CN102850247B - Preparation method of thiosulfuric acid derivative for rubber industry - Google Patents
Preparation method of thiosulfuric acid derivative for rubber industry Download PDFInfo
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Abstract
The present invention relates to an after-vulcanization stabilizer thiosulfuric acid derivative for rubber industry, especially to a preparation method for a thiosulfuric acid derivative. According to the preparation method, an alkaline buffer solution is adopted to adjust the pH value of a reaction solution to an alkaline state, such that an organic halogenated alkane and a water-soluble inorganic thiosulfate can be subjected to a complete reaction, and generation of a byproduct thiol compound is inhibited, such that reaction efficiency is effectively improved, the resulting product has high purity, and the preparation process has characteristics of simpleness, easy performing, and low energy consumption.
Description
Invention field
The invention belongs to rubber industry and use postcure stabiliser materials field, be specifically related to the preparation method of a kind of rubber industry Thiosulfuric acid derivant.
Background technology
The New-type adjuvant two hydration hexa-methylenes 1 of using as a kind of rubber industry, 6-dithio sulfuric acid disodium salt (Duralink HTS), its unique chemical structure makes it in vulcanization reaction, can between macromolecular S-S key, embed submissive hexa-methylene group, form composite crosslinking structure, the thermostability of cross-linked rubber is improved, thereby make the traditional vulcanization system that contains Duralink HTS can keep better dynamic property, as: tear and fatigue lifetime.
Duralink HTS is a kind of metal sodium salt with organic fatty chain, is that to be that raw material is synthetic with halogenated organic hydrocarbon (1,6-dichloro hexane) and Sulfothiorine obtain.Nineteen eighty-three U.S. Meng Shan has applied for the United States Patent (USP) that the patent No. is US4587296, employing water/organic solvent mixed solvent (as water/ethanol or water/ethylene glycol) is disclosed the earliest, temperature of reaction is 100～150 DEG C, the under reflux conditions preparation technology of thiosulphate and the reaction of organic dihalide, but, adopt this technique, in reaction process, cacodorous by product sulfur alcohol compound generates, thereby reduction productive rate, and make troubles to production.
After this, researchist is by constantly exploring, synthesize two hydration hexa-methylenes 1 by changing the means such as different solvents, differential responses condition, separation purification method, 6-dithio sulfuric acid disodium salt (Duralink HTS), on the one hand by changing reaction conditions, avoid thiosulphate and organic dihalide generation side reaction to generate sulfur alcohol compound, improve the productive rate of resultant; On the other hand, adopt different organic solvent (as methyl alcohol, acetone, Virahol etc.) and method for separating and processing, the content of sodium-chlor and Sulfothiorine in reduction product, the purity of raising Duralink HTS, improves yield.
Lanxess mentions along with the reacting of dichloro hexane and thiosulfate ion in US Patent No. 7217834, and reaction mixture becomes more aobvious acidity.In this patent, announce employing water and made solvent and avoid adding alcohol and/or glycol, avoided reaction soln souring by the pH value that adds organic bases or mineral alkali to carry out regulator solution on the other hand, reduced the generation of mercaptan compound, improved the transformation efficiency of thiosulphate.Although this method can effectively reduce side reaction, avoid generating the mercaptan compound of stench, but, need in process of production to introduce feeding equipment and continue to add organic bases or mineral alkali in reaction soln, and detect in real time the pH value of solution by pH electrode, make the pH value of reaction soln maintain 7.2 ± 0.1 always and avoid reaction soln to become acidity, can bring thus the increase in demand of production unit in plant produced, energy consumption increases.
UBE Industries Ltd. is that JP2005272330 and the patent No. are to adopt water/organic solvent to do reaction solvent in two sections of patents of JP2006306779 in the patent No., by adding sodium carbonate or sodium bicarbonate to regulate pH value to the alkalescence of reaction soln to prepare corresponding thiosulfuric acid sodium salt, after reaction finishes, filter and remove the halo an alkali metal salt that reaction generates by hot melt, wherein, organic solvent can be the water-miscible organic solvents such as methyl alcohol, acetone, acetonitrile, tetrahydrofuran (THF).In this method, adopted and had irritating volatile organic solvent, in reacting by heating and recycling process, organic solvent easily volatilizees, thereby reduces the security of production process.
The invention provides a kind of preparation method of new Thiosulfuric acid derivant, adopt water to make solvent, regulate the pH value of reaction soln with alkaline buffer solution, make reaction soln be stabilized in well alkaline environment, avoid thus in halogenated alkane and inorganic sulfur thiosulfate reaction process, reaction solution becomes acidic solution, can suppress the generation of by product mercaptan compound simultaneously, improve the purity of Thiosulfuric acid derivant, and preparation is simple, energy consumption is low.
Summary of the invention
In the present invention, do reaction solvent with water, adopt alkaline buffer solution to regulate the pH value of reaction soln to alkalescence, can make water-soluble inorganic thiosulphate and halogenated alkane react under stable alkaline condition, after reaction finishes by adding ethanol that Thiosulfuric acid derivant is separated out from reaction soln, after filtration drying.
Object of the present invention, is to provide a kind of technique simple, eco-friendly preparation technology, in alkaline buffer solution system, taking halogenated alkane and water-soluble inorganic thiosulphate as raw material China Synthetic Rubber Industry Thiosulfuric acid derivant.Specifically comprise following steps:
Step (1), the reaction vessel of mechanical stirring device, thermometer and reflux exchanger is equipped with in employing, taking water-soluble inorganic thiosulphate, to be dissolved in the pH value preparing be in 7.2～12.0 buffered soln, mechanical stirring is dissolved, and is mixed with the aqueous solution that inorganic sulfur thiosulfate volumetric molar concentration is 0.5～2.8mol/L;
Step (2) adds halogenated alkane under agitation condition, reacting by heating liquid, and controlling temperature of reaction is 80～120 DEG C, the pH value of solution is controlled at 7.0～12.0, under reflux conditions stirring reaction 4～9h;
Step (3), after reaction finishes, pours out solution and adds ethanol, separates out a large amount of solids after this solution is left standstill to 1～5h 0～20 DEG C time, filters out solid, and 45～55 DEG C obtain Thiosulfuric acid derivant after dry.
Wherein, water-soluble inorganic thiosulphate in step (1) can be the one in Sulfothiorine, Potassium Thiosulphate, ammonium thiosulfate, and alkaline buffer solution can be the one in boric acid-borax buffer solution, glycine-sodium hydroxide buffer solution, borax-sodium hydroxide buffer solution, Sodium phosphate dibasic-sodium hydroxide buffer solution, sodium bicarbonate-sodium hydroxide buffer solution;
In step (2), halogenated alkane can be chloroparaffin or brominated alkanes, and wherein, chloroparaffin is 1,4-dichlorobutane, 1,6-dichloro hexane, 1,8-bis-chloro-octanes, 1, one in 10-bis-chlorodecanes and 1,12-, bis-chlorododecanes, brominated alkanes is 1,4-dibromobutane, 1,6-bis-bromo-n-hexanes, 1,8-bis-bromooctanes, 1,10-dibromo-decane and 1, one in 12-dibromo-dodecane, water-soluble inorganic thiosulphate and halogenated alkane consumption mol ratio are 1.8: 1～2.1: 1;
In the ethanol adding in step (3) and step (1), the volume ratio of the aqueous solution is 1: 1～6: 1.
In the present invention, inorganic sulfur thiosulfate can use Sulfothiorine, Potassium Thiosulphate or ammonium thiosulfate to react with halogenated alkane, prepares corresponding Thiosulfuric acid derivant.The halogenated alkane adopting can be chloroparaffin, can be also brominated alkanes, under same reaction conditions, can obtain corresponding Thiosulfuric acid derivant.The present invention finishes to add ethanol to separate out target product in reaction, and ethanol can recycle and reuse, and reduces the pollution of production process to environment, and minimizing is produced the solvent bringing and consumed in a large number, reduces production costs.
Compared with prior art, usefulness is in the present invention:
(1) adopt alkaline buffer solution can effectively resist the fluctuation of solution acid-basicity in reaction process, the pH value that can control well reaction soln is alkalescence, do not need to introduce feeding equipment continues to add in reaction process, do not need the pH value of the real-time detection reaction solution of pH meter, thereby simplify production unit yet;
(2) can effectively solve solution souring, suppress the generation of by product mercaptan compound, improve reaction efficiency, improve product purity, reduce energy consumption;
(3) under reaction heating condition not with an organic solvent, reduce the volatilization of organic solvent, improve industrial security, preparation technology is environmental protection more.
Thiosulfuric acid derivant preparation process provided by the invention is simple, economical and effective, production technique 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 0.42g sodium bicarbonate and 0.04g sodium hydroxide, add 110mL water, to be mixed with pH value be sodium bicarbonate-sodium hydroxide buffer solution of 9.6 and be placed in reaction vessel, take 13.6g Sodium Thiosulfate Pentahydrate, join in above-mentioned solution, after mechanical stirring is dissolved, add while stirring 6.7g1, 6-bis-bromo-n-hexanes, the above-mentioned solution of heating heats up, make reacting liquid temperature rise to 102 DEG C, under reflux conditions after stirring reaction 5h, solution is poured out and added 110mL ethanol, there are a large amount of solids to separate out at 4 DEG C of standing 3h solution, filter out solid product, 45 DEG C 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 0.42g sodium bicarbonate and 0.04g sodium hydroxide, add 110mL water, to be mixed with pH value be sodium bicarbonate-sodium hydroxide buffer solution of 9.6 and be placed in reaction vessel, take 23.6g ammonium thiosulfate, join in above-mentioned solution, after mechanical stirring is dissolved, add while stirring 12.4g1, 6-dichloro hexane, the above-mentioned solution of heating heats up, make reacting liquid temperature rise to 80 DEG C, under reflux conditions after stirring reaction 6h, solution is poured out and added 200mL ethanol, there are a large amount of solids to separate out at 0 DEG C of standing 2h solution, filter out solid product, 55 DEG C obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid di-ammonium salts.
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 0.42g sodium bicarbonate and 0.09g sodium hydroxide, add 110mL water, to be mixed with pH value be sodium bicarbonate-sodium hydroxide buffer solution of 10.0 and be placed in reaction vessel, take 69.5g Sodium Thiosulfate Pentahydrate, join in above-mentioned solution, after mechanical stirring is dissolved, add while stirring 24.1g1, 6-dichloro hexane, the above-mentioned solution of heating heats up, make reacting liquid temperature rise to 90 DEG C, under reflux conditions after stirring reaction 9h, solution is poured out and added 600mL ethanol, there are a large amount of solids to separate out at 10 DEG C of standing 5h solution, filter out solid product, 50 DEG C 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 0.42g sodium bicarbonate and 0.18g sodium hydroxide, add 110mL water, to be mixed with pH value be sodium bicarbonate-sodium hydroxide buffer solution of 11.0 and be placed in reaction vessel, take 40.0g Potassium Thiosulphate, join in above-mentioned solution, after mechanical stirring is dissolved, add while stirring 15.5g1, 6-dichloro hexane, the above-mentioned solution of heating heats up, make reacting liquid temperature rise to 120 DEG C, under reflux conditions after stirring reaction 4h, solution is poured out and added 400mL ethanol, there are a large amount of solids to separate out at 5 DEG C of standing 3h solution, filter out solid product, 55 DEG C obtain two hydration hexa-methylenes 1 after dry, 6-dithio sulfuric acid di-potassium.
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 0.42g sodium bicarbonate and 0.18g sodium hydroxide, add 110mL water, to be mixed with pH value be sodium bicarbonate-sodium hydroxide buffer solution of 11.0 and be placed in reaction vessel, , take 33.0g Sodium Thiosulfate Pentahydrate, join in above-mentioned basic solution, after mechanical stirring is dissolved, add while stirring 12.5g1, 8-bis-chloro-octanes, the above-mentioned solution of heating heats up, make reacting liquid temperature keep reacting under 100 DEG C of conditions, under reflux conditions after stirring reaction 9h, pour out solution and add 400mL ethanol, this solution is placed in after 4 DEG C of standing 5h, filter out solid product, 55 DEG C obtain two hydration eight methylene radical 1 after dry, 8-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 0.82g bis-hypophosphite monohydrate sodium dihydrogens and 0.20g sodium hydroxide, add 100mL water, to be mixed with pH value be SODIUM PHOSPHATE, MONOBASIC-sodium hydroxide buffer solution of 12.0 and be placed in reaction vessel, take 33.0g Sodium Thiosulfate Pentahydrate, join in above-mentioned solution, after mechanical stirring is dissolved, add while stirring 8.5g1, 4-dichlorobutane, the above-mentioned solution of heating heats up, make reacting liquid temperature rise to 100 DEG C, under reflux conditions after stirring reaction 6h, solution is poured out and added 400mL ethanol, by solution at 5 DEG C of standing 3h, filter to isolate product, 50 DEG C obtain two hydration tetramethylenes 1 after dry, 4-dithio sulfuric acid disodium salt.
Embodiment 7～11 is according to the operating procedure of embodiment 6, reaction conditions is constant, the treating processes of reaction after product is constant, change the consumption of building-up process Raw, synthetic two hydration hexa-methylenes 1 in different alkaline buffer solution systems, 6-dithio sulfuric acid disodium salt, the consumption of raw material and the preparation of buffered soln are as shown in table 1.
Table 1. embodiment 7～11 Raw consumptions
According to the embodiment in embodiment 1, with Sodium Thiosulfate Pentahydrate and 1,6-, bis-bromo-n-hexanes, for raw material, the Thiosulfuric acid derivant obtaining is two hydration hexa-methylenes 1,6-dithio sulfuric acid disodium salt, and its chemical molecular formula is: NaO
3s
2(CH
2)
6s
2o
3na2H
2o.
Embodiment 1 is obtained to sample and adopts pellet technique test Fourier infrared spectra, conform to structural formula:
3564,3458,1619cm
-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
-1place: 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 2. above-described embodiment 1, obtain the results of elemental analyses of sample
| C(％) | H(％) | S(％) | NaCl(％) | |
| Calculated value | 18.46 | 4.10 | 32.82 | |
| Embodiment 1 | 17.96 | 3.98 | 30.81 | 0.62 |
Claims (5)
1. a preparation method for Thiosulfuric acid derivant for rubber industry, its feature is in containing following steps:
Step (1), the reaction vessel of mechanical stirring device, thermometer and reflux exchanger is equipped with in employing, taking water-soluble inorganic thiosulphate, to be dissolved in the pH value preparing be in 7.2～12.0 alkaline buffer solutions, mechanical stirring is dissolved, and is mixed with the alkaline aqueous solution that inorganic sulfur thiosulfate volumetric molar concentration is 0.5～2.8mol/L;
Step (2), under agitation condition, add halogenated alkane, reacting by heating liquid, controlling temperature of reaction is 80～120 DEG C, the pH value of solution is controlled at 7.2～12.0, under reflux conditions stirring reaction 4～9h, wherein water-soluble inorganic thiosulphate and halogenated alkane mol ratio are 1.8:1～2.1:1;
Step (3), after reaction finishes, pour out solution and add ethanol, this solution is left standstill after 1～5h under 0～10 DEG C of condition, filter to isolate product, 45～55 DEG C obtain Thiosulfuric acid derivant after dry, and the volume ratio of the middle aqueous solution of the ethanol wherein adding and step (1) is 1:1～6:1.
2. the preparation method of Thiosulfuric acid derivant according to claim 1, is characterized in that the water-soluble inorganic thiosulphate in step (1) can be the one in Sulfothiorine, Potassium Thiosulphate, ammonium thiosulfate.
3. the preparation method of Thiosulfuric acid derivant according to claim 1, is characterized in that the alkaline buffer solution in step (1) can be the one in boric acid-borax buffer solution, glycine-sodium hydroxide buffer solution, borax-sodium hydroxide buffer solution, Sodium phosphate dibasic-sodium hydroxide buffer solution, sodium bicarbonate-sodium hydroxide buffer solution.
4. the preparation method of Thiosulfuric acid derivant according to claim 1, is characterized in that the halogenated alkane in step (2) can be chloroparaffin or brominated alkanes.
5. the preparation method of Thiosulfuric acid derivant according to claim 4, is characterized in that described chloroparaffin is Isosorbide-5-Nitrae-dichlorobutane, 1,6-dichloro hexane, 1,8-bis-chloro-octanes, 1, the one in 10-bis-chlorodecanes and 1,12-, bis-chlorododecanes, brominated alkanes is 1,4-dibromobutane, 1,6-dibromo-hexane, 1,8-bis-bromooctanes, 1, one in 10-dibromo-decane and 1,12-dibromo-dodecane.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3054781A (en) * | 1959-03-24 | 1962-09-18 | Borden Co | Thiosulfate process of making organic polysulfides |
| US3153077A (en) * | 1960-03-08 | 1964-10-13 | Stevens & Co Inc J P | Process for preparing organic bis-thiosulfates |
| CN85102245A (en) * | 1985-04-01 | 1987-01-17 | 贵州省化工研究所 | The manufacture method of organic thiosulfate |
| CN1075956A (en) * | 1992-03-02 | 1993-09-08 | 段成钢 | The preparation method of organic thiosulfate raw powder |
| CN1699338A (en) * | 2004-04-15 | 2005-11-23 | 兰爱克谢斯德国有限责任公司 | Thiosulfuric acid derivant preparation |
| CN1861578A (en) * | 2006-05-25 | 2006-11-15 | 扬州大学 | Preparation process of post vulcanization agent dihydrated hexa methylene 1.6-disodium dithiosulfate |
-
2012
- 2012-09-06 CN CN201210325604.4A patent/CN102850247B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3054781A (en) * | 1959-03-24 | 1962-09-18 | Borden Co | Thiosulfate process of making organic polysulfides |
| US3153077A (en) * | 1960-03-08 | 1964-10-13 | Stevens & Co Inc J P | Process for preparing organic bis-thiosulfates |
| CN85102245A (en) * | 1985-04-01 | 1987-01-17 | 贵州省化工研究所 | The manufacture method of organic thiosulfate |
| CN1075956A (en) * | 1992-03-02 | 1993-09-08 | 段成钢 | The preparation method of organic thiosulfate raw powder |
| CN1699338A (en) * | 2004-04-15 | 2005-11-23 | 兰爱克谢斯德国有限责任公司 | Thiosulfuric acid derivant preparation |
| CN1861578A (en) * | 2006-05-25 | 2006-11-15 | 扬州大学 | Preparation process of post vulcanization agent dihydrated hexa methylene 1.6-disodium dithiosulfate |
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