CN107286018A - A kind of preparation method of environmentally friendly isooctyl thioglycolate - Google Patents
A kind of preparation method of environmentally friendly isooctyl thioglycolate Download PDFInfo
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- CN107286018A CN107286018A CN201710469150.0A CN201710469150A CN107286018A CN 107286018 A CN107286018 A CN 107286018A CN 201710469150 A CN201710469150 A CN 201710469150A CN 107286018 A CN107286018 A CN 107286018A
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- isooctyl
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- environmentally friendly
- isooctyl thioglycolate
- bunte salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/02—Thiosulfates
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of environmentally friendly isooctyl thioglycolate, it is characterised in that comprises the following steps：(1) rare earth solid super is added in isooctanol and chloroacetic acid solution, by the way of continuous uniform is mixed, generates Isooctyl chloroacetate；(2) prepared by bunte salt；(3) bunte is acidified, hydrolyzes and reduces, and then washing, rectifying, obtain isooctyl thioglycolate.A kind of preparation method of environmentally friendly isooctyl thioglycolate of the present invention, the reaction time is short, high conversion rate, cost are low, pollution is small.
Description
Technical field
The present invention relates to a kind of preparation method of Organic Chemicals mercapto-carboxylic ester, more particularly to a kind of TGA are different
The preparation method of monooctyl ester.
Background technology
Isooctyl thioglycolate（TGE）, it is synthetic plastic particularly polyvinyl chloride（PVC）Resin heat stabilizer it is important in
Mesosome, while also acting as inhibition side chain agent when polyvinyl chloride resin is manufactured for chloroethylene polymerization, molecular weight regulator, synthesis of bisphenol A
Catalyst, the new catalyst of synthesis of carboxylic acid acid amides etc., domestic and international market is very big.Due to domestic at present general using tradition
Production technology, produces large quantity of exhaust gas, waste water, waste residue in process of production, while economic benefit is produced, also pollutes ring
Border, influences the life of people.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of environmentally friendly isooctyl thioglycolate, the reaction time is short, convert
Rate is high, cost is low, pollution is small.
Technical scheme：A kind of preparation method of environmentally friendly isooctyl thioglycolate, it is characterised in that including following
Step：
(1) it is (1.3~1.6) in weight ratio: in 1 isooctanol and chloroacetic acid solution, adds 2%~5% monoxone weight meter
Rare earth solid super, by the way of continuous uniform is mixed, temperature be 70 DEG C~90 DEG C, pressure be 1~3,000,000
Reaction 0.5h~0.7h is carried out during handkerchief, Isooctyl chloroacetate is generated；
(2) according to weight ratio be 1: (1.4~1.8): 0.98 Isooctyl chloroacetate, sodium thiosulfate and isopropanol, normal pressure,
Under conditions of 120 DEG C~160 DEG C, the sulfhydrylation that flowed back after Isooctyl chloroacetate, sodium thiosulfate mixing in isopropanol solvent is anti-
0.5h~0.8h is answered, bunte salt is made；
(3) it is 2~5 the obtained bunte salt addition concentrated sulfuric acid to be acidified into PH values, hydrolyzes and reduces 0.8h~1.2h, temperature control
System is at 90 DEG C~110 DEG C, and then washing, rectifying, obtain isooctyl thioglycolate.
A kind of preparation method of foregoing environmentally friendly isooctyl thioglycolate, described bunte salt after it has been manufactured using temperature-
25 DEG C~-15 DEG C of chilled brine is circulated, by increasing amount of cooling water, is improved vapo(u)rizing temperature to 80 DEG C~90 DEG C, is made distillation
The isopropanol-water azeotropic mixture fast eliminating Bunte salt systems that kettle comes out.
A kind of preparation method of foregoing environmentally friendly isooctyl thioglycolate, described rare earth solid super is
SO42-/TiO2/La3+。
A kind of preparation method of foregoing environmentally friendly isooctyl thioglycolate, the continuous uniform mixing is continuously entered using pulse
The mode of material, charging rate is 1200L/h~1800L/h.
Compared with prior art, the present invention is used after first esterification into salt two-step method route, is such as adopted compared to general typical process
With first synthetic intermediate TGA, then using TGA and isooctanol as raw material, lactate synthesis isooctyl thioglycolate, it is to avoid
The severe contamination of TGA intermediate, the reaction time is greatly shortened, and conversion ratio is improved, and product purity is high, gradable to reach
Technical grade 95%, SILVER REAGENT 99% is required.
Catalyst progress esterification is made using the special rare earth solid super replacement concentrated sulfuric acid by designing,
Without neutralizing, washing, while catalyst is recyclable, reuse, wastewater flow rate in esterification reaction process is set to be reduced to zero, than one
As concentrated sulfuric acid technique reduce esterification waste water 1.3t/t, significantly abatement neutralize alkali and neutralize produce salt.
By having carried out a series of improvement to cooling technique, design two grades of deep condensation systems of increase are applied to salifying process
In the middle precipitation stage, circulated using the low chilled brine of temperature, by increasing amount of cooling water, vapo(u)rizing temperature can be improved, make steaming
Evaporate the isopropanol-water azeotropic mixture fast eliminating Bunte salt systems that kettle comes out；Effectively lower Bunte salt system solvent residual amounts, it is different
Reclamation rate of propyl alcohol about 70% brings up to 92% from what single-stage was condensed, cuts down sequential hydrolysis, layering, washing, rectification working process significantly
COD discharge capacitys in middle exhausted air quantity, waste water.
Present invention eliminates zinc powder reduction process, innovatively taking addition sulfuric acid to be hydrolyzed, to obtain TGA different pungent
Ester.The spent acid that hydrolysis layering is produced is main based on sulfuric acid, the higher NaHSO4 of inorganic salt content, NaCl, monoxone（And salt）, mercapto
Guanidine-acetic acid（And salt）Deng；A small amount of organic matter such as residual isopropanol, excessive isooctanol etc..Because Na2S2O3 is excessively more, sour water solution
When produce H2S gases, formed foul waste gas；Also due to Na2S2O3 presence, makes the thioorganic compounds of generation accessory substance two
The increase of side reaction probability, has the advantages that simplified technique, improves yield, clean environment firendly.
Embodiment
The present invention is further illustrated for example below, but is not intended as to the foundation of the invention limited.
Embodiment 1：
A kind of preparation method of environmentally friendly isooctyl thioglycolate, comprises the following steps：
(1) surpass in weight ratio in 1.3: 1 isooctanol and chloroacetic acid solution, to add the rare earth solid of 2% monoxone weight meter
Strong acid catalyst, by the way of continuous uniform is mixed, is 70 DEG C in temperature, and reaction 0.5h, generation are carried out when pressure is 1 MPa
Isooctyl chloroacetate；
(2) according to weight ratio be 1: 1.4: 0.98 Isooctyl chloroacetate, sodium thiosulfate and isopropanol, normal pressure, 120 DEG C
Under conditions of, flow back mercaptolation 0.5h after Isooctyl chloroacetate, sodium thiosulfate mixing in isopropanol solvent, is made
Bunte salt；
(3) it is 2 the obtained bunte salt addition concentrated sulfuric acid to be acidified into PH values, hydrolyzes and reduces 0.8h, temperature control is 90
DEG C, then washing, rectifying, obtain isooctyl thioglycolate.
Foregoing bunte salt is circulated using the chilled brine of -25 DEG C of temperature after it has been manufactured, by increasing amount of cooling water,
Vapo(u)rizing temperature is improved to 80 DEG C, the isopropanol-water azeotropic mixture fast eliminating Bunte salt systems for coming out distillation still.
Foregoing rare earth solid super is SO4 2-/TiO2/La3+。
Foregoing continuous uniform mixing is by the way of pulse continuous feed, and charging rate is 1200L/h.
Embodiment 2：
A kind of preparation method of environmentally friendly isooctyl thioglycolate, comprises the following steps：
(1) surpass in weight ratio in 1.6: 1 isooctanol and chloroacetic acid solution, to add the rare earth solid of 5% monoxone weight meter
Strong acid catalyst, by the way of continuous uniform is mixed, is 90 DEG C in temperature, and reaction 0.7h, generation are carried out when pressure is 3 MPas
Isooctyl chloroacetate；
(2) according to weight ratio be 1: 1.8: 0.98 Isooctyl chloroacetate, sodium thiosulfate and isopropanol, normal pressure, 160 DEG C
Under conditions of, flow back mercaptolation 0.8h after Isooctyl chloroacetate, sodium thiosulfate mixing in isopropanol solvent, is made
Bunte salt；
(3) it is 5 the obtained bunte salt addition concentrated sulfuric acid to be acidified into PH values, hydrolyzes and reduces 1.2h, temperature control is 110
DEG C, then washing, rectifying, obtain isooctyl thioglycolate.
Foregoing bunte salt is circulated using the chilled brine of -15 DEG C of temperature after it has been manufactured, by increasing amount of cooling water,
Vapo(u)rizing temperature is improved to 90 DEG C, the isopropanol-water azeotropic mixture fast eliminating Bunte salt systems for coming out distillation still.
Foregoing rare earth solid super is SO4 2-/TiO2/La3+。
Foregoing continuous uniform mixing is by the way of pulse continuous feed, and charging rate is 1800L/h.
Embodiment 3：
A kind of preparation method of environmentally friendly isooctyl thioglycolate, comprises the following steps：
(1) surpass in weight ratio in 1.5: 1 isooctanol and chloroacetic acid solution, to add the rare earth solid of 4% monoxone weight meter
Strong acid catalyst, by the way of continuous uniform is mixed, is 80 DEG C in temperature, and reaction 0.7h, generation are carried out when pressure is 2 MPas
Isooctyl chloroacetate；
(2) according to Isooctyl chloroacetate, sodium thiosulfate and the isopropanol that weight ratio is 1: 1.6: 0.98, normal pressure, 150 DEG C
Under the conditions of, flow back mercaptolation 0.7h after Isooctyl chloroacetate, sodium thiosulfate mixing in isopropanol solvent, is made
Bunte salt；
(3) by obtained bunte salt addition the concentrated sulfuric acid be acidified to PH values be 4, hydrolyze and reduce 1h, temperature control at 100 DEG C,
Then washing, rectifying, obtain isooctyl thioglycolate.
Foregoing bunte salt is circulated using the chilled brine of -20 DEG C of temperature after it has been manufactured, by increasing amount of cooling water,
Vapo(u)rizing temperature is improved to 85 DEG C, the isopropanol-water azeotropic mixture fast eliminating Bunte salt systems for coming out distillation still.
Foregoing rare earth solid super is SO4 2-/TiO2/La3+。
Foregoing continuous uniform mixing is by the way of pulse continuous feed, and charging rate is 1600L/h.
Embodiment 4：
A kind of preparation method of environmentally friendly isooctyl thioglycolate, comprises the following steps：
(1) surpass in weight ratio in 1.5: 1 isooctanol and chloroacetic acid solution, to add the rare earth solid of 4% monoxone weight meter
Strong acid catalyst, by the way of continuous uniform is mixed, is 90 DEG C in temperature, and reaction 0.7h, generation are carried out when pressure is 3 MPas
Isooctyl chloroacetate；
(2) according to weight ratio be 1: 1.7: 0.98 Isooctyl chloroacetate, sodium thiosulfate and isopropanol, normal pressure, 160 DEG C
Under conditions of, flow back mercaptolation 0.7h after Isooctyl chloroacetate, sodium thiosulfate mixing in isopropanol solvent, is made
Bunte salt；
(3) it is 3 the obtained bunte salt addition concentrated sulfuric acid to be acidified into PH values, hydrolyzes and reduces 0.9h, temperature control is 100
DEG C, then washing, rectifying, obtain isooctyl thioglycolate.
Foregoing bunte salt is circulated using the chilled brine of -15 DEG C of temperature after it has been manufactured, by increasing amount of cooling water,
Vapo(u)rizing temperature is improved to 90 DEG C, the isopropanol-water azeotropic mixture fast eliminating Bunte salt systems for coming out distillation still.
Foregoing rare earth solid super is SO4 2-/TiO2/La3+。
Foregoing continuous uniform mixing is by the way of pulse continuous feed, and charging rate is 1500L/h.
The present invention has following innovation：
1st, design substitutes the concentrated sulfuric acid using special rare earth solid super and carries out esterification, without neutralization, washing,
Catalyst is recyclable simultaneously, reuse, and wastewater flow rate in esterification reaction process is reduced to zero, subtracts than general concentrated sulfuric acid technique
Few esterification waste water 1.3t/t, significantly abatement neutralize alkali and neutralize the salt produced；
2nd, the precipitation stage in salifying process is applied to using two grades of deep condensation systems, greatly improves the recovery of solvent isopropanol again
Utilization rate, once reclaims yield and reaches more than 92%, reduce the volatilization loss amount of the solvent outwardly；
3rd, design substitutes concentrated hydrochloric acid using the common inexpensive concentrated sulfuric acid and reduction reaction is hydrolyzed in zinc powder, it is to avoid H2S production
It is raw, greatly reduce HCl spent acidic tolerance, eliminate the generation of new pollutant zinc in waste water, make finally to integrate waste liquid amount reduction, give up
Salt species is single in liquid, salt content reduction, it is easy to biochemical treatment.Simultaneously spent acid can also by separating-purifying reclaim meet industry can
Reuse；
4th, using after being first esterified into salt two-step method route, compared to general typical process, it is to avoid TGA intermediate it is serious
Pollution, greatly shortens the reaction time, improves conversion ratio, and product purity is high, gradable to reach that technical grade 95%, SILVER REAGENT 99%
Ask.
Claims (4)
1. a kind of preparation method of environmentally friendly isooctyl thioglycolate, it is characterised in that comprise the following steps：
(1) it is (1.3~1.6) in weight ratio: in 1 isooctanol and chloroacetic acid solution, adds 2%~5% monoxone weight meter
Rare earth solid super, by the way of continuous uniform is mixed, temperature be 70 DEG C~90 DEG C, pressure be 1~3,000,000
Reaction 0.5h~0.7h is carried out during handkerchief, Isooctyl chloroacetate is generated；
(2) according to weight ratio be 1: (1.4~1.8): 0.98 Isooctyl chloroacetate, sodium thiosulfate and isopropanol, normal pressure,
Under conditions of 120 DEG C~160 DEG C, the sulfhydrylation that flowed back after Isooctyl chloroacetate, sodium thiosulfate mixing in isopropanol solvent is anti-
0.5h~0.8h is answered, bunte salt is made；
(3) it is 2~5 the obtained bunte salt addition concentrated sulfuric acid to be acidified into PH values, hydrolyzes and reduces 0.8h~1.2h, temperature control
System is at 90 DEG C~110 DEG C, and then washing, rectifying, obtain isooctyl thioglycolate.
2. a kind of preparation method of environmentally friendly isooctyl thioglycolate as claimed in claim 1, it is characterised in that described
Bunte salt is circulated using the chilled brine of -25 DEG C~-15 DEG C of temperature after it has been manufactured, by increasing amount of cooling water, improves distillation
Temperature is to 80 DEG C~90 DEG C, the isopropanol-water azeotropic mixture fast eliminating Bunte salt systems for coming out distillation still.
3. a kind of preparation method of environmentally friendly isooctyl thioglycolate as claimed in claim 1, it is characterised in that described rare earth
Solid super acid catalyst is SO4 2-/TiO2/La3+。
4. a kind of preparation method of environmentally friendly isooctyl thioglycolate as claimed in claim 1, it is characterised in that described continuous equal
Even mixing is by the way of pulse continuous feed, and charging rate is 1200L/h~1800L/h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710469150.0A CN107286018A (en) | 2017-06-20 | 2017-06-20 | A kind of preparation method of environmentally friendly isooctyl thioglycolate |
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| CN201710469150.0A CN107286018A (en) | 2017-06-20 | 2017-06-20 | A kind of preparation method of environmentally friendly isooctyl thioglycolate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120646A (en) * | 1982-12-27 | 1984-07-12 | Adeka Argus Chem Co Ltd | Chlorinated vinyl chloride resin composition |
| CN102267930A (en) * | 2010-06-04 | 2011-12-07 | 湖州市菱湖佳润化工有限公司 | Preparation method of high concentration isooctylmercaptoacetate |
-
2017
- 2017-06-20 CN CN201710469150.0A patent/CN107286018A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120646A (en) * | 1982-12-27 | 1984-07-12 | Adeka Argus Chem Co Ltd | Chlorinated vinyl chloride resin composition |
| CN102267930A (en) * | 2010-06-04 | 2011-12-07 | 湖州市菱湖佳润化工有限公司 | Preparation method of high concentration isooctylmercaptoacetate |
Non-Patent Citations (1)
| Title |
|---|
| 黄德智等: "巯基乙酸异辛酯合成方法的研究", 《现代化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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: 20171024 |
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