CN101613309A - The preparation method of isooctyl mercaptoacetate - Google Patents
The preparation method of isooctyl mercaptoacetate Download PDFInfo
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- CN101613309A CN101613309A CN200910063368A CN200910063368A CN101613309A CN 101613309 A CN101613309 A CN 101613309A CN 200910063368 A CN200910063368 A CN 200910063368A CN 200910063368 A CN200910063368 A CN 200910063368A CN 101613309 A CN101613309 A CN 101613309A
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- concentrated hydrochloric
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- isooctyl mercaptoacetate
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Abstract
The invention discloses a kind of preparation method of isooctyl mercaptoacetate, it is to be main raw material with the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, through sulfhydrylation salify (being bunte salt), bunte salt obtains the isooctyl mercaptoacetate crude product after adding concentrated hydrochloric acid hydrolysis, this crude product adds and reduces processings behind concentrated hydrochloric acid and the zinc powder, then through wash and underpressure distillation after obtain finished product; After the layering of bunte salt hydrolysis, with waste liquid (lower aqueous layer) filter with crystallization after reclaim abraum salt (inorganic salt); Filter the remaining useless concentrated hydrochloric acid in back and store for future use, repeated application is in hydrolysis and reduction.Method provided by the invention; adopt the useless concentrated hydrochloric acid that reclaims in the production process to be hydrolyzed and reduction reaction; realized the recycle of starting material (concentrated hydrochloric acids); not only saved the usage quantity of concentrated hydrochloric acid; reduced production cost; and significantly reduced the quantity discharged of strongly acid wastewater, and protected environment, have good economic and social benefit.
Description
Technical field
The present invention relates to the fine chemistry industry production field, particularly relate to a kind of preparation method of isooctyl mercaptoacetate.
Background technology
Isooctyl mercaptoacetate is the important fine chemicals of a class, is the main raw material of preparation polyvinyl chloride (PVC) plastics thermo-stabilizer, agent of resistance side chain and dihydroxyphenyl propane synthetic catalyzer in the time of simultaneously can also be as the polyvinyl chloride resin polymerization.Along with the quick growth of the organo-tin het stabilizer market requirement, more and more come into one's own as the industrialization of its commercial important source material (isooctyl mercaptoacetate) research.
The domestic two kinds of operational paths that mainly contain that synthesize isooctyl mercaptoacetate at present: the one, direct esterification or elder generation's extraction resterification under katalysis with commodity Thiovanic acid and different monooctyl ester, as CN9010816.2, because the price of commodity Thiovanic acid is higher, cause production cost higher, be not suitable for China's actual conditions.Another route is the different monooctyl ester of first synthesis of chloroacetic acid, obtains product through salify, hydrolysis, reduction then, and this method is a bunte salt method, as the method for CN91106522.9, this method concentrated hydrochloric acid service efficiency is low, and wastewater discharge is big, environmental pollution is serious, is unfavorable for scale operation.
Summary of the invention
Technical problem to be solved by this invention is: big at existing bunte salt method production isooctyl mercaptoacetate strongly acid wastewater quantity discharged; with serious pollution weak point; a kind of preparation method of isooctyl mercaptoacetate is provided; this method is owing to realized the recycle of starting material (concentrated hydrochloric acids); not only save production cost, and protected environment.
The present invention solves its technical problem and adopts following technical scheme:
The preparation method of isooctyl mercaptoacetate provided by the invention, this method are to be main raw material with the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, prepare isooctyl mercaptoacetate through salify, hydrolysis, reduction, distillation, and be specific as follows:
(1) under normal pressure, 120～160 ℃ condition, different monooctyl ester of Mono Chloro Acetic Acid and Sulfothiorine are in the presence of Virahol, and backflow mercaptolation 0.5～2 hour makes bunte salt; By weight, the consumption proportion of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine and Virahol is 1: (1.33～1.61): 0.98;
(2) bunte salt is after adding concentrated hydrochloric acid hydrolysis, and standing demix divides and goes and collect lower aqueous layer; By volume, the concentrated hydrochloric acid add-on is 200～250mL;
(3) the isooctyl mercaptoacetate crude product that the upper strata obtained adds concentrated hydrochloric acid and zinc powder and reduces processing; By the weight of isooctyl mercaptoacetate crude product, concentrated hydrochloric acid and zinc powder add-on are respectively 100mL and 20～30g;
(4) will reduce and handle the isooctyl mercaptoacetate mixture obtain to wash the pH value with water be 6～8, obtain the target product isooctyl mercaptoacetate through underpressure distillation again.
Used concentrated hydrochloric acid is industrial concentrated hydrochloric acid in above-mentioned reduction reaction, or the useless concentrated hydrochloric acid that reclaims after the hydrolysis.
Above-mentioned useless concentrated hydrochloric acid can recycle in hydrolysis or reduction reaction 1～10 time.
In said hydrolyzed or reduction reaction, the mass concentration of employed concentrated hydrochloric acid can be 35～37%.
The different monooctyl ester of described Mono Chloro Acetic Acid can be produced by ordinary method, produces as the described method of patent CN91106522.9.
The present invention compared with prior art; mainly contain following advantage: adopt the useless concentrated hydrochloric acid that reclaims in the production process to be hydrolyzed and reduction reaction; realized the recycle of starting material (hydrochloric acid); not only saved the usage quantity of concentrated hydrochloric acid; reduced production cost; and significantly reduced the quantity discharged of strongly acid wastewater, and protected environment, have high economic and social benefit.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The preparation method of isooctyl mercaptoacetate provided by the invention, as shown in Figure 1: with the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine is main raw material, through sulfhydrylation salify (being bunte salt), bunte salt obtains the isooctyl mercaptoacetate crude product after adding concentrated hydrochloric acid hydrolysis, this crude product adds and reduces processings behind concentrated hydrochloric acid and the zinc powder, then through wash and underpressure distillation after obtain finished product.
After the layering of above-mentioned bunte salt hydrolysis, with waste liquid (lower aqueous layer) filter with crystallization after reclaim abraum salt (inorganic salt).Filter the remaining useless concentrated hydrochloric acid in back and store for future use, repeated application is in hydrolysis and reduction.
The present invention is further illustrated below in conjunction with embodiment.
Example 1:
1. produce bunte salt
In the there-necked flask of the 1000ml with agitator, condenser, thermometer, add the different monooctyl ester 214g of Mono Chloro Acetic Acid (ester content 97.5%), Sulfothiorine (Na
2S
2O
35H
2O) 285g, Virahol 210g under agitation, is heated to backflow gradually, keeps 65～85 ℃ of temperature, behind the reaction 1h, steams Virahol, is cooled to 70～90 ℃, and is standby.
2. produce isooctyl mercaptoacetate
In above-mentioned reaction solution, the adding mass concentration is 35～37% concentrated hydrochloric acid 200ml, stirring reaction 1.5h under boiling, and standing demix also is cooled to 30 ℃, divides the sub-cloud water layer, the isooctyl mercaptoacetate crude product that the upper strata obtains.With the lower aqueous layer decrease temperature crystalline, reclaim remaining useless concentrated hydrochloric acid, obtain 182g, and store for future use.The isooctyl mercaptoacetate crude product adds 100ml concentrated hydrochloric acid and 30g zinc powder again, and under 40～50 ℃, stirring reaction 1.5h washes neutrality then, and underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa cut obtains target product isooctyl mercaptoacetate 190.5g, in the different monooctyl ester of Mono Chloro Acetic Acid, yield 92.42%.
Example 2:
1. produce bunte salt
In the there-necked flask of the 1000ml with agitator, condenser, thermometer, add the different monooctyl ester 214g of Mono Chloro Acetic Acid (ester content 98.1%), Sulfothiorine (Na
2S
2O
35H
2O) 305g, Virahol 210g under agitation, is heated to backflow gradually, keeps 65～85 ℃ of temperature, behind the reaction 1.5h, steams Virahol, is cooled to 70～90 ℃, and is standby.
2. produce isooctyl mercaptoacetate
In above-mentioned reaction solution, the adding mass concentration is 35～37% concentrated hydrochloric acid 250ml, stirring reaction 1h under boiling, and standing demix also is cooled to 30 ℃, divides the sub-cloud water layer, the isooctyl mercaptoacetate crude product that the upper strata obtains.With the lower aqueous layer decrease temperature crystalline, reclaim remaining useless concentrated hydrochloric acid, obtain 241g, and store for future use.The isooctyl mercaptoacetate crude product adds 100ml concentrated hydrochloric acid and 35g zinc powder again, and under 40～50 ℃, stirring reaction 1h washes neutrality then, and underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa cut obtains target product isooctyl mercaptoacetate 191.8g, in the different monooctyl ester of Mono Chloro Acetic Acid, yield 92.48%
Example 3:
1. produce bunte salt
In the there-necked flask of the 1000ml with agitator, condenser, thermometer, add the different monooctyl ester 214g of Mono Chloro Acetic Acid (ester content 98.6%), Sulfothiorine (Na
2S
2O
35H
2O) 325g, Virahol 210g under agitation, is heated to backflow gradually, keeps 65～85 ℃ of temperature, behind the reaction 1.5h, steams Virahol, is cooled to 70～90 ℃, and is standby.
2. produce isooctyl mercaptoacetate
In above-mentioned reaction solution, the adding mass concentration is 35～37% concentrated hydrochloric acid 250ml, stirring reaction 2h under boiling, and standing demix also is cooled to 30 ℃, divides the sub-cloud water layer, the isooctyl mercaptoacetate crude product that the upper strata obtains.With the lower aqueous layer decrease temperature crystalline, reclaim remaining useless concentrated hydrochloric acid, obtain 235g, and store for future use.The isooctyl mercaptoacetate crude product adds 100ml concentrated hydrochloric acid and 25g zinc powder again, and under 40～50 ℃, stirring reaction 1.5h washes neutrality then, and underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa cut obtains target product isooctyl mercaptoacetate 192.9g, in the different monooctyl ester of Mono Chloro Acetic Acid, yield 92.54%.
Example 4:
1. produce bunte salt
In the there-necked flask of the 1000ml with agitator, condenser, thermometer, add the different monooctyl ester 214g of Mono Chloro Acetic Acid (ester content 98.0%), Sulfothiorine (Na
2S
2O
35H
2O) 335g, Virahol 210g under agitation, is heated to backflow gradually, keeps 65～85 ℃ of temperature, behind the reaction 1.5h, steams Virahol, is cooled to 70～90 ℃, and is standby.
2. produce isooctyl mercaptoacetate
In above-mentioned reaction solution, the mass concentration that adds recovery is 35～37% useless concentrated hydrochloric acid 250ml, stirring reaction 1.5h under boiling, and standing demix also is cooled to 30 ℃, divides the sub-cloud water layer, the isooctyl mercaptoacetate crude product that the upper strata obtains.With the lower aqueous layer decrease temperature crystalline, reclaim remaining useless concentrated hydrochloric acid, obtain 228g, and store for future use.The isooctyl mercaptoacetate crude product adds the useless concentrated hydrochloric acid 100ml and the 30g zinc powder of recovery again, and under 40～50 ℃, stirring reaction 1.5h washes neutrality then, and underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa cut obtains target product isooctyl mercaptoacetate 191.1g, in the different monooctyl ester of Mono Chloro Acetic Acid, yield 92.24%.
Example 5:
1. produce bunte salt
In the there-necked flask of the 1000ml with agitator, condenser, thermometer, add the different monooctyl ester 214g of Mono Chloro Acetic Acid (ester content 97.2%), Sulfothiorine (Na
2S
2O
35H
2O) 345g, Virahol 210g under agitation, is heated to backflow gradually, keeps 65～85 ℃ of temperature, behind the reaction 1h, steams Virahol, is cooled to 70～90 ℃, and is standby.
2. produce isooctyl mercaptoacetate
In above-mentioned reaction solution, the mass concentration that adds recovery is 35～37% useless concentrated hydrochloric acid 250ml, stirring reaction 1h under boiling, and standing demix also is cooled to 30 ℃, divides the sub-cloud water layer, the isooctyl mercaptoacetate crude product that the upper strata obtains.With the lower aqueous layer decrease temperature crystalline, reclaim remaining useless concentrated hydrochloric acid, obtain 236g, and store for future use.The isooctyl mercaptoacetate crude product adds the useless concentrated hydrochloric acid 100ml and the 20g zinc powder of recovery again, and under 40～50 ℃, stirring reaction 1h washes neutrality then, and underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa cut obtains target product isooctyl mercaptoacetate 192.1g, in the different monooctyl ester of Mono Chloro Acetic Acid, yield 93.48%.
Claims (5)
1. the preparation method of an isooctyl mercaptoacetate, it is a main raw material with the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine, prepares isooctyl mercaptoacetate through salify, hydrolysis, reduction, distillation, it is characterized in that:
(1) under normal pressure, 120～160 ℃ condition, different monooctyl ester of Mono Chloro Acetic Acid and Sulfothiorine are in the presence of Virahol, and backflow mercaptolation 0.5～2 hour makes bunte salt; By weight, the consumption proportion of the different monooctyl ester of Mono Chloro Acetic Acid, Sulfothiorine and Virahol is 1: (1.33～1.61): 0.98;
(2) bunte salt is after adding concentrated hydrochloric acid hydrolysis, and standing demix divides and goes and collect lower aqueous layer; By volume, the concentrated hydrochloric acid add-on is 200～250mL;
(3) the isooctyl mercaptoacetate crude product that the upper strata obtained adds concentrated hydrochloric acid and zinc powder and reduces processing; By the weight of isooctyl mercaptoacetate crude product, concentrated hydrochloric acid and zinc powder add-on are respectively 100mL and 20～30g;
(4) will reduce and handle the isooctyl mercaptoacetate mixture obtain to wash the pH value with water be 6～8, obtain the target product isooctyl mercaptoacetate through underpressure distillation again.
2. the preparation method of isooctyl mercaptoacetate according to claim 1 is characterized in that: lower aqueous layer is carried out crystallization reclaim abraum salt, remaining useless concentrated hydrochloric acid stores for future use.
3. the preparation method of isooctyl mercaptoacetate according to claim 1 and 2, it is characterized in that: the used concentrated hydrochloric acid of hydrolysis reaction is industrial concentrated hydrochloric acid, or the useless concentrated hydrochloric acid that reclaims after the hydrolysis.
4. the preparation method of isooctyl mercaptoacetate according to claim 1 and 2, it is characterized in that: the used concentrated hydrochloric acid of reduction reaction is industrial concentrated hydrochloric acid, or the useless concentrated hydrochloric acid that reclaims after the hydrolysis.
5. the preparation method of isooctyl mercaptoacetate according to claim 2, it is characterized in that: described useless concentrated hydrochloric acid recycles in hydrolysis or reduction reaction 1～10 time.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249964A (en) * | 2011-05-27 | 2011-11-23 | 连云港升南化学有限公司 | Process for preparing isooctyl thioglycolate |
| CN106397286A (en) * | 2016-08-25 | 2017-02-15 | 湖北犇星化工有限责任公司 | Treatment method of isooctyl thioglycolate rectification waste material |
| CN110713447A (en) * | 2019-11-15 | 2020-01-21 | 山东国邦药业有限公司 | Preparation method of p-methylthio benzaldehyde |
| CN111925323A (en) * | 2020-09-01 | 2020-11-13 | 山东京博生物科技有限公司 | Synthetic method of 2-aminosulfonyl-N, N-dimethylnicotinamide |
-
2009
- 2009-07-28 CN CN200910063368A patent/CN101613309A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249964A (en) * | 2011-05-27 | 2011-11-23 | 连云港升南化学有限公司 | Process for preparing isooctyl thioglycolate |
| CN106397286A (en) * | 2016-08-25 | 2017-02-15 | 湖北犇星化工有限责任公司 | Treatment method of isooctyl thioglycolate rectification waste material |
| CN106397286B (en) * | 2016-08-25 | 2018-02-16 | 湖北犇星化工有限责任公司 | A kind of processing method of isooctyl thioglycolate rectifying waste material |
| CN110713447A (en) * | 2019-11-15 | 2020-01-21 | 山东国邦药业有限公司 | Preparation method of p-methylthio benzaldehyde |
| CN111925323A (en) * | 2020-09-01 | 2020-11-13 | 山东京博生物科技有限公司 | Synthetic method of 2-aminosulfonyl-N, N-dimethylnicotinamide |
| CN111925323B (en) * | 2020-09-01 | 2022-05-31 | 山东京博生物科技有限公司 | Synthetic method of 2-aminosulfonyl-N, N-dimethylnicotinamide |
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Application publication date: 20091230 |