CN106187842A - A kind of preparation method of many mercapto-carboxylic esters - Google Patents
A kind of preparation method of many mercapto-carboxylic esters Download PDFInfo
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- CN106187842A CN106187842A CN201610554561.5A CN201610554561A CN106187842A CN 106187842 A CN106187842 A CN 106187842A CN 201610554561 A CN201610554561 A CN 201610554561A CN 106187842 A CN106187842 A CN 106187842A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
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Abstract
The invention provides the preparation method of a kind of many mercapto-carboxylic esters, including: by mercaptan carboxylic acid and polyhydric alcohol at pressure≤0.07MPa, react under conditions of temperature 80～100 DEG C, obtain many mercapto-carboxylic esters.The present invention, under conditions of high temperature, negative pressure, carries out the esterification of mercaptan carboxylic acid and polyhydric alcohol, it is not necessary to use water entrainer, solves the series of problems using water entrainer to bring, and saves water entrainer loss, improves reaction rate, improve product quality simultaneously.
Description
Technical field
The present invention relates to chemical field, particularly relate to the preparation method of a kind of many mercapto-carboxylic esters.
Background technology
Many mercapto-carboxylic esters are important chemical industry and organic synthesis intermediate, wherein tetramethylolmethane four (3-mercaptopropionic acid)
Ester is the esterification products of tetramethylolmethane and mercaptopropionic acid, is mainly used in synthesizing optical resin, be simultaneously available for UV coating, ink,
Modifying agent in the polyreactions such as binding agent, cross-linking agent, acid ion exchange modifying agent etc..
The synthetic method of current many mercapto-carboxylic esters has esterification process, ester-interchange method, and wherein esterification process is current most study
Method, and have been carried out industrialization；Ester-interchange method is less because of the sterically hindered bigger research of tetramethylolmethane.
But in esterification process, owing to being affected by sterically hindered, polyhydric alcohol needs to be esterified step by step.And polyhydric alcohol and carboxylic acid
The reaction equilibrium constant of esterification is the least, needs constantly to remove in course of reaction the water that reaction generates, and reaction could be towards ester
The direction changed is carried out.The most general water-eliminating method is to use water entrainer azeotrope with water to take water out of reaction system, is then dividing
Being separated with water entrainer by water in hydrophone, water entrainer is back to reaction system, and moisture goes out reaction system.But use a point water preparation have with
Lower shortcoming:
(1) in course of reaction, need to heat and make water entrainer boiling that water to be taken out of reaction system, energy consumption is high, simultaneously need to use
The mixed vapour of water entrainer with water is cooled down by cooling water, and cooling water amount is relatively big, causes the wasting of resources；
(2) post processing needs to isolate water entrainer, adds operation easier, and whole during water entrainer have loss
(loss amount about 20%), adds production cost；
(3) use of water entrainer dilutes raw material, reduces the collision probability between raw material, reduces reaction rate, and
And the low molecular balance that has a strong impact on of water entrainer band water efficiency, conditioned response speed, raw material reaction is incomplete, needs in post processing
Journey removes remaining reaction raw materials, but is very difficult to, except thoroughly, cause product acid number higher, affect product quality.
Meanwhile, in order to improve esterification reaction rate, course of reaction needs add the mineral acid such as sulphuric acid and phosphoric acid, titanate esters
The organic acid esters stronger with the lewis acidity such as zirconate, has the organic acid such as p-methyl benzenesulfonic acid and pyrovinic acid of stronger acids to make
Catalyst for esterification.These catalyst have a common shortcoming, the most miscible in reaction system, separate back
Receive difficulty, etching apparatus etc..
In sum, the method synthesizing many mercapto-carboxylic esters at present, owing to water entrainer divides water efficiency to limit, except water is relatively slow,
Phase after the reaction, reaction rate is extremely slow, and starting carboxylic acid is difficult to reaction completely.Simultaneously because containing acidic catalyst in system
Agent, so post-processing difficulty is bigger.And acid is difficult to except thoroughly, the acid number thus causing product is higher.Simultaneously because it is anti-
Use water entrainer, extractant, water equal solvent with last handling process during Ying, cause product remains low boiling substance, impact
Properties of product, and make product carry the bad smell of one solvent and raw material, product quality is low.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the preparation method of a kind of many mercapto-carboxylic esters, tool
There is higher reaction rate, and the many mercapto-carboxylic esters prepared have higher quality.
The invention provides the preparation method of a kind of many mercapto-carboxylic esters, including:
By mercaptan carboxylic acid and polyhydric alcohol at pressure≤-0.07MPa, react under conditions of temperature 80～100 DEG C, obtain
Many mercapto-carboxylic esters.
Preferably, the reaction unit of described reaction includes negative pressure condensing unit.
Preferably, described mercaptan carboxylic acid has a structure shown in formula (I):
HS-R-COOH (I)；
Wherein, R is C1～6Straight or branched or cyclic alkylidene.
Preferably, described mercaptan carboxylic acid is TGA, 2 mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutyric acid, 3-sulfydryl
One or more in butanoic acid.
Preferably, described polyhydric alcohol is 2-methyl isophthalic acid, ammediol, butanediol, neopentyl glycol, hexanediol, glycerol, three hydroxyls
Methylpropane, ethoxyquin trimethylolpropane, the third oxidation trimethylolpropane, tetramethylolmethane, Bis(pentaerythritol), tripentaerythritol
In one or more.
Preferably, in described mercaptan carboxylic acid, in carboxyl total amount and polyhydric alcohol, the mol ratio of hydroxyl total amount is 0.95～1.
Preferably, described reaction is carried out under the catalysis of solid super-strong acid.
Preferably, described solid super-strong acid is SO4 2-/Al2O3-ZrO2。
Preferably, described solid super-strong acid is prepared in accordance with the following methods:
A) in aluminum nitrate solution, add five water zirconium nitrates, heating for dissolving, obtain colourless transparent solution；
B) ethylenediamine solution is added in above-mentioned colourless transparent solution, obtain the jelly with white precipitate；
C) above-mentioned jelly is carried out crystallization, obtain crystal；
D) above-mentioned crystal sequentially passes through roasting, ammonium sulfate solution soaks, dry, calcination process, obtains solid super strong
Acid SO4 2-/Al2O3-ZrO2。
Preferably, described mercaptan carboxylic acid is mercaptopropionic acid, and described polyhydric alcohol is tetramethylolmethane.
Compared with prior art, the invention provides the preparation method of a kind of many mercapto-carboxylic esters, including: by mercaptan carboxylic acid
With polyhydric alcohol at pressure≤-0.07MPa, react under conditions of temperature 80～100 DEG C, obtain many mercapto-carboxylic esters.This
Bright under conditions of high temperature, negative pressure, carry out the esterification of mercaptan carboxylic acid and polyhydric alcohol, it is not necessary to use water entrainer, solve and make
The series of problems brought with water entrainer, saves water entrainer loss, improves reaction rate, improve product quality simultaneously.
Accompanying drawing explanation
Fig. 1 is the liquid phase Overlay chromatograms of tetramethylolmethane four (3-mercaptopropionic acid) ester prepared of the application and standard substance；
Fig. 2 is the liquid matter figure of tetramethylolmethane four (3-mercaptopropionic acid) ester prepared by the application.
Detailed description of the invention
The invention provides the preparation method of a kind of many mercapto-carboxylic esters, including: by mercaptan carboxylic acid and polyhydric alcohol at pressure
≤-0.07MPa, reacts under conditions of temperature 80～100 DEG C, obtains many mercapto-carboxylic esters.
The present invention, under conditions of high temperature, negative pressure, carries out the esterification of mercaptan carboxylic acid and polyhydric alcohol, it is not necessary to use band water
Agent, solves the series of problems using water entrainer to bring, and saves water entrainer loss, improves reaction rate, improve simultaneously
Product quality.
The preparation method of many mercapto-carboxylic esters that the present invention provides, in course of reaction, uses vacuum equipped to make reaction system
It is in the negative pressure state of pressure≤-0.07MPa, and to keep reaction temperature be 80～100 DEG C, use the negative pressure condensing unit will reaction
The vaporous water generated is cooled to liquid, flows into water tank, reaches the purpose except water.
In the present invention, described mercaptan carboxylic acid has a structure shown in formula (I):
HS-R-COOH (I)；
Wherein, R is preferably C1～6Straight or branched or cyclic alkylidene, more preferably C1～4Straight or branched alkylene
Base, more preferably C1～2Straight-chain alkyl-sub-.
It is furthermore preferred that described mercaptan carboxylic acid is TGA, 2 mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutyric acid, 3-mercapto
One or more in base butanoic acid；Most preferably TGA, 2 mercaptopropionic acid or 3-mercaptopropionic acid；Some tool in the present invention
In body embodiment, described mercaptan carboxylic acid is 3-mercaptopropionic acid.
Described polyhydric alcohol is preferably 2-methyl-1,3-propanediol, butanediol, neopentyl glycol, hexanediol, glycerol, three hydroxyl first
In base propane, ethoxyquin trimethylolpropane, the third oxidation trimethylolpropane, tetramethylolmethane, Bis(pentaerythritol), tripentaerythritol
One or more, more preferably tetramethylolmethane, glycerol, trimethylolpropane or Bis(pentaerythritol)；More preferably tetramethylolmethane
Or trimethylolpropane；In some embodiments of the invention, described polyhydric alcohol is tetramethylolmethane.
In described mercaptan carboxylic acid, in carboxyl total amount and polyhydric alcohol, the mol ratio of hydroxyl total amount is preferably 0.95～1, more preferably
It is 0.97～0.99.
The present invention there is no particular determination to the source of above-mentioned mercaptan carboxylic acid and polyhydric alcohol, can be the most commercially available.
The present invention, in course of reaction, is generated the quality of water, or is followed the tracks of by liquid phase by detection, when the water generated reaches
After theoretical water yield or liquid chromatograph show that raw material reaction is completely, stopped reaction.
Currently preferred, described reaction is carried out under the catalysis of solid super-strong acid.
Described solid super-strong acid is preferably the zirconium aluminum system that sulfate radical promotes, i.e. SO4 2-/Al2O3-ZrO2。
Preferably, described solid super-strong acid is prepared in accordance with the following methods:
A) in aluminum nitrate solution, add five water zirconium nitrates, heating for dissolving, obtain colourless transparent solution；
B) ethylenediamine solution is added in above-mentioned colourless transparent solution, obtain the jelly with white precipitate；
C) above-mentioned jelly is carried out crystallization, obtain crystal；
D) above-mentioned crystal sequentially passes through roasting, ammonium sulfate solution soaks, dry, calcination process, obtains solid super strong
Acid SO4 2-/Al2O3-ZrO2。
Above-mentioned aluminum nitrate solution is the aqueous solution of aluminum nitrate and dispersant.
Described dispersant is preferably ethylene glycol.
The mass volume ratio of described aluminum nitrate and dispersant is preferably (0.2～0.6) g:(2～6) mL.
The mass ratio of described aluminum nitrate and five water zirconium nitrates is preferably 1:(20～30).
Described ethylenediamine solution is the aqueous solution of ethylenediamine.
The mass concentration of described ethylenediamine solution is preferably 4%～8%.
Above-mentioned crystallization is preferably carried out in crystallizing kettle, and the temperature of described crystallization is preferably 80～120 DEG C, and crystallization time is preferred
It is 3～5h.
Filter after crystallization, be dried to obtain crystal, then described crystal carried out roasting.The temperature of described roasting is preferably
400～800 DEG C, the time of described roasting is preferably 2～8h.Currently preferred, described roasting is carried out in Muffle furnace.
After roasting terminates, take out and use ammonium sulfate solution immersion treatment.The concentration of described ammonium sulfate solution is preferably 0.3
～1mol/L, the time of described immersion is preferably 4～8h.
After immersion terminates, finished product is taken out and dries.The temperature of described drying is preferably 100～140 DEG C, described drying time
Between be preferably 10～15h.
Finished product after drying carries out roasting again, i.e. can get solid super-strong acid SO4 2-/Al2O3-ZrO2.The temperature of described roasting
Degree is preferably 400～800 DEG C, and the time of described roasting is preferably 2～8h.Currently preferred, described roasting is in Muffle furnace
Carry out.
The present invention uses homemade solid super acid catalyst, and catalytic efficiency is high, low cost, and environmental protection prepares
Product colourity low, purity is high, and free from extraneous odour, acid number is low.
After reaction terminates, while hot crude product is filtered, isolate solid super acid catalyst, i.e. can get target and produce
Product, catalyst can recycle.
In order to further illustrate the present invention, below in conjunction with the preparation side of many mercapto-carboxylic esters that the present invention is provided by embodiment
Method is described in detail.
Embodiment 1
In beaker add 80ml deionized water, 5ml dispersant ethylene glycol, the aluminum nitrate of 0.44g mix homogeneously, after add
Enter five water zirconium nitrate 10g, heating for dissolving, and be stirred continuously and obtain colourless transparent solution.Take 3.0g ethylenediamine and be slowly dropped to 50g
In deionized water, also mix homogeneously configures ethylenediamine solution, and is slowly dropped in above-mentioned solution by the ethylenediamine solution prepared,
Produce white precipitate.Above-mentioned jelly is loaded in crystallizing kettle, crystallization 4h under the conditions of 100 DEG C.After taking-up, first sucking filtration is dried, after
Roasting 4h under the conditions of 500 DEG C in Muffle furnace, soaks with the ammonium sulfate solution of 0.5mol/L after taking-up, stirring again, stands 6h.
Being dried 12h in the baking oven of 120 DEG C, then roasting 4h under the conditions of 500 DEG C, obtains solid super acid catalyst SO4 2-/Al2O3-
ZrO2。
Embodiment 2
Equipped with mechanical agitation, thermometer, negative pressure condensing unit 500ml four-hole boiling flask in, add tetramethylolmethane 68.8g
(0.50mol), 3-mercaptopropionic acid 214.1g (2.0mol), the catalyst SO of embodiment 1 preparation4 2-/Al2O3-ZrO25.66g, adjust
Whole negative pressure-0.08MPa, oil bath heating, 80-100 DEG C of reaction, also except water, reaches stopped reaction after theoretical water yield.After reacting
Mixture be placed in buchner funnel filtration, reclaiming the solid catalyst filtered out can reuse, in filtering flask colourless
Transparent tetramethylolmethane four (3-mercaptopropionic acid) ester 244.2g, purity 99.2%.
Using liquid chromatograph and liquid chromatography mass spectrometric to detect product structure, result is shown in Fig. 1 and Fig. 2, and wherein, Fig. 1 is this
Tetramethylolmethane four (3-mercaptopropionic acid) ester of application preparation and the liquid phase Overlay chromatograms of standard substance, wherein, spectrogram a is standard substance
Spectrogram, spectrogram b is tetramethylolmethane four (3-mercaptopropionic acid) ester spectrogram prepared by the application；Fig. 2 is Ji Wusi prepared by the application
The liquid matter figure of alcohol four (3-mercaptopropionic acid) ester.
Liquid phase analysis display product is the most identical with standard sample；The molecular formula of liquid matter analysis display product is
C17H28O8S4, consistent with target product.Visible, the application has prepared tetramethylolmethane four (3-mercaptopropionic acid) ester.
Embodiment 3
Equipped with mechanical agitation, thermometer, negative pressure condensing unit 500ml four-hole boiling flask in, add tetramethylolmethane 68.8g
(0.50mol), 3-mercaptopropionic acid 214.1g (2.0mol), the catalyst SO that embodiment 2 reclaims4 2-/Al2O3-ZrO25.60g, press
The method of embodiment 2 operates to obtain water white tetramethylolmethane four (3-mercaptopropionic acid) ester 244.0g, purity 99.1%.
Embodiment 4
Equipped with mechanical agitation, thermometer, negative pressure condensing unit 500ml four-hole boiling flask in, add tetramethylolmethane 68.8g
(0.50mol), TGA 186.1g (2.0mol), catalyst SO4 2-/Al2O3-ZrO25.10g, adjusts negative pressure-0.08MPa,
Oil bath is heated, and 80-100 DEG C of reaction also removes water, reaches stopped reaction after theoretical water yield.Reacted mixture is placed in Bu Shi
Filtering in funnel, reclaiming the solid catalyst filtered out can reuse, and obtains water white tetramethylolmethane four in filtering flask
(TGA) ester 216.3g, purity 99.3%.
Embodiment 5
Equipped with mechanical agitation, thermometer, negative pressure condensing unit 500ml four-hole boiling flask in, add trimethylolpropane
67.7g (0.50mol), 3-mercaptopropionic acid 160.7g (1.5mol), catalyst SO4 2-/Al2O3-ZrO26.23g, adjustment negative pressure-
0.08MPa, oil bath heating, 80-100 DEG C of reaction, also except water, reaches stopped reaction after theoretical water yield.By reacted mixture
Being placed in buchner funnel filtration, reclaiming the solid catalyst filtered out can reuse, and obtains water white three in filtering flask
Hydroxymethyl-propane three (3-mercaptopropionic acid) ester 199.1g, purity 99.2%.
Embodiment 6
Equipped with mechanical agitation, thermometer, negative pressure condensing unit 1000ml four-hole boiling flask in, add Bis(pentaerythritol)
127.1g (0.50mol), 3-mercaptopropionic acid 318.4g (3.0mol), catalyst SO4 2-/Al2O3-ZrO28.91g, adjustment negative pressure-
0.08MPa, oil bath heating, 80-100 DEG C of reaction, also except water, reaches stopped reaction after theoretical water yield.By reacted mixture
Being placed in buchner funnel filtration, reclaiming the solid catalyst filtered out can reuse, and obtains water white transparency thickness in filtering flask
Bis(pentaerythritol) six (3-mercaptopropionic acid) ester 390.5g, purity 99.1%.
Embodiment 7
Equipped with mechanical agitation, thermometer, negative pressure condensing unit 1000ml four-hole boiling flask in, add tripentaerythritol
186.2g (0.50mol), 3-mercaptopropionic acid 424.6g (4.0mol), catalyst SO4 2-/Al2O3-ZrO210.77g, adjust negative
Pressure-0.08MPa, oil bath heating, 80-100 DEG C of reaction, also except water, reaches stopped reaction after theoretical water yield.By reacted mixed
Compound is placed in buchner funnel filtration, and reclaiming the solid catalyst filtered out can reuse, and obtains faint yellow viscous in filtering flask
Thick tripentaerythritol eight (3-mercaptopropionic acid) ester 537.0g, purity 99.0%.
Comparative example 1
Ji Wusi is added in equipped with the 1000ml four-hole boiling flask of mechanical agitation, thermometer, reflux condensing tube and water knockout drum
Alcohol 68.8g (0.5mol), 3-mercaptopropionic acid 235.8g (2.2mol), pyrovinic acid aqueous solution 3.0g, the hexamethylene 150g of 70%,
Heating mantle heats, 78～85 DEG C of reflux water-dividings, reach stopped reaction after theoretical water yield, cooling.Reacted mixture is put
In separatory funnel, stratification, reclaims supernatant hexamethylene 120g；Lower coarse product extracts with 200g dehydrated alcohol every time
Taking, extract three times, extraction phase merges.Raffinate phase decompression is distilled off the ethanol of remnants, obtains tetramethylolmethane four (3-sulfydryl third
Acid) ester 224.4g, purity 94.4%.Will merge extraction phase Distillation recovery extractant ethanol 412g, substrate be pyrovinic acid and
The mixture of 3-mercaptopropionic acid, about 40.3g, wherein pyrovinic acid 1.9g, 3-mercaptopropionic acid 38.4g.
Many mercapto-carboxylic esters prepared by the embodiment of the present application 2 and comparative example 1 are carried out performance detection, the results are shown in Table 1.
Many mercapto-carboxylic esters performance test results of table 1 the embodiment of the present application 2 and comparative example 1 preparation collects
From above-described embodiment and comparative example, many mercapto-carboxylic esters prepared by the present invention have higher reaction rate,
Higher quality.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. the preparation method of mercapto-carboxylic ester more than a kind, it is characterised in that including:
By mercaptan carboxylic acid and polyhydric alcohol at pressure≤-0.07MPa, react under conditions of temperature 80～100 DEG C, obtain many mercaptos
Yl carboxylic acid ester.
Preparation method the most according to claim 1, it is characterised in that the reaction unit of described reaction includes negative pressure condensation dress
Put.
Preparation method the most according to claim 1, it is characterised in that described mercaptan carboxylic acid has a structure shown in formula (I):
HS-R-COOH(I)；
Wherein, R is C1～6Straight or branched or cyclic alkylidene.
Preparation method the most according to claim 1, it is characterised in that described mercaptan carboxylic acid is TGA, 2-sulfydryl third
One or more in acid, 3-mercaptopropionic acid, 2-mercaptobutyric acid, 3-mercaptobutyric acid.
Preparation method the most according to claim 1, it is characterised in that described polyhydric alcohol is 2-methyl isophthalic acid, ammediol, fourth
Glycol, neopentyl glycol, hexanediol, glycerol, trimethylolpropane, ethoxyquin trimethylolpropane, third oxidation trimethylolpropane,
One or more in tetramethylolmethane, Bis(pentaerythritol), tripentaerythritol.
Preparation method the most according to claim 1, it is characterised in that in described mercaptan carboxylic acid in carboxyl total amount and polyhydric alcohol
The mol ratio of hydroxyl total amount is 0.95～1.
Preparation method the most according to claim 1, it is characterised in that described reaction is entered under the catalysis of solid super-strong acid
OK.
Preparation method the most according to claim 7, it is characterised in that described solid super-strong acid is SO4 2-/Al2O3-ZrO2。
Preparation method the most according to claim 8, it is characterised in that described solid super-strong acid is prepared in accordance with the following methods:
A) in aluminum nitrate solution, add five water zirconium nitrates, heating for dissolving, obtain colourless transparent solution；
B) ethylenediamine solution is added in above-mentioned colourless transparent solution, obtain the jelly with white precipitate；
C) above-mentioned jelly is carried out crystallization, obtain crystal；
D) above-mentioned crystal sequentially passes through roasting, ammonium sulfate solution soaks, dry, calcination process, obtains solid super-strong acid
SO4 2-/Al2O3-ZrO2。
Preparation method the most according to claim 1, it is characterised in that described mercaptan carboxylic acid is mercaptopropionic acid, described polynary
Alcohol is tetramethylolmethane.
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| CN113710651A (en) * | 2019-04-26 | 2021-11-26 | 三井化学株式会社 | Thiol-containing composition for optical material, and polymerizable composition for optical material |
| CN110041238A (en) * | 2019-05-24 | 2019-07-23 | 山东益丰生化环保股份有限公司 | A method of reducing more mercapto-carboxylic ester smells |
| CN110041238B (en) * | 2019-05-24 | 2021-06-15 | 山东益丰生化环保股份有限公司 | Method for reducing odor of multi-mercapto carboxylic ester |
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