CN102875435A - Organic thiosulfuric acid derivative preparation method - Google Patents
Organic thiosulfuric acid derivative preparation method Download PDFInfo
- Publication number
- CN102875435A CN102875435A CN2012103663356A CN201210366335A CN102875435A CN 102875435 A CN102875435 A CN 102875435A CN 2012103663356 A CN2012103663356 A CN 2012103663356A CN 201210366335 A CN201210366335 A CN 201210366335A CN 102875435 A CN102875435 A CN 102875435A
- Authority
- CN
- China
- Prior art keywords
- preparation
- solution
- organic
- reaction
- thiosulphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 rubber industry postcure stablizer organosulfur thiosulfuric acid derivant material field, particularly a kind of preparation method of organic Thiosulfuric acid derivant.
Background technology
About Monsanto Chemicals is used for improving the stability of polysulfide crosslink bond, but found afterwards that it can also increase processing safety at initial development 1980s Duralink HTS (two hydration hexa-methylenes 1,6-dithio sulfuric acid disodium salt).Duralink HTS contains sulphur atom and carbon atom, HTS inserts a hexa-methylene disulfide group group during sulfuration in polysulfide crosslink bond, embed long softness and the alkyl with thermostability in the cross-link bond structure, the generation of this composite crosslinking key can make the cross-linked rubber aging resistance of anti-the 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 researchs and report.Duralink HTS is raw material with 1,6-dichloro hexane and Sulfothiorine, and reacting by heating in water or water/organic solvent mixed solvent synthetic obtains hexa-methylene 1, and 6-dithio sulfuric acid disodium salt generates sodium-chlor simultaneously.Under the industrial production condition; 1; 6-dichloro hexane price is higher than Sulfothiorine far away; consider from economic benefit, can adopt usually that Sulfothiorine is excessive to reduce production costs, still; separate out in the process of product at the adding organic solvent; excessive Sulfothiorine meeting and hexa-methylene 1,6-dithio sulfuric acid disodium salt is separated out from solution together, thereby reduces the purity of product.
Propose normal temperature alcohol crystal method among the Chinese patent CN200610040688.1 and come the separation and purification product, after building-up reactions, added ethanol, be cooled to 60~70 ℃ after 70~90 ℃ of backflows, added entry, filtered the product that obtains crystallization.Although avoided use methyl alcohol among the present invention, improved the purity of product,, adding the entry meeting behind the alcohol reflux and make part hexa-methylene 1,6-dithio sulfuric acid disodium salt is dissolved in the water, and product yield reduces.
Lanxess mentions the carrying out along with 1,6-dichloro hexane and thiosulfate ion reaction in U.S. Patent number is the patent document of US7217834, the reaction mixture more aobvious acidity that becomes.Adopt water to make solvent and avoid adding alcohol and/or glycol, in reaction process, continue to add organic bases or mineral alkali by volume pump on the other hand, avoid reaction soln aobvious acid, improve transformation efficiency, this preparation technology can reduce the generation of sulfur alcohol compound, but see that from results of elemental analyses embodiment obtains that S content differs less in the product, and C and H numerical value and calculated value differ larger, compare with calculated value such as the C constituent content, differ 1.16%, explanation is slightly not enough by the purity that this production technique obtains product, may be may have other impurity owing in the product, such as the inorganic sulfur sodium thiosulfate.
Although adopt published preparation method can obtain product---organic Thiosulfuric acid derivant, but because Sulfothiorine and organic Thiosulfuric acid derivant---hexa-methylene 1,6-dithio sulfuric acid disodium salt all is dissolved in water, be insoluble to organic solvent, cause to be difficult to and to purify with organic Thiosulfuric acid derivant of thiosulfuric acid sodium impurity.The present invention proposes a kind of simple treatment process, after the 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 purpose 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 and the excessive inorganic sulfur thiosulfate reaction of not participating in reaction, the inorganic sulfur thiosulfate is changed into other inorganic salts, because different inorganic salts different solubility, organic Thiosulfuric acid derivant that mode by crystallisation by cooling will generate is separated out from solution, and inorganic salts still is dissolved in the 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 may further comprise the steps:
Step (1) adopts the reaction vessel that mechanical stirring device, thermometer and reflux exchanger are housed, and takes by weighing the water-soluble inorganic thiosulphate and places reaction vessel, adds the dissolving of entry mechanical stirring, is mixed with the aqueous solution of inorganic sulfur thiosulfate;
Step (2) adds halogenated alkane under agitation condition, 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 refluxad stirring reaction 4~9h;
Step (4), after reaction finishes, stop to add 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 placing 0~10 ℃ to leave standstill 1~6h this solution after the filtration, filter out solid, namely get organic Thiosulfuric acid derivant after 45~55 ℃ of dryings.
Wherein, the water-soluble inorganic thiosulphate in the step (1) can be a kind of in Sulfothiorine, Potassium Thiosulphate, the 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, the 6-dibromo-hexane in the 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 the step (2) is 80~120 ℃.
The mass percentage concentration of the sodium hydroxide solution in the step (3) is 1%~2%.
Acid in the step (4) can be a kind of in hydrochloric acid, sulfuric acid, the nitric acid, considers from the industrial production security standpoint, preferred hydrochloric acid, and the mass percentage concentration of hydrochloric acid soln is 0.05~5%.
The halogenated alkane that adopts among the present invention can be chloroparaffin, also can be brominated alkanes, can obtain corresponding organic Thiosulfuric acid derivant under same reaction conditions.Finish to separate out product by the mode of crystallisation by cooling in reaction, need not to add organic solvent in the whole preparation process, thereby reduce production process to the pollution of environment.
The present invention compared with prior art, usefulness is:
(1) can effectively remove the impact of reacting rear inorganic sulfur sodium thiosulfate, improve the purity of organic Thiosulfuric acid derivant;
(2) do not add organic solvent in the reaction process, reduce the pollution to environment, preparation technology is environmental protection more; Simultaneously, after reaction finishes, add the alkaline solution that acid adds in can the neutralization reaction process, avoided the aftertreatment of basic solution.
Technique of the present invention is simple, energy consumption is low, good reproducibility, meets the developing direction of safety, green, environmental protection, therefore has great development prospect.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.It should be noted that; what below enumerate only is some specific embodiments of the present invention; these embodiment only are not used in for the present invention's that explains in detail technical scheme and limit the scope of the invention among obvious the present invention; all distortion that other are directly derived from content of the present invention or associate all should be thought 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 by weighing the 12.4g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding the dissolving of 100mL water mechanical stirring, add while stirring 3.9g1, the 6-dichloro hexane, the heating mentioned solution heats up, when making reacting liquid temperature rise to 100 ℃, slowly add 1% sodium hydroxide solution by peristaltic pump, the pH value of conditioned reaction solution is 7.5, under refluxad behind the stirring reaction 6h, stops to add sodium hydroxide solution, the pH value that drips concentration and be 0.05% hydrochloric acid soln regulator solution is 7, solution is poured out, and leaving standstill 3h at 4 ℃ after filtering has a large amount of solids to separate out, and filters out solid product, namely get two hydration hexa-methylenes 1 after 45 ℃ of dryings, 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 by weighing the 24.8g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding the dissolving of 100mL water mechanical stirring, add while stirring 7.4g1, the 6-dichloro hexane, the heating mentioned solution heats up, when making reacting liquid temperature rise to 90 ℃, slowly add 1.2% sodium hydroxide solution by peristaltic pump, the pH value of conditioned reaction solution is 7, under refluxad behind the stirring reaction 9h, stops to add sodium hydroxide solution, the pH value that drips concentration and be 0.5% hydrochloric acid soln regulator solution is 6.5, solution is poured out, and leaving standstill 1h at 0 ℃ after filtering has a large amount of solids to separate out, and filters out solid product, namely get two hydration hexa-methylenes 1 after 55 ℃ of dryings, 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 by weighing the 52.1g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding the dissolving of 100mL water mechanical stirring, add while stirring 14.8g1, the 6-dichloro hexane, the heating mentioned solution heats up, when making reacting liquid temperature rise to 115 ℃, slowly add 2% sodium hydroxide solution by peristaltic pump, the pH value of conditioned reaction solution is 9, under refluxad behind the stirring reaction 6h, stops to add sodium hydroxide solution, the pH value that drips concentration and be 0.1% hydrochloric acid soln regulator solution is 7, solution is poured out, and leaving standstill 1h at 5 ℃ after filtering has a large amount of solids to separate out, and filters out solid product, namely get two hydration hexa-methylenes 1 after 45 ℃ of dryings, 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 by weighing the 19.8g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding the dissolving of 120mL water mechanical stirring, add while stirring 6.9g1, the 6-dichloro hexane, the heating mentioned solution heats up, make reacting liquid temperature keep reacting under 100 ℃ of conditions, slowly add 1% sodium hydroxide solution by peristaltic pump, the pH value of conditioned reaction solution is 8, behind the stirring reaction 5h, stops to add sodium hydroxide solution under the reflux conditions, the pH value that drips concentration and be 3% hydrochloric acid soln regulator solution is 7, pour out solution, filter be placed on 4 ℃ leave standstill 5h after, filter out solid product, namely get two hydration hexa-methylenes 1 after 55 ℃ of dryings, 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 by weighing the 39.6g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding the dissolving of 120mL water mechanical stirring, add while stirring 19.6g1, the 6-dibromo-hexane, the heating mentioned solution heats up, make reacting liquid temperature remain on 80 ℃, slowly add 1.5% sodium hydroxide solution by peristaltic pump, the pH value of conditioned reaction solution is 9, under refluxad behind the stirring reaction 7h, stops to add sodium hydroxide solution, the pH value that drips concentration and be 5% hydrochloric acid soln regulator solution is 9, pour out solution, filter be placed on 10 ℃ leave standstill 6h after, filter out solid product, namely get two hydration hexa-methylenes 1 after 50 ℃ of dryings, 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 by weighing the 19.8g Sodium Thiosulfate Pentahydrate in four-hole boiling flask, after adding the dissolving of 120mL water mechanical stirring, add while stirring 10.3g1, the 6-dibromo-hexane, the heating mentioned solution heats up, make reacting liquid temperature keep reacting under 90 ℃ of conditions, slowly add 1% sodium hydroxide solution by peristaltic pump, the pH value of conditioned reaction solution is 8, behind the stirring reaction 4h, stops to add sodium hydroxide solution under the reflux conditions, the pH value that drips concentration and be 2% hydrochloric acid soln regulator solution is 7, pour out solution, filter be placed on 4 ℃ leave standstill 5h after, filter out solid product, namely get two hydration hexa-methylenes 1 after 55 ℃ of dryings, 6-dithio sulfuric acid disodium salt.
According to the embodiment among the embodiment 1, be raw material with Sodium Thiosulfate Pentahydrate and 1,6-dichloro hexane, 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 sample adopts pellet technique test infrared spectra, conform to structural formula:
3564,3457,1619cm
-1: the infrared absorption peak of OH in the 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 that obtains is carried out ultimate analysis, test C, H, the percentage composition of three kinds of elements of S wherein, and the percentage composition of NaCl in the specimen, the result is as follows:
Obtain the results of elemental analyses of sample in table 1. above-described embodiment 1
C(%) | H(%) | S(%) | NaCl(%) | |
Calculated value | 18.46 | 4.10 | 32.82 - | |
Embodiment 1 | 18.20 | 4.06 | 30.81 | 0.32 |
Claims (9)
1. the preparation method of an 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 by weighing the water-soluble inorganic thiosulphate and places reaction vessel, adds the dissolving of entry mechanical stirring, is mixed with the aqueous solution of inorganic sulfur thiosulfate;
Step (2) adds halogenated alkane under agitation condition, 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 refluxad stirring reaction 4~9h;
Step (4), after reaction finishes, stop to add 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 placing 0~10 ℃ to leave standstill 1~6h this solution after the filtration, filter out solid, namely get organic Thiosulfuric acid derivant after 45~55 ℃ of dryings.
2. the preparation method of organic sodium thiosulphate compound as claimed in claim 1 is characterized in that the water-soluble inorganic thiosulphate described in the step (1) can be a kind of in Sulfothiorine, Potassium Thiosulphate, the ammonium thiosulfate.
3. the preparation method of organic sodium thiosulphate compound as claimed in claim 2 is characterized in that described water-soluble inorganic thiosulphate is Sulfothiorine, and its mass percentage concentration is 10%~40%.
4. the preparation method of organic sodium thiosulphate compound as claimed in claim 1 is characterized in that the halogenated alkane described in the step (2) can be a kind of in 1,6-dichloro hexane and 1, the 6-dibromo-hexane.
5. the preparation method of organic sodium thiosulphate compound as claimed in claim 1 is characterized in that described water-soluble inorganic thiosulphate and halogenated alkane consumption mol ratio are 1.8: 1~2.2: 1.
6. the preparation method of organic sodium thiosulphate compound as claimed in claim 1 is characterized in that the temperature of reaction described in the step (2) is 80~120 ℃.
7. the preparation method of organic sodium thiosulphate compound as claimed in claim 1, the mass percentage concentration that it is characterized in that the sodium hydroxide solution described in the step (3) is 1%~2%.
8. the preparation method of organic sodium thiosulphate compound as claimed in claim 1 is characterized in that the acid described in the step (4) can be a kind of in hydrochloric acid, sulfuric acid, the nitric acid.
9. the preparation method of organic sodium thiosulphate compound as claimed in claim 8 is characterized in that described acid can be hydrochloric acid, and the mass percentage concentration of hydrochloric acid soln is 0.05~5%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210366335.6A CN102875435B (en) | 2012-09-28 | 2012-09-28 | Organic thiosulfuric acid derivative preparation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210366335.6A CN102875435B (en) | 2012-09-28 | 2012-09-28 | Organic thiosulfuric acid derivative preparation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102875435A true CN102875435A (en) | 2013-01-16 |
CN102875435B CN102875435B (en) | 2014-04-09 |
Family
ID=47476991
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210366335.6A Active CN102875435B (en) | 2012-09-28 | 2012-09-28 | Organic thiosulfuric acid derivative preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102875435B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103788372A (en) * | 2013-12-27 | 2014-05-14 | 北京彤程创展科技有限公司 | Polymer containing ether polysulfide structure and preparation method thereof |
CN103819377A (en) * | 2013-12-16 | 2014-05-28 | 菏泽佳成化工有限公司 | Preparation method of dihydrate hexamethylene-1,6-disodium dithiosulfate |
CN105218419A (en) * | 2015-10-14 | 2016-01-06 | 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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
2012
- 2012-09-28 CN CN201210366335.6A patent/CN102875435B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
Non-Patent Citations (2)
Title |
---|
刘红霞等: "2-甲基-2-苯基-1,3-二硫环庚烷的合成及香气研究", 《食品科学》 * |
朱旭容,孙晓娟: "2-二甲胺基-1-硫代磺酸钠基-3-硫代磺酸基丙烷的合成", 《南京化工大学学报》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103819377A (en) * | 2013-12-16 | 2014-05-28 | 菏泽佳成化工有限公司 | Preparation method of dihydrate hexamethylene-1,6-disodium dithiosulfate |
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 |
CN103788372A (en) * | 2013-12-27 | 2014-05-14 | 北京彤程创展科技有限公司 | Polymer containing ether polysulfide structure and preparation method thereof |
CN105218419A (en) * | 2015-10-14 | 2016-01-06 | 北京彤程创展科技有限公司 | A kind of preparation method of organic mercaptan zinc salt |
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 |
Also Published As
Publication number | Publication date |
---|---|
CN102875435B (en) | 2014-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2015158157A1 (en) | Method for cyclically preparing taurine from hydroxyethyl sulfonic acid alkali metal salt and vinyl sulfonic acid alkali metal salt | |
CN102875435B (en) | Organic thiosulfuric acid derivative preparation method | |
WO2018000404A1 (en) | Method for preparing taurine | |
CN102276663B (en) | Preparation method of glucosamine sulfate | |
CN105523674A (en) | Treatment method for 1-amino-8-naphthol-3,6-disulfonic acid monosodium salt production wastewater and equipment for implementing method | |
CN102911122A (en) | Metronidazole preparation method | |
CN103539707A (en) | Preparation process of 2-naphthylamine-3,6,8-trisulfonic acid | |
CN104311448A (en) | Preparation method of dinitolmide | |
CN101239919B (en) | Method for synthesizing aromatic diamines monomer | |
CN103130697A (en) | Preparation method of post-vulcanization stabilizing agent organic thiosulfate | |
CN102816095B (en) | Preparation method for organic thiosulfate | |
CN103508974B (en) | A kind of method processing adjacent sulfonamide benzoic acid methyl esters crystalline mother solution | |
CN104592044B (en) | The low temperature synthetic method of 2,6-Dichloro-4-nitroaniline | |
CN104276928B (en) | The preparation method of two [1-(4-hydroxy phenyl)-1-the methylethyl]-Resorcinol of a kind of 4,6- | |
CN106831517A (en) | A kind of synthetic method of thiocarbohydrazide | |
CN102936213B (en) | Clean preparation method of 1, 8-dinitro-3, 6-naphthalenedisulfonic acid | |
CN1986518A (en) | Preparing process of 4,4-dinitro diphenyl ether | |
CN107129446A (en) | The technique of sulfate ion is reduced in a kind of methyl propane sulfonic acid building-up process of 2 acrylamido 2 | |
CN102838513A (en) | Preparation method of 2-naphthylamine 3, 6, 8 trisulfonic acid | |
CN107344921A (en) | A kind of intermediate DAS of paratonere 177 preparation method | |
CN107033044B (en) | A kind of preparation method of pair of trifluoromethylthio phenol | |
CN102731352B (en) | Preparation method of 4-methylthio benzaldehyde | |
CN102690222A (en) | Preparation method of (R,S)-4-hydroxy-2-oxo-1-pyrrolidineacetamide | |
CN102850247B (en) | Preparation method of thiosulfuric acid derivative for rubber industry | |
CN110483303A (en) | A kind of 3- nitro -4- chlorobenzotrifluoride spent acid emission reduction new process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |