CN112142631A - Synthesis process of high-purity sodium polydithio-dipropyl sulfonate - Google Patents
Synthesis process of high-purity sodium polydithio-dipropyl sulfonate Download PDFInfo
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- CN112142631A CN112142631A CN202011065367.3A CN202011065367A CN112142631A CN 112142631 A CN112142631 A CN 112142631A CN 202011065367 A CN202011065367 A CN 202011065367A CN 112142631 A CN112142631 A CN 112142631A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis process of high-purity sodium polydithio-dipropyl sulfonate, which comprises the following steps: adding sodium sulfide, sulfur powder and alkali into a solvent, heating to react for a period of time, adding 1, 3-propane sultone, heating to react for a period of time, cooling, adding an oxidant, continuing to react for a period of time, and performing aftertreatment to obtain the sodium polydithio-dipropyl sulfonate. In the scheme, a side reaction product of sodium sulfide and sulfur powder and alkali are subjected to disproportionation reaction to reduce byproducts, and an oxidant is added to react sodium thiosulfate synchronously generated in the disproportionation reaction with 1, 3-propane sultone to generate a target product sodium polydithio-dipropyl sulfonate.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis process of high-purity sodium polydithio-dipropyl sulfonate.
Background
The sodium polydithio-dipropyl sulfonate SPS is used as an acid copper plating intermediate, belongs to a main additive component in a copper plating additive, can play a role in refining the crystallization of a plating layer and effectively improving the current density, and can be used as an acid copper plating brightener to obtain a decorative and functional plating layer.
In recent years, sodium polydithio-dipropyl sulfonate (SPS) is also widely used for producing electrolytic copper foil of lithium batteries, and the SPS plays the roles of a grain refiner, a brightener and a leveler in the copper foil production process, and can improve the tensile strength and the elongation of the electrolytic copper foil.
At present, the requirement of sodium polydithio-dipropyl sulfonate (SPS) is large in the whole markets of electrolytic copper foil and acid copper plating intermediates, but the preparation process of the product has the prominent problems of insufficient purity and more impurities, so that the application of the product in the markets is limited.
Disclosure of Invention
The method is based on sodium sulfide, sulfur powder and 1, 3-propane sultone as raw materials, and the ideal reaction process is that the sodium sulfide and the sulfur powder react to generate sodium disulfide Na2S2Then reacting with 1, 3-propane sultone to obtain sodium polydithio-dipropyl sulfonate SPS, but the synthetic method has the defects that: the side reaction between sodium sulfide and sulfur powder is excessive, so that a large amount of polysulfide impurities (such as sodium trisulfide Na) are easily generated2S3) The impurities participate in the subsequent reaction, which results in that the purity of the produced sodium polydithio-dipropyl sulfonate SPS is too low,
in order to solve the technical problem, the invention provides a synthesis process of high-purity sodium polydithio-dipropyl sulfonate, which comprises the following steps:
(1) adding sodium sulfide, sulfur powder and alkali into a solvent, heating and reacting for a period of time,
wherein, the solvent is the mixture of water and alcohol or other (except water) hydrophilic solvents, and this mixed solvent is favorable to improving the mixed state of sodium sulfide and sulphur powder, and when water and alcohol mix as the solvent, the mass ratio of water and alcohol is 8 ~ 1: 2 to 9 parts of a first resin composition,
the dosage of the sulfur powder is 0.5-1.5 mol times of the sodium sulfide,
the alkali is sodium hydroxide or potassium hydroxide, etc., the dosage is determined according to the amount of the polysulfide compound impurities generated under different reaction conditions,
the temperature rise reaction is carried out at 60-100 ℃ for 0.5-4 hours, and the reaction can be carried out under normal pressure or under pressure (the same as the step (2));
(2) adding 1, 3-propane sultone into the reaction system obtained in the step (1), heating for reaction for a period of time, cooling, performing post-treatment to obtain sodium polydithio-dipropyl sulfonate,
the temperature rise reaction is carried out by raising the temperature to 70-120 ℃, the reaction time is 1-15 hours,
preferably, after cooling, adding an oxidant into the reaction system in the step (2), continuing the reaction for a period of time, and then carrying out post-treatment,
the oxidant is hydrogen peroxide or potassium permanganate, the reaction temperature after the oxidant is added is 10-50 ℃, the reaction time is 0.5-2 hours,
the post-processing operation is as follows: and (3) adding activated carbon into the reaction system obtained in the step (2) for decoloring, filtering to remove the activated carbon, concentrating the obtained filtrate, crystallizing by using ethanol, and centrifugally drying.
In the process of generating sodium disulfide by reacting sodium sulfide and sulfur powder in the step (1), a side reaction product (polysulfide impurity) and added alkali are subjected to disproportionation reaction to generate sodium disulfide again, so that the amount of by-products is reduced, for example:
6Na2S3+6NaOH＝8Na2S2+Na2S2O3+3H2O
considering that in the process there is sodium thiosulfate Na2S2O3Thus, adding an oxidizing agent to the reaction mixture in step (2) to promote the formation of sodium thiosulfate Na2S2O3And reacting with 1, 3-propane sultone to generate the target product of sodium polydithio-dipropyl sulfonate.
Detailed Description
Example 1
140g of 60 wt% sodium sulfide (56.0 g of crystal water, Na) was added to the reaction flask at room temperature under normal pressure284.0g of S), 34g of sulfur powder, 12.1g of anhydrous sodium hydroxide, 80.0g of methanol and 130g of water, and stirring and reacting for 2 hours at 65 ℃; after cooling to normal temperature, 190g of 1, 3-propane sultone is added into the mixture, and the mixture is stirred and reacted for 8 hours at 80 ℃; cooling to 45 deg.C, adding hydrogen peroxide (H)2O230%) 17g and reacted at 45 c with stirring for 1 hour,
adding sufficient active carbon into the obtained reaction system, fully stirring, filtering to remove the active carbon, concentrating the obtained filtrate at 60 ℃ under reduced pressure until the mass percent of the solvent is 25%, crystallizing by using ethanol, cooling to normal temperature, centrifuging and drying to obtain 220g of sodium polydithio-dipropyl sulfonate, wherein the purity of the sodium polydithio-dipropyl sulfonate is 95.8% by HPLC detection.
Comparative example 1
The preparation method is carried out according to the traditional process for preparing the sodium polydithio-dipropyl sulfonate from the sodium sulfide, the sulfur powder and the 1, 3-propane sultone, alkali and an oxidant are not used, and the rest components and the operation are the same as those in the embodiment 1:
140g of 60 wt% sodium sulfide (56.0 g of crystal water, Na) was added to the reaction flask at room temperature under normal pressure284.0g of S), 34g of sulfur powder, 80.0g of methanol and 130g of water, and stirring and reacting for 2 hours at 65 ℃; after cooling to normal temperature, 190g of 1, 3-propane sultone is added into the mixture, and the mixture is stirred and reacted for 8 hours at 80 ℃; cooling to 45 ℃, continuing stirring and reacting for 1 hour,
adding sufficient active carbon into the obtained reaction system, fully stirring, filtering to remove the active carbon, concentrating the obtained filtrate at 60 ℃ under reduced pressure until the mass percent of the solvent is 25%, crystallizing by using ethanol, cooling to normal temperature, centrifuging and drying to obtain 215.3g of product, wherein the purity of the product is 78.7% by HPLC detection.
Claims (7)
1. A synthesis process of high-purity sodium polydithio-dipropyl sulfonate is characterized by comprising the following steps: the synthesis process comprises
(1) Adding sodium sulfide, sulfur powder and alkali into a solvent, heating and reacting for a period of time,
(2) and (2) adding 1, 3-propane sultone into the reaction system obtained in the step (1), heating to react for a period of time, cooling, and performing aftertreatment to obtain the sodium polydithio-dipropyl sulfonate.
2. The process for synthesizing sodium polydithiodipropanesulfonate as claimed in claim 1, wherein: and (3) after cooling in the step (2), adding an oxidant into the obtained reaction system, continuing to react for a period of time, and then performing the post-treatment.
3. The process for synthesizing sodium polydithiodipropanesulfonate as claimed in claim 2, wherein: the oxidant is hydrogen peroxide or potassium permanganate, the reaction temperature after the oxidant is added is 10-50 ℃, and the reaction time is 0.5-2 hours.
4. The process for synthesizing sodium polydithiodipropanesulfonate as claimed in claim 1, wherein: the solvent in the step (1) is a mixture of water and a hydrophilic solvent except water.
5. The process for synthesizing sodium polydithiodipropanesulfonate as claimed in claim 1, wherein: in the step (1), the amount of the sulfur powder is 0.5-1.5 molar times of that of the sodium sulfide.
6. The process for synthesizing sodium polydithiodipropanesulfonate as claimed in claim 1, wherein: the temperature rise reaction in the step (1) is carried out until the temperature rises to 60-100 ℃, and the reaction time is 0.5-4 hours.
7. The process for synthesizing sodium polydithiodipropanesulfonate as claimed in claim 1, wherein: the temperature rise reaction in the step (2) is carried out until the temperature rises to 70-120 ℃, and the reaction time is 1-15 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114853645A (en) * | 2022-04-22 | 2022-08-05 | 苏州亚科科技股份有限公司 | Preparation process of sodium polydithio-dipropyl sulfonate |
Citations (4)
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| CN101519369A (en) * | 2009-04-03 | 2009-09-02 | 武汉中德远东精细化工有限公司 | Synthetic method of sodium polydithio-dipropyl sulfonate |
| CN106810481A (en) * | 2016-12-30 | 2017-06-09 | 武汉工程大学 | A kind of new synthetic method of sodium polydithio-dipropyl sulfonate |
| CN106946753A (en) * | 2017-02-21 | 2017-07-14 | 湖北吉和昌化工科技有限公司 | The synthesis technique of sodium polydithio-dipropyl sulfonate |
| CN107686458A (en) * | 2017-09-29 | 2018-02-13 | 江苏梦得新材料科技有限公司 | A kind of synthetic method of sodium polydithio-dipropyl sulfonate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519369A (en) * | 2009-04-03 | 2009-09-02 | 武汉中德远东精细化工有限公司 | Synthetic method of sodium polydithio-dipropyl sulfonate |
| CN106810481A (en) * | 2016-12-30 | 2017-06-09 | 武汉工程大学 | A kind of new synthetic method of sodium polydithio-dipropyl sulfonate |
| CN106946753A (en) * | 2017-02-21 | 2017-07-14 | 湖北吉和昌化工科技有限公司 | The synthesis technique of sodium polydithio-dipropyl sulfonate |
| CN107686458A (en) * | 2017-09-29 | 2018-02-13 | 江苏梦得新材料科技有限公司 | A kind of synthetic method of sodium polydithio-dipropyl sulfonate |
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| 杨永等: "阴离子表面活性剂聚二硫二丙烷磺酸钠的合成", 《广州化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853645A (en) * | 2022-04-22 | 2022-08-05 | 苏州亚科科技股份有限公司 | Preparation process of sodium polydithio-dipropyl sulfonate |
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