CN102875435B - Organic thiosulfuric acid derivative preparation method - Google Patents
Organic thiosulfuric acid derivative preparation method Download PDFInfo
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Abstract
The invention provides an organic thiosulfuric acid derivative preparation method. The method specifically includes the steps: synthesizing organic thiosulfuric acid derivative in alkaline aqueous solution, adding acid solution to convert unreacted inorganic thiosulfate into other inorganic salts, filtering, and precipitating the organic thiosulfuric acid derivative from the solution by means of cooling and crystallizing. By the organic thiosulfuric acid derivative prepared by the method, influences of the inorganic thiosulfate in the product can be effectively reduced, so that product purity is improved. In addition, the preparation method is simple, feasible and environment-friendly, no organic solvent is added during preparation, and accordingly environment pollution during production is reduced.
Description
Technical field
The invention belongs to postcure stablizer organosulfur thiosulfuric acid derivant material field, particularly a kind of preparation method of organic Thiosulfuric acid derivant for rubber industry.
Background technology
About Monsanto Chemicals, at initial development 1980s Duralink HTS (two hydration hexa-methylenes 1,6-dithio sulfuric acid disodium salt), is used for improving the stability of polysulfide crosslink bond, but found afterwards that it can also increase processing safety.Duralink HTS contains sulphur atom and carbon atom, during sulfuration, HTS inserts a hexa-methylene disulfide group group in polysulfide crosslink bond, in cross-link bond structure, embed the softness of growing and the alkyl with thermostability, the generation of this composite crosslinking key can make the cross-linked rubber aging resistance of resistance to anaerobism improve, improve the thermostability of cross-link bond, thereby improve the flexibility of sizing material under dynamic operation, improve the antireversion of sizing material.
The synthetic method of relevant Duralink HTS, existing a lot of research and report.Duralink HTS is with 1,6-dichloro hexane and Sulfothiorine for raw material, and reacting by heating in water or water/organic solvent mixed solvent, syntheticly obtains hexa-methylene 1, and 6-dithio sulfuric acid disodium salt generates sodium-chlor simultaneously.Under industrial production condition; 1; 6-dichloro hexane price is far away higher than Sulfothiorine; from economic benefit, consider, conventionally can adopt that Sulfothiorine is excessive to reduce production costs, still; separate out in the process of product adding organic solvent; excessive Sulfothiorine meeting and hexa-methylene 1,6-dithio sulfuric acid disodium salt is separated out together from solution, thereby reduces the purity of product.
In Chinese patent CN200610040688.1, propose normal temperature alcohol crystal method and carried out separation and purification product, after building-up reactions, added ethanol, after 70～90 ℃ of backflows, be cooled to 60～70 ℃, added water, filtered the product that obtains crystallization.Although avoided use methyl alcohol in the present invention, improved the purity of product,, after alcohol reflux, add water can make part hexa-methylene 1,6-dithio sulfuric acid disodium salt is dissolved in water, and product yield reduces.
In the patent document that Lanxess is US7217834 at U.S. Patent number, mention the carrying out reacting with thiosulfate ion along with 1,6-dichloro hexane, the reaction mixture more aobvious acidity that becomes.Adopt water to make solvent and avoid adding alcohol and/or glycol, by volume pump, in reaction process, continue to add on the other hand organic bases or mineral alkali, avoid reaction soln aobvious acid, improve transformation efficiency, this preparation technology can reduce the generation of sulfur alcohol compound, but from results of elemental analyses, see that embodiment obtains S content in product and differs less, and C and H numerical value and calculated value differ larger, as C constituent content is compared with calculated value, differ 1.16%, the purity that explanation obtains product by this production technique is slightly not enough, may be owing to may having other impurity in product, as inorganic sulfur sodium thiosulfate.
Although adopt published preparation method can obtain product---organic Thiosulfuric acid derivant, but due to Sulfothiorine and organic Thiosulfuric acid derivant---hexa-methylene 1,6-dithio sulfuric acid disodium salt is all dissolved in water, be insoluble to organic solvent, cause the organic Thiosulfuric acid derivant being difficult to thiosulfuric acid sodium impurity to be purified.The present invention proposes a kind of simple treatment process, after organic halogenated alkane complete reaction, add acid solution, the pH value of regulator solution be 6.5～7 stablize constant after, crystallisation by cooling can obtain organic Thiosulfuric acid derivant.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of organic Thiosulfuric acid derivant, specifically in alkaline aqueous solution, make organic halogenated alkane and inorganic water-soluble thiosulfuric acid reactant salt, after reaction finishes, add acid solution to react with the excessive inorganic sulfur thiosulfate reacting of not participating in, inorganic sulfur thiosulfate is changed into other inorganic salts, due to different inorganic salts different solubilities, mode by crystallisation by cooling is separated out the organic Thiosulfuric acid derivant generating from solution, and inorganic salts is still dissolved in water, thereby improve the purity of organic Thiosulfuric acid derivant, and reduce the use of organic solvent.
The preparation method of organic Thiosulfuric acid derivant provided by the invention, comprises the following steps:
Step (1), adopts the reaction vessel that mechanical stirring device, thermometer and reflux exchanger are housed, and takes water-soluble inorganic thiosulphate and is placed in reaction vessel, adds water mechanical stirring to dissolve, and is mixed with the aqueous solution of inorganic sulfur thiosulfate;
Step (2) adds halogenated alkane under agitation condition, and intensification reacting by heating liquid is to temperature of reaction;
Step (3), adopts peristaltic pump to add aqueous sodium hydroxide solution, makes the pH value of reaction soln be controlled at 7～9, under reflux conditions stirring reaction 4～9h;
Step (4), after reaction finishes, stop adding sodium hydroxide solution, slowly add acid solution, the pH value of solution is remained 6.5～7 constant, pour out solution, separate out a large amount of solids after this solution being placed in to 0～10 ℃ of standing 1～6h after filtration, filter out solid, 45～55 ℃ obtain organic Thiosulfuric acid derivant after dry.
Wherein, the water-soluble inorganic thiosulphate in step (1) can be a kind of in Sulfothiorine, Potassium Thiosulphate, ammonium thiosulfate, preferred Sulfothiorine, and the mass percentage concentration of inorganic sulfur thiosulfate is 10%～40%.
Halogenated alkane can be a kind of in 1,6-dichloro hexane and 1,6-dibromo-hexane in step (2), and water-soluble inorganic thiosulphate and halogenated alkane consumption mol ratio are 1.8: 1～2.2: 1, and the temperature of reaction in step (2) is 80～120 ℃.
The mass percentage concentration of the sodium hydroxide solution in step (3) is 1%～2%.
Acid in step (4) can be a kind of in hydrochloric acid, sulfuric acid, nitric acid, from industrial production security standpoint, considers, and preferred hydrochloric acid, the mass percentage concentration of hydrochloric acid soln is 0.05～5%.
The halogenated alkane adopting in the present invention can be chloroparaffin, can be also brominated alkanes, can obtain corresponding organic Thiosulfuric acid derivant under same reaction conditions.In reaction, finish to separate out product by the mode of crystallisation by cooling, in whole preparation process without adding organic solvent, thereby reduce the pollution of production process to environment.
Compared with prior art, usefulness is in the present invention:
(1) can effectively remove the impact of the rear inorganic sulfur sodium thiosulfate of reaction, improve the purity of organic Thiosulfuric acid derivant;
(2) in reaction process, do not add organic solvent, reduce the pollution to environment, preparation technology is environmental protection more; Meanwhile, the alkaline solution that adds acid to add in can neutralization reaction process after reaction finishes, has avoided the aftertreatment of basic solution.
Technique of the present invention is simple, energy consumption is low, reproducible, meet the developing direction of safety, green, environmental protection, therefore there is great development prospect.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.It should be noted that; what below enumerate is only some specific embodiments of the present invention; obviously in the present invention, these embodiment are only not used in and limit the scope of the invention for the present invention's that explains in detail technical scheme; all distortion that other directly derive or associate from content of the present invention, all should think protection scope of the present invention.
Embodiment 1
Mechanical stirring device is equipped with in employing, the 200mL four-hole boiling flask of thermometer and reflux exchanger is as reaction vessel, take 12.4g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding 100mL water mechanical stirring to dissolve, add while stirring 3.9g1, 6-dichloro hexane, the above-mentioned solution of heating heats up, while making reacting liquid temperature rise to 100 ℃, by peristaltic pump, slowly add 1% sodium hydroxide solution, regulating the pH value of reaction soln is 7.5, under reflux conditions after stirring reaction 6h, stop adding sodium hydroxide solution, the pH value of the hydrochloric acid soln regulator solution that dropping concentration is 0.05% is 7, solution is poured out, after filtration, at 4 ℃ of standing 3h, there are a large amount of solids to separate out, filter out solid product, 45 ℃ obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid disodium salt.
Embodiment 2
Mechanical stirring device is equipped with in employing, the 200mL four-hole boiling flask of thermometer and reflux exchanger is as reaction vessel, take 24.8g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding 100mL water mechanical stirring to dissolve, add while stirring 7.4g1, 6-dichloro hexane, the above-mentioned solution of heating heats up, while making reacting liquid temperature rise to 90 ℃, by peristaltic pump, slowly add 1.2% sodium hydroxide solution, regulating the pH value of reaction soln is 7, under reflux conditions after stirring reaction 9h, stop adding sodium hydroxide solution, the pH value of the hydrochloric acid soln regulator solution that dropping concentration is 0.5% is 6.5, solution is poured out, after filtration, at 0 ℃ of standing 1h, there are a large amount of solids to separate out, filter out solid product, 55 ℃ obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid disodium salt.
Embodiment 3
Mechanical stirring device is equipped with in employing, the 200mL four-hole boiling flask of thermometer and reflux exchanger is as reaction vessel, take 52.1g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding 100mL water mechanical stirring to dissolve, add while stirring 14.8g1, 6-dichloro hexane, the above-mentioned solution of heating heats up, while making reacting liquid temperature rise to 115 ℃, by peristaltic pump, slowly add 2% sodium hydroxide solution, regulating the pH value of reaction soln is 9, under reflux conditions after stirring reaction 6h, stop adding sodium hydroxide solution, the pH value of the hydrochloric acid soln regulator solution that dropping concentration is 0.1% is 7, solution is poured out, after filtration, at 5 ℃ of standing 1h, there are a large amount of solids to separate out, filter out solid product, 45 ℃ obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid disodium salt.
Embodiment 4
Mechanical stirring device is equipped with in employing, the 200mL four-hole boiling flask of thermometer and reflux exchanger is as reaction vessel, take 19.8g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding 120mL water mechanical stirring to dissolve, add while stirring 6.9g1, 6-dichloro hexane, the above-mentioned solution of heating heats up, make reacting liquid temperature keep reacting under 100 ℃ of conditions, by peristaltic pump, slowly add 1% sodium hydroxide solution, regulating the pH value of reaction soln is 8, under reflux conditions after stirring reaction 5h, stop adding sodium hydroxide solution, the pH value of the hydrochloric acid soln regulator solution that dropping concentration is 3% is 7, pour out solution, filtration is placed on after 4 ℃ of standing 5h, filter out solid product, 55 ℃ obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid disodium salt.
Embodiment 5
Mechanical stirring device is equipped with in employing, the 200mL four-hole boiling flask of thermometer and reflux exchanger is as reaction vessel, take 39.6g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding 120mL water mechanical stirring to dissolve, add while stirring 19.6g1, 6-dibromo-hexane, the above-mentioned solution of heating heats up, make reacting liquid temperature remain on 80 ℃, by peristaltic pump, slowly add 1.5% sodium hydroxide solution, regulating the pH value of reaction soln is 9, under reflux conditions after stirring reaction 7h, stop adding sodium hydroxide solution, the pH value of the hydrochloric acid soln regulator solution that dropping concentration is 5% is 9, pour out solution, filtration is placed on after 10 ℃ of standing 6h, filter out solid product, 50 ℃ obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid disodium salt.
Embodiment 6
Mechanical stirring device is equipped with in employing, the 200mL four-hole boiling flask of thermometer and reflux exchanger is as reaction vessel, take 19.8g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding 120mL water mechanical stirring to dissolve, add while stirring 10.3g1, 6-dibromo-hexane, the above-mentioned solution of heating heats up, make reacting liquid temperature keep reacting under 90 ℃ of conditions, by peristaltic pump, slowly add 1% sodium hydroxide solution, regulating the pH value of reaction soln is 8, under reflux conditions after stirring reaction 4h, stop adding sodium hydroxide solution, the pH value of the hydrochloric acid soln regulator solution that dropping concentration is 2% is 7, pour out solution, filtration is placed on after 4 ℃ of standing 5h, filter out solid product, 55 ℃ obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid disodium salt.
According to the embodiment in embodiment 1, with Sodium Thiosulfate Pentahydrate and 1,6-dichloro hexane for raw material, the two hydration hexa-methylenes 1 that obtain, 6-dithio sulfuric acid disodium salt chemical molecular formula is: NaO
3s
2(CH
2)
6s
2o
3na2H
2o.
Embodiment 1 is obtained to sample and adopts pellet technique test infrared spectra, conform to structural formula:
3564,3457,1619cm
-1: the infrared absorption peak of OH in crystal water
2927,2858,1465cm
-1: methylene radical symmetry and antisymmetric stretching vibration peak
1216,1043cm
-1: the symmetry of S=O and antisymmetric stretching vibration peak
728cm
-1: the charateristic avsorption band of methylene radical wagging vibration
The sample obtaining is carried out to ultimate analysis, test C, H wherein, the percentage composition of tri-kinds of elements of S, and test the percentage composition of NaCl in sample, result is as follows:
In table 1. above-described embodiment 1, obtain the results of elemental analyses of sample
Claims (6)
1. a preparation method for organic Thiosulfuric acid derivant, is characterized in that containing following steps:
Step (1), adopts the reaction vessel that mechanical stirring device, thermometer and reflux exchanger are housed, and takes Sulfothiorine and is placed in reaction vessel, adds water mechanical stirring to dissolve, and is mixed with the aqueous solution of Sulfothiorine;
Step (2) adds halo hexane under agitation condition, and intensification reacting by heating liquid is to temperature of reaction;
Step (3), adopts peristaltic pump to add aqueous sodium hydroxide solution, makes the pH value of reaction soln be controlled at 7.5～9, under reflux conditions stirring reaction 4～9h;
Step (4), after reaction finishes, stop adding sodium hydroxide solution, slowly add acid solution, the pH value of solution is remained 6.5～7 constant, pour out solution, separate out a large amount of solids after this solution being placed in to 0～10 ℃ of standing 1～6h after filtration, filter out solid, 45～55 ℃ obtain organic Thiosulfuric acid derivant after dry;
Wherein, the halo hexane described in step (2) can be a kind of in 1,6-dichloro hexane and 1,6-dibromo-hexane, and the organic Thiosulfuric acid derivant described in step (4) is two hydration hexa-methylenes 1,6-dithio sulfuric acid disodium salt.
2. preparation method as claimed in claim 1, the mass percentage concentration that it is characterized in that described sodium thiosulfate solution is 10%～40%.
3. preparation method as claimed in claim 1, is characterized in that described Sulfothiorine and halo hexane consumption mol ratio are 1.8: 1～2.2: 1.
4. preparation method as claimed in claim 1, is characterized in that the temperature of reaction described in step (2) is 80～120 ℃.
5. preparation method as claimed in claim 1, the mass percentage concentration that it is characterized in that the sodium hydroxide solution described in step (3) is 1%～2%.
6. preparation method as claimed in claim 1, is characterized in that described acid can be hydrochloric acid, and the mass percentage concentration of hydrochloric acid soln is 0.05～5%.
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| CN103130697A (en) * | 2013-02-26 | 2013-06-05 | 北京彤程创展科技有限公司 | Preparation method of post-vulcanization stabilizing agent organic thiosulfate |
| CN103819377B (en) * | 2013-12-16 | 2016-01-06 | 菏泽佳成化工有限公司 | The preparation method of two hydration hexa-methylene 1,6-bisthiosulfate disodium salts |
| CN103788372B (en) * | 2013-12-27 | 2016-01-20 | 北京彤程创展科技有限公司 | A kind of polymkeric substance containing polythiaether structure and preparation method thereof |
| CN105218419B (en) * | 2015-10-14 | 2017-03-29 | 北京彤程创展科技有限公司 | A kind of preparation method of organic mercaptan zinc salt |
| CN110294700A (en) * | 2019-07-05 | 2019-10-01 | 山东阳谷华泰化工股份有限公司 | A kind of synthetic method of two hydrations hexa-methylene -1,6- bisthiosulfate disodium salt |
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| CN85102245A (en) * | 1985-04-01 | 1987-01-17 | 贵州省化工研究所 | The manufacture method of organic thiosulfate |
| EP1586563A2 (en) * | 2004-04-15 | 2005-10-19 | Lanxess Deutschland GmbH | Preparation of thiosulphuric acid derivatives |
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| CN85102245A (en) * | 1985-04-01 | 1987-01-17 | 贵州省化工研究所 | The manufacture method of organic thiosulfate |
| EP1586563A2 (en) * | 2004-04-15 | 2005-10-19 | Lanxess Deutschland GmbH | Preparation of thiosulphuric acid derivatives |
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