follows:
In above-mentioned chemical reaction, being first that di-n-butylamine reacts with carbon disulfide, generate intermediate, sulfydryl is to activation subsequentlyα,β-unsaturated compound carries out Michael addition reaction, generates N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester.
N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is insoluble in water, but dissolve in the organic solvent such as ethanol, ether, belong to nonionic polar collecting agent, have collecting and frothing capacity concurrently, in flotation, consumption is few can effectively be enriched with some rare precious metals even without adding foaming agent, reduces reagent cost while improving mineral processing index.
Method of the present invention by by di-n-butylamine, carbon disulfide and methyl acrylate according to certain technological parameter, one-step synthesis goes out N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester, di-n-butylamine and carbon disulfide directly act on, need not move through intermediate product, synthesis technique is simple, efficiency is high, low cost, environmental protection, and synthesize product high efficiency low cost, broad range of applicability.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention.
Embodiment 1
A kind of N, the synthetic method of N-dibutyl dithio methyl acrylate sulphur nitrogen ester, N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is mining floating agent, it is prepared from by the raw material of following parts by weight: di-n-butylamine 40 parts, methyl acrylate 32 parts, carbon disulfide 26 parts, its preparation method comprises the following steps:
Step one, equipped with in the there-necked flask of condensation reflux unit, add 26 parts of carbon disulfide, 32 parts of methyl acrylates mix；
Step 2, being slowly added dropwise in there-necked flask by 40 parts of di-n-butylamines, rate of addition controls 0.5～1mL/min again, just the stirring of dropping limit, uses ice-water bath to cool down, control dropping temperature less than 20 DEG C in whipping process；
Step 3, treat step 2 dropping and after exothermic reaction terminates, be incubated under the conditions of 30～50 DEG C and stir 1～2h, preparing N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product；
Step 4, at 0.06Mpa～-0.1Mpa, under conditions of 60 DEG C of hot water heat up, decompression distills out the carbon disulfide of excess in the N prepared by step 3, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product, i.e. obtain qualified N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester product.
In check analysis, the product prepared by step 4, the content of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is 89%, and yield is 92.4%.
Embodiment 2
A kind of N, the synthetic method of N-dibutyl dithio methyl acrylate sulphur nitrogen ester, N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is mining floating agent, it is prepared from by the raw material of following parts by weight: di-n-butylamine 52 parts, methyl acrylate 20 parts, carbon disulfide 32 parts, its preparation method comprises the following steps:
Step one, equipped with in the there-necked flask of condensation reflux unit, add 32 parts of carbon disulfide, 20 parts of methyl acrylates mix；
Step 2, being slowly added dropwise in there-necked flask by 52 parts of di-n-butylamines, rate of addition controls 0.5～1mL/min again, just the stirring of dropping limit, uses ice-water bath to cool down, control dropping temperature less than 20 DEG C in whipping process；
Step 3, treat step 2 dropping and after exothermic reaction terminates, be incubated under the conditions of 30～50 DEG C and stir 1～2h, preparing N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product；
Step 4, at 0.06Mpa～-0.1Mpa, under conditions of 60 DEG C of hot water heat up, decompression distills out the carbon disulfide of excess in the N prepared by step 3, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product, i.e. obtain qualified N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester product.
In check analysis, the product prepared by step 4, the content of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is 91%, and yield is 95.8%.
Embodiment 3
A kind of N, the synthetic method of N-dibutyl dithio methyl acrylate sulphur nitrogen ester, N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is mining floating agent, it is prepared from by the raw material of following parts by weight: di-n-butylamine 48 parts, methyl acrylate 26 parts, carbon disulfide 26 parts, its preparation method comprises the following steps:
Step one, equipped with in the there-necked flask of condensation reflux unit, add 26 parts of carbon disulfide, 26 parts of methyl acrylates mix；
Step 2, being slowly added dropwise in there-necked flask by 48 parts of di-n-butylamines, rate of addition controls 0.5～1mL/min again, just the stirring of dropping limit, uses ice-water bath to cool down, control dropping temperature less than 20 DEG C in whipping process；
Step 3, treat step 2 dropping and after exothermic reaction terminates, be incubated under the conditions of 30～50 DEG C and stir 1～2h, preparing N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product；
Step 4, at 0.06Mpa～-0.1Mpa, under conditions of 60 DEG C of hot water heat up, decompression distills out the carbon disulfide of excess in the N prepared by step 3, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product, i.e. obtain qualified N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester product.
In check analysis, the product prepared by step 4, the content of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is 90%, and yield is 93.2%.
Embodiment 4
A kind of N, the synthetic method of N-dibutyl dithio methyl acrylate sulphur nitrogen ester, N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is mining floating agent, it is prepared from by the raw material of following parts by weight: di-n-butylamine 42 parts, methyl acrylate 28 parts, carbon disulfide 30 parts, its preparation method comprises the following steps:
Step one, equipped with in the there-necked flask of condensation reflux unit, add 30 parts of carbon disulfide, 28 parts of methyl acrylates mix；
Step 2, being slowly added dropwise in there-necked flask by 42 parts of di-n-butylamines, rate of addition controls 0.5～1mL/min again, just the stirring of dropping limit, uses ice-water bath to cool down, control dropping temperature less than 20 DEG C in whipping process；
Step 3, treat step 2 dropping and after exothermic reaction terminates, be incubated under the conditions of 30～50 DEG C and stir 1～2h, preparing N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product；
Step 4, at 0.06Mpa～-0.1Mpa, under conditions of 60 DEG C of hot water heat up, decompression distills out the carbon disulfide of excess in the N prepared by step 3, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product, i.e. obtain qualified N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester product.
In check analysis, the product prepared by step 4, the content of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is 91%, and yield is 92.6%.
Claims (3)
1. a N, the synthetic method of N-dibutyl dithio methyl acrylate sulphur nitrogen ester, N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester is mining floating agent, it is characterized in that: it is prepared from by the raw material of following parts by weight: di-n-butylamine 40～52 parts, methyl acrylate 20～32 parts, carbon disulfide 26～32 parts, its preparation method comprises the following steps:
Step one, equipped with in the there-necked flask of condensation reflux unit, add 6～32 parts of carbon disulfide, 20～32 parts of methyl acrylates mix；
Step 2, being slowly added dropwise in there-necked flask by 40～52 parts of di-n-butylamines, rate of addition controls 0.5～1mL/min again, just the stirring of dropping limit, uses ice-water bath to cool down, control dropping temperature less than 20 DEG C in whipping process；
Step 3, treat step 2 dropping and after exothermic reaction terminates, be incubated under the conditions of 30～50 DEG C and stir 1～2h, preparing N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product；
Step 4, decompression distill out the carbon disulfide of excess in the N prepared by step 3, N-dibutyl dithio methyl acrylate sulphur nitrogen ester crude product, i.e. obtain qualified N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester product.
The synthetic method of a kind of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester the most according to claim 1, it is characterised in that: the distillation condition that reduces pressure in described step 4 is 0.06Mpa～-0.1Mpa, and 60 DEG C of hot water heat up.
The synthetic method of a kind of N, N-dibutyl dithio methyl acrylate sulphur nitrogen ester the most according to claim 1, it is characterised in that: described di-n-butylamine, carbon disulfide and methyl acrylate raw material are AR.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438305A (en) * | 2018-11-16 | 2019-03-08 | 西北矿冶研究院 | Purification method of methyl dithioacrylate sulphur nitrogen ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4758362A (en) * | 1986-03-18 | 1988-07-19 | The Lubrizol Corporation | Carbamate additives for low phosphorus or phosphorus free lubricating compositions |
| US4963282A (en) * | 1989-05-11 | 1990-10-16 | The Lubrizol Corporation | Liquid compositions containing thiocarbamates |
| US5569644A (en) * | 1995-05-18 | 1996-10-29 | The Lubrizol Corporation | Additive combinations for lubricants and functional fluids |
| US5693598A (en) * | 1995-09-19 | 1997-12-02 | The Lubrizol Corporation | Low-viscosity lubricating oil and functional fluid compositions |
| US5759965A (en) * | 1995-10-18 | 1998-06-02 | The Lubrizol Corporation | Antiwear enhancing composition for lubricants and functional fluids |
| US6121211A (en) * | 1998-07-17 | 2000-09-19 | The Lubrizol Corporation | Engine oil having dithiocarbamate and aldehyde/epoxide for improved seal performance, sludge and deposit performance |
-
2016
- 2016-04-21 CN CN201610252637.9A patent/CN105859597A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4758362A (en) * | 1986-03-18 | 1988-07-19 | The Lubrizol Corporation | Carbamate additives for low phosphorus or phosphorus free lubricating compositions |
| US4963282A (en) * | 1989-05-11 | 1990-10-16 | The Lubrizol Corporation | Liquid compositions containing thiocarbamates |
| US5569644A (en) * | 1995-05-18 | 1996-10-29 | The Lubrizol Corporation | Additive combinations for lubricants and functional fluids |
| US5693598A (en) * | 1995-09-19 | 1997-12-02 | The Lubrizol Corporation | Low-viscosity lubricating oil and functional fluid compositions |
| US5759965A (en) * | 1995-10-18 | 1998-06-02 | The Lubrizol Corporation | Antiwear enhancing composition for lubricants and functional fluids |
| US6121211A (en) * | 1998-07-17 | 2000-09-19 | The Lubrizol Corporation | Engine oil having dithiocarbamate and aldehyde/epoxide for improved seal performance, sludge and deposit performance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438305A (en) * | 2018-11-16 | 2019-03-08 | 西北矿冶研究院 | Purification method of methyl dithioacrylate sulphur nitrogen ester |
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