CN1058393A - The method for preparing thioglycollic acid-2-ethyl hexyl ester - Google Patents
The method for preparing thioglycollic acid-2-ethyl hexyl ester Download PDFInfo
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- CN1058393A CN1058393A CN 91106522 CN91106522A CN1058393A CN 1058393 A CN1058393 A CN 1058393A CN 91106522 CN91106522 CN 91106522 CN 91106522 A CN91106522 A CN 91106522A CN 1058393 A CN1058393 A CN 1058393A
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Abstract
A kind of is main raw material by Mono Chloro Acetic Acid, 2-Ethylhexyl Alcohol, Sulfothiorine, prepares the method for thioglycollic acid-2-ethyl hexyl ester through esterification, salify, hydrolysis, reduction, it is characterized in that: the negative pressure esterification, become salt solvent be can be miscible with water C
2～C
7Fatty Alcohol(C12-C14 and C12-C18), back hydrolysis.Solvent is applied mechanically; The productive rate height; The crude product straight run distillation, technology is easy; Quality is better than external product.Be fit to national conditions, pollution-free, cost is low, save foreign exchange, is the industrial production of domestic organotin stabilizer, provides raw material together.
Description
The present invention relates to a kind of preparation method of Organic Chemicals, particularly a kind of preparation method of thioglycollic acid-2-ethyl hexyl ester.
Thioglycollic acid-2-ethyl hexyl ester (Thioglycolic acid-2-ethylhexylester) is a kind of important Organic Chemicals, is mainly used in the manufacturing of organotin stabilizer.
In the prior art, the route of external synthetic thioglycollic acid-2-ethyl hexyl ester mainly contains two at present:
Article one, be to produce Thiovanic acid from Mono Chloro Acetic Acid, again with the 2-Ethylhexyl Alcohol direct esterification, (as, CA Vol 77 151000d, 1972; Ger, (East) 127,117) though this method is fairly simple, but must be with the Thiovanic acid more than 97%, and prepare Thiovanic acid more than 97%, price is just too expensive; If the Thiovanic acid with 80%, equipment are just complicated, not easy to operate, cost is also high; And it is very big to build a plant investment of producing the Thiovanic acid dilute solution, extracts, the esterification equipment requirements is also high.From domestic, take the factory of this method, the Thiovanic acid concentration of producing is generally 70%, total recovery is 60 ± 5%, one ton 70% Thiovanic acid cost is about 2.5 ten thousand yuan, and is also more expensive than the thioglycollic acid-2-ethyl hexyl ester of import, thereby, domestic direct esterification method is produced thioglycollic acid-2-ethyl hexyl ester, can't accept economically.
Another strip adoption is that raw material is produced thioglycollic acid-2-ethyl hexyl ester from 2-Ethylhexyl Chloroacetate, as DD 270,063(1989) with DD 214126(1984) etc., the solvent when it produces Bunte salt is DMF/ water.The deficiencies in the prior art part is, solvent high price and toxic (when adopting DMF/ water); Or, and yield all low (report 90%) more loaded down with trivial details because of there being the part by product to cause aftertreatment.
Purpose of the present invention, be to look for suitable national conditions, work simplification, non-environmental-pollution, cost quite or lower new processing method than external product, the home-made thioglycollic acid-2-ethyl hexyl ester is provided, saves foreign exchange, for raw material is provided in the preparation of organotin together.
Task of the present invention realizes as follows:
Developing one is main raw material by Mono Chloro Acetic Acid, 2-Ethylhexyl Alcohol, Sulfothiorine, produces the method for thioglycollic acid-2-ethyl hexyl ester through esterification, salify, hydrolysis, reduction, that is:
It is characterized in that:
1. esterification is to carry out under negative pressure;
The solvent of salt-forming reaction be can be miscible with water C
2～C
7Fatty Alcohol(C12-C14 and C12-C18) (for example, ethanol, n-propyl alcohol, Virahol, isopropylcarbinol, n-Heptyl alcohol etc.);
3. hydrolysis reaction is to carry out under refluxing,
4. apply mechanically the distillation foreshot during hydrolysis reaction.
The preparation method of above-mentioned thioglycollic acid-2-ethyl hexyl ester is characterized in that described esterification is to carry out under negative pressure, be meant that reaction is to carry out under 90.66～99.99kPa pressure when making 2-Ethylhexyl Chloroacetate.
The preparation method of above-mentioned thioglycollic acid-2-ethyl hexyl ester is characterized in that the mol ratio of Mono Chloro Acetic Acid and 2-Ethylhexyl Alcohol is 1: 1.05～1.2 when making 2-Ethylhexyl Chloroacetate, in the presence of sulfuric acid, in 100～150 ℃ of reaction 1～3h.
The preparation method of above-mentioned thioglycollic acid-2-ethyl hexyl ester, the solvent that it is characterized in that described salt-forming reaction be can be miscible with water C
2～C
7Fatty Alcohol(C12-C14 and C12-C18), be meant when producing Bunte salt, with volume ratio be 1: 0.8～1.5 can be miscible with water C
2～C
7Fatty Alcohol(C12-C14 and C12-C18)/aqueous solution make reaction solvent.
The preparation method of above-mentioned thioglycollic acid-2-ethyl hexyl ester is characterized in that the mol ratio of 2-Ethylhexyl Chloroacetate and Sulfothiorine is 1: 1.0～1.2 when making Bunte salt, in refluxing down reaction 0.5～2h.
The preparation method of above-mentioned thioglycollic acid-2-ethyl hexyl ester, it is characterized in that described hydrolysis reaction is to carry out under refluxing, be meant when producing thioglycollic acid-2-ethyl hexyl ester, prior to 100～120 ℃ of back flow reaction 0.5～1.5h, be as cold as again≤40 ℃, react 0.5～1.5h at 45～60 ℃ behind the adding zinc powder.
The preparation method of above-mentioned thioglycollic acid-2-ethyl hexyl ester, when it is characterized in that described reductive hydrolysis reacts, the mol ratio between Bunte salt, hydrolysis acid, the zinc powder is 1: 0.3～2: 0.2～0.6.
The preparation method of above-mentioned thioglycollic acid-2-ethyl hexyl ester is applied mechanically the distillation foreshot when it is characterized in that described hydrolysis reaction, is meant when adding hydrolysis acid, adds the distillation foreshot of going up batch simultaneously.
The present invention compared with the prior art, its advantage is:
(1) solvent inexpensive, be easy to get, low toxicity, rate of recovery Gao Bingke applies mechanically repeatedly;
(2) evidence, the temperature height of salify, hydrolysis carries out under refluxing, and helps the raising of productive rate;
(3) crude product thioglycollic acid-2-ethyl hexyl ester need not can directly to distill work simplification through operations such as neutralization, washing, dryings;
(4) during hydrolysis, directly be inserted in the distillation foreshot of last consignment of, help suppressing side reaction, thioglycollic acid-2-ethyl hexyl ester has been played provide protection.
The quality of the sulfydryl ethyl ester-2-ethylhexyl of explained hereafter provided by the invention, outward appearance is a colourless transparent oil liquid, sulfydryl S content 〉=15.0%, acid number mg, KOH/g≤1.0 are compared with external product, omit.
The invention provides the yield of the thioglycollic acid-2-ethyl hexyl ester of method, in 2-Ethylhexyl Chloroacetate, is 92～93%, compares with foreign literature, omits.
On probation through Beijing Chemical Factory No. 3, its quality and price are all felt satisfied.
Found out suitable national conditions, work simplification, non-environmental-pollution, cost quite or lower new processing method than external product, the home-made thioglycollic acid-2-ethyl hexyl ester is provided, save foreign exchange, provide raw material together for the preparation of organotin stabilizer, realized predetermined purpose of the present invention.
The present invention is further elaborated below in conjunction with embodiment:
[embodiment one]
1. produce 2-Ethylhexyl Chloroacetate
In the there-necked flask of the 500ml with agitator, condenser and thermometer, add Mono Chloro Acetic Acid 94.5g, 2-Ethylhexyl Alcohol 140g, vitriol oil 0.4g is heated to 100～120 ℃, under agitation, being evacuated to pressure is 90.66～98.66kPa, recovers normal pressure behind the reaction 3h, is cooled to 80 ± 10 ℃, with 2% sodium carbonate solution neutralization, aqueous phase discarded gets product 188.8g, measure with saponification method, ester content 95.70%, in Mono Chloro Acetic Acid, productive rate 96.5%.
2. produce Bunte salt
In the there-necked flask of the 1000ml with agitator, condenser and thermometer, add 2-Ethylhexyl Chloroacetate 214g(ester content 95.70%), Sulfothiorine (Na
2S
2O
35H
2O) 261g, water 160ml and C that can be miscible with water
2～C
7Fatty Alcohol(C12-C14 and C12-C18) 200ml, under agitation, be heated to backflow gradually, the reaction 0.5h after, steam etoh solvent, be cooled to 80 ± 10 ℃, standby.
3. produce thioglycollic acid-2-ethyl hexyl ester
In above-mentioned reaction solution, add concentrated hydrochloric acid 250ml, at 95～100 ℃ of stirring reaction 0.5h, be cooled to 30 ℃, stir adding zinc powder 14g down, under 45～50 ℃, continue stirring reaction 1.5h, filtration, static layering, get organic layer, underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa fraction gets product 187.68g, uses iodometric determination, sulfydryl S content 15.3%, and in 2-Ethylhexyl Chloroacetate, productive rate 92.0%.
[embodiment two]
1. produce 2-Ethylhexyl Chloroacetate
In the there-necked flask of the 500ml with agitator, condenser and thermometer, add Mono Chloro Acetic Acid 94.5g, 2-Ethylhexyl Alcohol 140g, vitriol oil 0.4g is heated to 145～150 ℃, under agitation, being evacuated to pressure is 90.66～98.66kPa, recovers normal pressure behind the reaction 1h, is cooled to 80 ± 10 ℃, with 2% sodium carbonate solution neutralization, aqueous phase discarded gets product 190.7g, measure with saponification method, ester content 96.51%, in Mono Chloro Acetic Acid, productive rate 98.3%.
2. produce Bunte salt
In the there-necked flask of the 1000ml with agitator, condenser and thermometer, add 2-Ethylhexyl Chloroacetate 214g(ester content 96.51%), Sulfothiorine (Na
2S
2O
35H
2O) 313.3g, water 300ml and C that can be miscible with water
2～C
7Fatty Alcohol(C12-C14 and C12-C18) 200ml, under agitation, be heated to backflow gradually, the reaction 2h after, steam etoh solvent, be cooled to 80 ± 10 ℃, standby.
3. produce thioglycollic acid-2-ethyl hexyl ester
In above-mentioned reaction solution, add concentrated hydrochloric acid 40ml, at 100～120 ℃ of stirring reaction 1.5h, be cooled to 30 ℃, stir adding zinc powder 42g down, under 50～60 ℃, continue stirring reaction 0.5h, filtration, static layering, get organic layer, underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa fraction gets product 188.29g, uses iodometric determination, sulfydryl S content 15.4%, and in 2-Ethylhexyl Chloroacetate, productive rate 92.30%.
[embodiment three]
1. produce 2-Ethylhexyl Chloroacetate
In the there-necked flask of the 500ml with agitator, condenser and thermometer, add Mono Chloro Acetic Acid 94.5g, 2-Ethylhexyl Alcohol 131g, vitriol oil 0.4g is heated to 140～150 ℃, under agitation, being evacuated to pressure is 90.66～98.66kPa, recovers normal pressure behind the reaction 1h, is cooled to 80 ± 10 ℃, with 2% sodium carbonate solution neutralization, aqueous phase discarded gets product 188g, measure with saponification method, ester content 96.80%, in Mono Chloro Acetic Acid, productive rate 97.2%.
2. produce Bunte salt
In the there-necked flask of the 1000ml with agitator, condenser and thermometer, add 2-Ethylhexyl Chloroacetate 214g(ester content 96.80%), Sulfothiorine (Na
2S
2O
35H
2O) 298g, water 180ml and C that can be miscible with water
2～C
7Fatty Alcohol(C12-C14 and C12-C18) 200ml, under agitation, be heated to backflow gradually, the reaction 1h after, steam etoh solvent, be cooled to 80 ± 10 ℃, standby.
3. produce thioglycollic acid-2-ethyl hexyl ester
In above-mentioned reaction solution, add concentrated hydrochloric acid 150ml and foreshot 80g, at 105～110 ℃ of following stirring reaction 1h, be cooled to 30 ℃, stir adding zinc powder 40g down, under 45～50 ℃, continue stirring reaction 1h, filtration, static layering, get organic layer, underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa fraction gets product 189.1g, uses iodometric determination, sulfydryl S content 15.35%, and in 2-Ethylhexyl Chloroacetate, productive rate 92.7%.
[embodiment four]
1. produce 2-Ethylhexyl Chloroacetate
In the there-necked flask of the 500ml with agitator, condenser and thermometer, add Mono Chloro Acetic Acid 94.5g, 2-Ethylhexyl Alcohol 148.8g, vitriol oil 0.4g is heated to 120～140 ℃, under agitation, being evacuated to pressure is 90.66～98.66kPa, recovers normal pressure behind the reaction 1.5h, is cooled to 80 ± 10 ℃, with 2% sodium carbonate solution neutralization, aqueous phase discarded gets product 190.4g, measure with saponification method, ester content 95.30%, in Mono Chloro Acetic Acid, productive rate 96.9%.
2. produce Bunte salt
In the there-necked flask of the 1000ml with agitator, condenser and thermometer, add 2-Ethylhexyl Chloroacetate 214g(ester content 95.30%), Sulfothiorine (Na
2S
2O
35H
2O) 298g, water 200ml and C that can be miscible with water
2～C
7Fatty Alcohol(C12-C14 and C12-C18) 200ml, under agitation, be heated to backflow gradually, the reaction 1.5h after, steam etoh solvent, be cooled to 80 ± 10 ℃, standby.
3. produce thioglycollic acid-2-ethyl hexyl ester
In above-mentioned reaction solution, add concentrated hydrochloric acid 150ml and foreshot 90g, at 110～120 ℃ of following stirring reaction 1.5h, be cooled to 30 ℃, stir adding zinc powder 35g down, under 55～60 ℃, continue stirring reaction 1.5h, filtration, static layering are got organic layer, underpressure distillation collects 125～130 ℃/1.6 * 10
3The Pa fraction gets product 187.6g, uses the iodine flow measurement, sulfydryl S content 15.42%, and in 2-Ethylhexyl Chloroacetate, productive rate 93.10%.
Claims (8)
1, a kind of is main raw material by Mono Chloro Acetic Acid, 2-ethylhexanol, Sulfothiorine, prepares the Organic Chemicals thioglycollic acid-2-ethyl method of ester through esterification, salify, hydrolysis, reduction, and feature of the present invention is:
1.1. esterification is to carry out under negative pressure,
1.2. the solvent of salt-forming reaction be can be miscible with water C
2～C
7Fatty Alcohol(C12-C14 and C12-C18),
1.3. hydrolysis reaction is to carry out under refluxing,
1.4. apply mechanically the distillation foreshot during hydrolysis reaction.
2, according to the described method for preparing thioglycollic acid-2-ethyl hexyl ester of claim 1, it is characterized in that described esterification is to carry out under negative pressure, be meant that reaction is to carry out when making 2-Ethylhexyl Chloroacetate under 90.66～99.99kPa pressure.
3, according to claim 1 or the 2 described methods that prepare thioglycollic acid-2-ethyl hexyl ester, it is characterized in that when making 2-Ethylhexyl Chloroacetate, the mol ratio of Mono Chloro Acetic Acid and 2-Ethylhexyl Alcohol is 1: 1.05～1.2, in the presence of sulfuric acid, in 100～150 ℃ of reaction 1～3h.
4, according to the described method for preparing thioglycollic acid-2-ethyl hexyl ester of claim 1, the solvent that it is characterized in that described salt-forming reaction be can be miscible with water C
2～C
7Fatty Alcohol(C12-C14 and C12-C18), be meant when producing Bunte salt, with volume ratio be 1: 0.8～1.5 can be miscible with water C
2～C
7Fatty Alcohol(C12-C14 and C12-C18)/aqueous solution make reaction solvent.
5,, it is characterized in that the mol ratio of 2-Ethylhexyl Chloroacetate and Sulfothiorine is 1: 1.0～1.2 when making Bunte salt, in refluxing down reaction 0.5～2h according to claim 1 or the 4 described methods that prepare thioglycollic acid-2-ethyl hexyl ester.
6, according to the described method for preparing thioglycollic acid-2-ethyl hexyl ester of claim 1, it is characterized in that described hydrolysis reaction is to carry out under refluxing, be meant when producing thioglycollic acid-2-ethyl hexyl ester, prior to 100～120 ℃ of back flow reaction 1～1.5h, be as cold as again≤40 ℃, react 0.5～1.5h at 45～60 ℃ behind the adding zinc powder.
7, according to claim 1 or the 6 described methods that prepare thioglycollic acid-2-ethyl hexyl ester, when it is characterized in that described hydrolysis, reduction reaction, the mol ratio between Bunte salt, hydrolysis acid, the zinc powder is 1: 0.3～2: 0.2～0.6.
8, according to the described method for preparing thioglycollic acid-2-ethyl hexyl ester of claim 1, apply mechanically the distillation foreshot when it is characterized in that described hydrolysis reaction, be meant when adding hydrolysis acid, add the distillation foreshot of going up batch simultaneously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106522 CN1058393A (en) | 1991-08-17 | 1991-08-17 | The method for preparing thioglycollic acid-2-ethyl hexyl ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106522 CN1058393A (en) | 1991-08-17 | 1991-08-17 | The method for preparing thioglycollic acid-2-ethyl hexyl ester |
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Cited By (3)
| 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 |
| CN102958982A (en) * | 2010-06-30 | 2013-03-06 | 住友化学株式会社 | Method for using s-(3-aminopropyl)thiosulfuric acid and/or metal salt thereof |
| CN112457228A (en) * | 2020-12-15 | 2021-03-09 | 山东沾化金嘉利化工科技有限公司 | Preparation method of thioglycollic acid-2-ethylhexyl ester in molten salt hydrate |
-
1991
- 1991-08-17 CN CN 91106522 patent/CN1058393A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102958982A (en) * | 2010-06-30 | 2013-03-06 | 住友化学株式会社 | Method for using s-(3-aminopropyl)thiosulfuric acid and/or metal salt thereof |
| CN102249964A (en) * | 2011-05-27 | 2011-11-23 | 连云港升南化学有限公司 | Process for preparing isooctyl thioglycolate |
| CN112457228A (en) * | 2020-12-15 | 2021-03-09 | 山东沾化金嘉利化工科技有限公司 | Preparation method of thioglycollic acid-2-ethylhexyl ester in molten salt hydrate |
| CN112457228B (en) * | 2020-12-15 | 2022-07-29 | 山东沾化金嘉利化工科技有限公司 | Preparation method of thioglycollic acid-2-ethylhexyl ester in fused salt hydrate |
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