CN102329257A - Production method of thioglycolic acid pentaerythritol ester - Google Patents
Production method of thioglycolic acid pentaerythritol ester Download PDFInfo
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- CN102329257A CN102329257A CN201110286172A CN201110286172A CN102329257A CN 102329257 A CN102329257 A CN 102329257A CN 201110286172 A CN201110286172 A CN 201110286172A CN 201110286172 A CN201110286172 A CN 201110286172A CN 102329257 A CN102329257 A CN 102329257A
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- pentaerythritol ester
- thiovanic acid
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Abstract
The invention discloses a production method of thioglycolic acid pentaerythritol ester. The method comprises the following steps: 1) the charging reaction stage: adding pentaerythritol and thioglycolic acid into a reaction device according to the molar ratio of 1: (4.4-4.8), then adding a catalyst and reacting for 8-10 hours under the vacuum condition, at the temperature of 100-110 DEG C and under the stirring state; 2) the skimming and distillation stage: reducing the temperature of material solution obtained by the reaction to 40-55 DEG C after completing the reaction, adding an organic inert solvent and water in the equal water with the organic inert solvent, stirring and washing for 10-20 minutes, skimming to get a solvent layer and an ester layer, washing the solvent layer and the ester layer with the water till the pH value of the material solution is 5.5-6.5, and then performing skimming and distillation on the material solution to prepare the thioglycolic acid pentaerythritol ester. The organic inert solvent is added to reduce the viscosity of the material solution, the content of free remnant acid in the product is reduced to the greatest extent on the premise of high acid-alcohol ratio, and the product quality is ensured.
Description
Technical field
The present invention relates to the fine chemical technology field, relate in particular to a kind of working method of Thiovanic acid pentaerythritol ester.
Background technology
The Thiovanic acid pentaerythritol ester is claimed thioglycolic acid pentaerythritol ester, thioglycollic acid tetramethylolmethane etc. again, English name: Pentaerythritoltetrakis (2-mercaptoacetate); Molecular formula C13H20O8S4; Molecular weight 432.55; CAS accession number 10193-99-4.As organic intermediate, acidic lon exchange catalysts, coupler also can be used as polymeric modifier in the industry.
In the production of Thiovanic acid pentaerythritol ester is synthetic; Because Thiovanic acid must be excessive greatly; The viscosity of Thiovanic acid pentaerythritol ester own is big; Be not easy in the washing process to clean remaining free acid, and its derived product production process has certain requirement to residual acid content, therefore performance of products is exerted a certain influence.
Summary of the invention
Technical problem to be solved by this invention provides free residual acid content in a kind of obvious minimizing product, guarantees the working method of the Thiovanic acid pentaerythritol ester of quality product.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of working method of Thiovanic acid pentaerythritol ester comprises step:
1) the charging reaction stage:
Tetramethylolmethane and Thiovanic acid are pressed in the mol ratio adding reaction unit of 1:4.4～4.8, added catalyzer afterwards, under the vacuum,, and under whipped state, reacted 8～10 hours at 100～110 ℃;
2) the separatory distillation stage:
After above-mentioned reaction finishes; The resulting feed liquid of said reaction is cooled to 40～55 ℃; Add organic inert solvent and with the water of quality such as said organic inert solvent, stir and washed 10～20 minutes, separatory obtains solvent layer and ester layer; Is 5.5～6.5 with said solvent layer and ester layer use water washing until said material liquid PH value, subsequently said feed liquid is carried out the separatory distillation and makes said Thiovanic acid pentaerythritol ester.
As optimized technical scheme, the purity of said tetramethylolmethane >=95%, the purity of said Thiovanic acid >=95%.
As optimized technical scheme, said catalyzer is tosic acid, solid acid catalyst such as solid phosphoric acid; Solid super acid catalyst such as s-/Fe
30
4-Al
20
3, said catalyst consumption is reaction raw materials 0.5%～1.0% of the total mass that feeds intake.
As optimized technical scheme, the vacuum tightness of the vacuum state of said charging reaction in the stage is-0.098～-0.1MPa
As optimized technical scheme; Said organic inert solvent does; Said No. 60 sherwood oils are that boiling range is that 60～90 ℃ sherwood oil, isopropyl ether or boiling range is 60～120 ℃ ethers, benzene kind solvent, and the mass ratio of said organic inert solvent and Thiovanic acid is 1:1.3～2.0.
As optimized technical scheme, the distillation of said separatory be-0.098～-0.1MPa under underpressure distillation, tell front-end volatiles, and, reclaim residual free acid through extractive distillation afterwards the water outlet in static minute of said front-end volatiles.
As optimized technical scheme, the ether extration agent is used in said extractive distillation, like anhydrous diethyl ether or ketone extraction agent,, reclaim said free acid like MIBK, the mass ratio of said extraction agent and said Thiovanic acid is 1:1～3.
As improvement to technique scheme, the free acid of said recovery is continued to recycle, practiced thrift cost.
Owing to adopted technique scheme; A kind of working method of Thiovanic acid pentaerythritol ester comprises step: 1) the charging reaction stage: tetramethylolmethane and Thiovanic acid are pressed in the mol ratio adding reaction unit of 1:4.4～4.8, added catalyzer afterwards; Under the vacuum; At 100～110 ℃, and under whipped state, reacted 8～10 hours; 2) the separatory distillation stage: after above-mentioned reaction finishes, the resulting feed liquid of said reaction is cooled to 40～55 ℃, add organic inert solvent and with the water of quality such as said organic inert solvent; Stir and wash 10～20 minutes, separatory obtains solvent layer and ester layer, is 5.5～6.5 with said solvent layer and ester layer use water washing until said material liquid PH value; Subsequently said feed liquid is carried out the separatory distillation and make said Thiovanic acid pentaerythritol ester, reduced the free acid content of Thiovanic acid pentaerythritol ester, and in the building-up process; The main raw material Thiovanic acid that uses can be excessive greatly, strengthened main reaction, increased output; Effectively reduce cost; Improved competition capability, produce the Thiovanic acid pentaerythritol ester, content >=95.0%.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment one:
1500L have electric mixer, a TM, in the reaction unit of vacuum unit etc., add purity and be 95% Thiovanic acid 426.7Kg and purity and be 95% tetramethylolmethane 143.3Kg, and tosic acid 2.85Kg, in-0.098 vacuum tightness; 100 ℃ of refluxed stirring reactions 8 hours stop to stir, and feed temperature is reduced to about 45 ℃, add the 202.7Kg60 sherwood oil; 202.7Kg water continues to stir 10 minutes, tells the solvent layer on upper strata, the ester layer of lower floor with liquid distributing device, and solvent and ester layer are washed with 40 ℃ of water; Each water consumption 202.7Kg washes 2 times, and material liquid PH value is 5, underpressure distillation under-0.098MPa; Tell front-end volatiles, Thiovanic acid pentaerythritol ester product is retained at the bottom of the still, and front-end volatiles 220Kg is through leaving standstill the branch water outlet; Merge with washing water, send extractive distillation, make extraction agent, reclaim free acid with the 135.1Kg anhydrous diethyl ether; Recovered acid continues to recycle, product volume 380Kg at the bottom of the still, content 96.0%, acid number (KOH mg/g) 1.00.
Embodiment two:
1500L have electric mixer, a TM, in the reaction unit of vacuum unit, add purity and be 96% Thiovanic acid 446.0Kg and purity and be 96% tetramethylolmethane 139.0Kg, and solid acid catalyst solid phosphoric acid 5.9Kg; At vacuum tightness-0.099MPa, 105 ℃ of refluxed stirring reactions 9 hours stop to stir; Feed temperature is reduced to about 45 ℃, adds the 300Kg isopropyl ether, 300Kg water; Continue to stir 15 minutes, and told the ester layer of lower floor, the ester layer is washed with 45 ℃ of water with liquid distributing device; Each water consumption 300Kg washes 3 times, and material liquid PH value is 6; Front-end volatiles are told in underpressure distillation under the-0.099MPa, and Thiovanic acid pentaerythritol ester product is retained at the bottom of the still.Front-end volatiles 250Kg through leaving standstill the branch water outlet, merges with washing water, send extractive distillation; Make extraction agent with the 214.1Kg MIBK, reclaim wherein free acid, recovered acid continues to recycle; Product volume 405Kg at the bottom of the still, content 96.0%, acid number (KOH mg/g) 0.90.
Embodiment three:
1500L have electric mixer, a TM, in the reaction unit of vacuum unit, add purity and be 97% Thiovanic acid 455.9Kg and purity and be 97% tetramethylolmethane 140.4Kg, and solid super acid catalyst s-/Fe
30
4-Al
20
35.8Kg at-0.1MPa, 110 ℃ of refluxed stirring reactions 10 hours stop to stir, and feed temperature is reduced to 50 ℃; Add No. 60 sherwood oils of 340.2Kg, the 340.2Kg warm water continues to stir 20 minutes, tells the ester layer of lower floor with liquid distributing device, and the water of ester layer with 50 ℃ is washed; Each water consumption 263.9Kg washes 4 times, and material liquid PH value is 7, under-0.1MPa, and underpressure distillation; Tell front-end volatiles, Thiovanic acid pentaerythritol ester product is retained at the bottom of the still, and front-end volatiles are 250Kg, through leaving standstill the branch water outlet; Merge with washing water, send extractive distillation, make extraction agent, reclaim free acid with the 442.2Kg anhydrous diethyl ether; Free acid continues to recycle, product volume 408Kg at the bottom of the still, content 96.0%, acid number (KOH mg/g) 0.85.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
All are from design of the present invention, and the structural transformation of having done without creative work all drops within protection scope of the present invention.
Claims (9)
1. the working method of a Thiovanic acid pentaerythritol ester is characterized in that, comprises step:
1) the charging reaction stage:
Tetramethylolmethane and Thiovanic acid are pressed in the mol ratio adding reaction unit of 1:4.4～4.8, added catalyzer afterwards, under the vacuum,, and under whipped state, reacted 8～10 hours at 100～110 ℃;
2) the separatory distillation stage:
After above-mentioned reaction finishes; The resulting feed liquid of said reaction is cooled to 40～55 ℃; Add organic inert solvent and with the water of quality such as said organic inert solvent, stir and washed 10～20 minutes, separatory obtains solvent layer and ester layer; Is 5.5～6.5 with said solvent layer and said ester layer use water washing until said material liquid PH value, subsequently said feed liquid is carried out the separatory distillation and makes said Thiovanic acid pentaerythritol ester.
2. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 1 is characterized in that: the purity of said tetramethylolmethane >=95%, the purity of said Thiovanic acid >=95%.
3. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 1; It is characterized in that: said catalyzer is tosic acid, solid acid catalyst or solid super acid catalyst, and said catalyst consumption is reaction raw materials 0.5%～1.0% of the total mass that feeds intake.
4. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 1 is characterized in that: the vacuum tightness of the vacuum state of said charging reaction in the stage is-0.098～-0.1MPa.
5. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 1; It is characterized in that: said organic inert solvent is that No. 60 sherwood oils, isopropyl ether or boiling ranges are 60～120 ℃ ethers, benzene kind solvent, and the mass ratio of said organic inert solvent and said Thiovanic acid is 1:1.3～2.0.
6. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 1 is characterized in that: the water washing that said solvent layer and said ester layer washing use are 40～50 ℃ 2～4 times, each bath water amount and said organic inert solvent are identical in quality.
7. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 1; It is characterized in that: the distillation of said separatory be-0.098～-0.1MPa under underpressure distillation; Tell front-end volatiles, and, reclaim residual free acid through extractive distillation afterwards the water outlet in static minute of said front-end volatiles.
8. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 7 is characterized in that: use ether extration agent or ketone extraction agent to reclaim said free acid said extractive distillation.
9. the working method of a kind of Thiovanic acid pentaerythritol ester as claimed in claim 7 is characterized in that: the free acid of said recovery is continued to recycle.
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| CN201110286172A CN102329257A (en) | 2011-09-24 | 2011-09-24 | Production method of thioglycolic acid pentaerythritol ester |
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| CN201110286172A CN102329257A (en) | 2011-09-24 | 2011-09-24 | Production method of thioglycolic acid pentaerythritol ester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187842A (en) * | 2016-07-13 | 2016-12-07 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of many mercapto-carboxylic esters |
| CN110256311A (en) * | 2019-05-24 | 2019-09-20 | 潍坊加华化工有限公司 | A kind of methyl thioglycolate process for refining |
| CN112002458A (en) * | 2020-08-03 | 2020-11-27 | 浙江泰仑电力集团有限责任公司 | Inorganic filler surface coated silver, waterborne photocuring conductive silver paste thereof and preparation method thereof |
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| EP0718282A1 (en) * | 1994-12-19 | 1996-06-26 | MERCK PATENT GmbH | Process for preparing alkyl esters of thioglycolic acid |
| CN101580485A (en) * | 2009-06-01 | 2009-11-18 | 潍坊加华化工有限公司 | Method for producing methyl thioglycolate |
| JP2011084479A (en) * | 2009-10-13 | 2011-04-28 | Showa Denko Kk | Method of producing mercaptocarboxylate of polyhydric alcohol |
-
2011
- 2011-09-24 CN CN201110286172A patent/CN102329257A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0718282A1 (en) * | 1994-12-19 | 1996-06-26 | MERCK PATENT GmbH | Process for preparing alkyl esters of thioglycolic acid |
| CN101580485A (en) * | 2009-06-01 | 2009-11-18 | 潍坊加华化工有限公司 | Method for producing methyl thioglycolate |
| JP2011084479A (en) * | 2009-10-13 | 2011-04-28 | Showa Denko Kk | Method of producing mercaptocarboxylate of polyhydric alcohol |
Non-Patent Citations (2)
| Title |
|---|
| 李健 等: "季戊四醇四(2-巯基乙酸)酯的合成研究", 《广州化工》 * |
| 胡应喜等: "SO4~(2-)/TiO2La2O3催化合成季戊四醇四乙酸酯", 《化学工业与工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187842A (en) * | 2016-07-13 | 2016-12-07 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of many mercapto-carboxylic esters |
| CN110256311A (en) * | 2019-05-24 | 2019-09-20 | 潍坊加华化工有限公司 | A kind of methyl thioglycolate process for refining |
| CN112002458A (en) * | 2020-08-03 | 2020-11-27 | 浙江泰仑电力集团有限责任公司 | Inorganic filler surface coated silver, waterborne photocuring conductive silver paste thereof and preparation method thereof |
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Application publication date: 20120125 |