CN115385833A - Method for reducing odor of multi-sulfhydryl compound - Google Patents
Method for reducing odor of multi-sulfhydryl compound Download PDFInfo
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- CN115385833A CN115385833A CN202211077254.4A CN202211077254A CN115385833A CN 115385833 A CN115385833 A CN 115385833A CN 202211077254 A CN202211077254 A CN 202211077254A CN 115385833 A CN115385833 A CN 115385833A
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- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000005406 washing Methods 0.000 claims abstract description 128
- 230000008569 process Effects 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229920006295 polythiol Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000873 masking effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- 239000012043 crude product Substances 0.000 description 220
- 238000003756 stirring Methods 0.000 description 102
- 239000007788 liquid Substances 0.000 description 99
- 238000010438 heat treatment Methods 0.000 description 60
- 239000000047 product Substances 0.000 description 45
- 239000012153 distilled water Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000010790 dilution Methods 0.000 description 16
- 239000012895 dilution Substances 0.000 description 16
- -1 thiol compounds Chemical class 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 14
- 238000007865 diluting Methods 0.000 description 14
- 238000002390 rotary evaporation Methods 0.000 description 13
- 238000009423 ventilation Methods 0.000 description 13
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 12
- 230000009965 odorless effect Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 230000009967 tasteless effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000001877 deodorizing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000013027 odor testing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical industry, in particular to a method for reducing the odor of a multi-sulfhydryl compound. The process of combining alkali washing, steam stripping and acid washing is used for effectively removing the odor impurities of the multi-sulfhydryl compound, and the odor stability of the product in the storage process is realized. The substrate applicability is strong, and the process has better effect on multi-sulfhydryl compounds, such as thiol containing more than 2 sulfydryl and the like; the odor is removed more thoroughly, and compared with a mode of adding the odor masking agent, the odor masking agent is more beneficial to occupational health in downstream application fields.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for reducing the odor of a multi-sulfhydryl compound.
Background
The multi-mercapto compound is an important chemical and organic synthesis intermediate, and thiol compounds such as pentaerythritol tetra (3-mercaptopropionic acid) ester and 2, 3-dithio (2-mercapto) -1-propanethiol are mainly used for synthesizing optical resins in the fields of lenses, grating films and the like, and can be used as a modifier, a cross-linking agent, an acidic ion exchange modifier and the like in polymerization reactions such as UV coatings, inks, adhesives and the like.
In the preparation process of the multi-sulfhydryl compound, trace impurity residues such as hydrogen sulfide or mercaptan bring strong unpleasant odor to the product, and negative effects are brought to the environment and the personnel health in the downstream application process. With the development of society, the demand for environment protection is increased and the awareness of environment protection is enhanced, and the market demand for low-odor or odorless multi-thiol compounds is increasingly urgent.
At present, many methods for reducing the odor of compounds are reported in the literature, such as: CN103113525 reports that the oxidizing agent is used to oxidize the trace amount of thiol in the acrylate emulsion to achieve the goal of deodorizing, and for the multi-thiol compound, the product itself contains a large amount of thiol, and this method is not suitable. CN105339421, CN102795981 report that odor masking agent or malodor counteractant is added into the compound to reduce odor, and this method only changes the sense of human olfaction on odor, but the substance which generates irritant odor still exists, and the health hazard to human body still exists.
To address the above problem, we tried to treat by alkaline washing and N 2 The odor of the multi-mercapto carboxylic ester is reduced by a combined mode of reduced pressure distillation under protection (CN 110041238A), although the odor of the product is reduced to a certain degree, the requirement of extremely low odor or no odor is still not met, the sample can smell obvious pungent odor after being sealed and stored for a long time, and the small molecules generating the odor are not completely removed.
Disclosure of Invention
The invention provides a method for reducing the odor of a multi-sulfhydryl compound, aiming at the problem that the odor of the multi-sulfhydryl compound is not ideal in the prior art. The process of alkali washing, steam stripping and acid washing is combined to effectively remove the odor impurities of the multi-sulfhydryl compound and realize the odor stability of the product in the storage process.
The technical scheme of the invention is as follows:
a process for reducing the odor of polymercapto compounds, the process comprising alkaline washing or/and acid washing and stripping, and the sequence of each process being adjustable.
Preferably, the method for reducing the odor of the multi-sulfhydryl compound comprises the processes of alkaline washing, acid washing and steam stripping, and the sequence of each process can be adjusted; more preferably, the washing with water is carried out after the alkali washing and the acid washing.
In the method, the deodorizing effect can be best achieved by the three-step process, but only two steps can be adopted, a steam stripping process is required, and the better deodorizing effect can be achieved by adopting the two-step process combination of alkali washing or acid washing and steam stripping for some samples with lower odor.
In the above processes, the order of the respective processes may be adjusted. For example, the alkali washing, steam stripping and acid washing, wherein the operation sequence of the alkali washing, steam stripping and acid washing combined process can be adjusted, and the effective odor reduction effect can be achieved by the alkali washing, steam stripping and acid washing combined process and the alkali washing, steam stripping and acid washing combined process.
In the method for reducing the odor of the multi-sulfhydryl compound, the equipment forms of the alkali washing, steam stripping and acid washing processes are not limited, the batch mode of the kettle type process can be adopted, the tower type continuous process can also be adopted, and for convenience of description, the batch kettle type process is introduced. In the method for reducing the odor of the mercapto compound, the mercapto compound may be a commercially available product or a crude synthetic product without being subjected to a refining treatment.
In the method for reducing the odor of the mercapto compound, the alkali washing process adopts weak alkali. The weak base is selected from one or more of sodium carbonate, sodium bicarbonate, sodium sulfite, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium bisulfite and ammonia water. The weak base is selected because not only can the effective removal of acidic substances be realized, but also the salt formation loss of the multi-sulfhydryl compound can be inhibited. In the invention, the weak base is more preferably ammonia water, because ammonia water is adopted for alkali washing, the solution is clear and transparent, the layering speed is high during liquid separation, the layering surface is clearer, and the yield of the sulfhydryl compound is high.
In the method for reducing the odor of the sulfhydryl compound, the addition amount of the weak base is 1.5-10% of the mass of the multi-sulfhydryl compound in the alkali washing process. The addition of weak base is further reduced, the odor removing effect cannot be achieved, the addition of weak base is further improved, the product yield is influenced, and the production cost is increased.
In the method for reducing the odor of the sulfhydryl compound, the alkali washing process is diluted by adding 0.5-2 equivalents of water into the multi-sulfhydryl compound. On one hand, water is added for better contacting with impurities after solid weak base is dissolved, so as to achieve the effect of deodorizing, and on the other hand, for the convenience of liquid separation operation, the separation of the multi-sulfhydryl compound and the impurities is realized. Too little water is added to be beneficial to liquid separation operation and solid weak base dissolution, and too much water is added to increase the generation amount of wastewater.
In the method for reducing the odor of mercapto compounds of the present invention, the temperature of the stripping process is 80 to 135 deg.C, more preferably 100 to 110 deg.C. Further reducing the stripping temperature, maintaining the temperature of the reaction liquid by cooling measures, and simultaneously keeping the system at a higher vacuum degree, so that the production cost is higher; the steam stripping temperature is further increased, and some multi-sulfhydryl compounds are easy to generate decomposition reaction in the steam stripping process, so that the odor removal effect is reduced, and the product quality is influenced.
In the method for reducing the odor of the sulfhydryl compound, the steam consumption of the stripping process is 1 to 4 times of the mass of the sulfhydryl compound. The stripping amount is further reduced, the best deodorization effect cannot be achieved, the stripping amount is further increased, the deodorization effect cannot be increased, and the production cost is increased.
In the method for reducing the odor of the sulfhydryl compound, the acid of the acid washing process is selected from one or a mixture of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, maleic acid and citric acid. Preferably, the pH of the reaction solution of the acid washing process is controlled to be 2-5. More preferably 2-3. The purpose of adding acid is to remove a small amount of alkali possibly remained in the alkali washing process on one hand, and to remove alkali impurities in the product on the other hand, so that the odor of the product is further reduced, and the stability of the odor of the product is maintained. According to the scheme, the pH value of the system is further reduced, the odor removal effect is not enhanced, the pH value of the system is further improved, alkaline substances cannot be effectively removed, and the stability of the odor of the product and the odor removal effect are affected.
In the method for reducing the odor of the mercapto compound, the temperature of the acid washing process is 30-60 ℃, and the temperature of the alkali washing process is 30-60 ℃. Further reducing the temperature, the acid washing and alkaline effects are reduced, further increasing the temperature, and some multi-sulfhydryl compounds, especially ester bond-containing multi-sulfhydryl compounds are easy to generate hydrolysis reaction, thus reducing the product quality.
In the method for reducing the odor of the mercapto compound, the acid washing process time is preferably 5-30min, and the alkali washing process time is preferably 5-30min. Further reducing the time, reducing the acid washing and alkali washing effects, further prolonging the time, having no obvious difference in the odor removal effects of acid washing and alkali washing, and reducing the risk of product quality due to the hydrolysis reaction of certain multi-sulfhydryl compounds, particularly ester bond-containing multi-sulfhydryl compounds.
In summary, compared with the prior art, the method for reducing the odor of the multi-mercapto compound provided by the invention has the following beneficial effects:
(1) The substrate applicability is strong, and the process has better effect on multi-sulfhydryl compounds, such as thiol containing more than 2 sulfydryl and the like;
(2) The odor is removed more thoroughly, and compared with a mode of adding the odor masking agent, the odor masking agent is more beneficial to occupational health in downstream application fields.
In addition, compared with the nitrogen protection reduced pressure distillation adopted in the prior patent application CN110041238A, the steam stripping process has higher gas phase partial pressure of water vapor, can better carry out odor substances, can better remove the odor substances after subsequent water vapor condensation, and is more thorough in odor removal by combining the acid washing and alkali washing processes of the invention.
Detailed Description
The invention provides a method for reducing the odor of a multi-sulfhydryl compound, which comprises reducing the odor of a product by a combined process of alkali washing, steam stripping and acid washing. Those skilled in the art can modify the process parameters appropriately in view of the disclosure herein. It is expressly intended that all such alterations and modifications, and even adjustment of the sequence of operations, which are obvious to those skilled in the art, are deemed to be within the scope of the invention. The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. The techniques realized based on the above contents of the present invention all belong to the scope of the present invention, and the following embodiments are all completed by using the conventional prior art except for the specific description.
Example 1
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) ester crude product (the crude product cut by the production process is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with a stirrer, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of a system to be 50 ℃, keeping for 10min, stopping heating, and separating to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the washing steps for 1 time, and separating liquid to obtain a washing crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the amount of the steam is observed to be 4 times of the mass of the steam stripping crude product, cooling, and separating liquid to obtain a steam-stripped crude product C;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product D;
and repeating the washing process after alkaline washing for 2 times to obtain the acid-washed crude product D, separating liquid to obtain the crude product, and performing rotary evaporation to obtain an odorless fine product 141.7g, wherein the yield is 94.5%.
Example 2
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (the crude product cut by the production process is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the obtained crude product B into a four-neck round-bottom flask with a stirring paddle, adding 1.62g of hydrochloric acid (37 w%) of the mass of the crude product, diluting uniformly by using water of which the mass is 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain an acid-washed crude product C;
adding the crude product C into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the amount of the steam is observed to be 4 times of the mass of the steam stripping crude product, cooling, and separating liquid to obtain a steam-stripped crude product D;
and repeating the washing process after the alkaline washing for 2 times to obtain the acid washing crude product D, separating liquid to obtain the crude product, and performing rotary evaporation to obtain an odorless fine product 143g with the yield of 95.3%.
Example 3
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (which is cut out by a production process and is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 30g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of a system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 100 ℃, inserting or at least contacting the liquid level of the product at a steam inlet pipe, starting stirring, keeping steam stripping steam to stably circulate, stopping ventilation when the amount of steam is observed to be 4 times of the mass of the crude product, cooling, and separating liquid to obtain a crude product C after steam stripping;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding 1.62g of hydrochloric acid (37 w%) of the mass of the crude product, diluting uniformly by using water of which the mass is 1 time that of the crude product, adjusting the pH to 3, heating to 30 ℃, keeping for 20min, stopping heating, and separating to obtain an acid-washing crude product D;
and (3) repeating the process of washing with water after the alkali washing for 2 times to obtain crude product D, separating liquid to obtain crude product, and performing rotary evaporation to obtain odorless refined product 139.5g with yield of 93%.
Example 4
Adding 150g of pentaerythritol tetra (3-mercaptopropionate) crude product (which is cut out by a production process and is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 60g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of a system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the obtained crude product B into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product C;
repeating the washing process after the alkali washing for 2 times to obtain a crude product C after acid washing, and separating liquid to obtain a crude product D;
and adding the crude product D into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of a system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the steam consumption is observed to be 4 times of the mass of the crude product subjected to steam stripping, cooling, separating liquid to obtain crude product subjected to steam stripping, and performing rotary steaming to obtain 135.0g of tasteless fine product, wherein the yield is 90%.
Example 5
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (the crude product cut by the production process is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 66g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 15min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the obtained crude product B into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product C;
repeating the washing process after the alkali washing for 2 times to obtain a crude product C after acid washing, and separating liquid to obtain a crude product D;
and adding the crude product D into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of a system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the steam consumption is observed to be 4 times of the mass of the crude product subjected to steam stripping, cooling, separating liquid to obtain crude product subjected to steam stripping, and performing rotary steaming to obtain 132.0g of tasteless fine product, wherein the yield is 88%.
Example 6
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (the crude product cut by the production process is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 6g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 40 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washed crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 105 ℃, inserting or at least contacting the liquid level of the product at a steam inlet pipe, starting stirring, keeping steam stripping steam to stably circulate, stopping ventilation when the amount of steam is observed to be 4 times of the mass of the crude product, cooling, and separating liquid to obtain a crude product C after steam stripping;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding 1.62g of hydrochloric acid (37 w%) of the mass of the crude product, diluting uniformly by using water of which the mass is 1 time that of the crude product, adjusting the PH to be 2, heating to 40 ℃, keeping for 10min, stopping heating, and separating to obtain an acid-washing crude product D;
and repeating the process of washing with water after the alkali washing for 2 times to obtain crude product D, and performing rotary evaporation to obtain odorless refined product 142.8g with yield of 95.2%.
Example 7
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (the crude product cut by the production process is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 15min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the washing steps for 1 time, and separating liquid to obtain a washing crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the amount of the steam is observed to be 1 time of the mass of the steam stripping crude product, cooling, and separating liquid to obtain a steam-stripped crude product C;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product D;
and repeating the washing process after the alkaline washing for 2 times to obtain the acid washing crude product D, separating liquid to obtain the crude product, and performing rotary evaporation to obtain an odorless fine product 141.5g, wherein the yield is 94.3%.
Example 8
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (the crude product cut by the production process is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 105 ℃, inserting or at least contacting the liquid level of the product at a steam inlet pipe, starting stirring, keeping steam stripping steam stably circulating, stopping ventilation when the amount of steam is observed to be 0.5 times of the mass of the crude product, cooling, and separating liquid to obtain a crude product C after steam stripping;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product D;
and repeating the process of washing with water after the alkaline washing for 2 times to obtain crude product D, and performing rotary evaporation to obtain a tasteless fine product 141.2g with a yield of 94.1%.
Example 9
Adding 150g of pentaerythritol tetra (3-mercaptopropionate) crude product (which is cut by a production process and is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 3g of sodium carbonate into the flask, immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of a system to be 300 ℃, keeping the temperature for 30min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 2 times, and separating liquid to obtain a water-washed crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the amount of the steam is observed to be 4 times of the mass of the steam stripping crude product, cooling, and separating liquid to obtain a steam-stripped crude product C;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 3, heating to 40 ℃, keeping for 20min, stopping heating, and separating to obtain an acid-washed crude product D;
and repeating the washing process after the alkali washing for 3 times to obtain the acid washing crude product D, separating liquid to obtain a crude product, and performing rotary evaporation to obtain an odorless fine product 138g with the yield of 92%.
Example 10
Adding 150g of crude 2, 3-dithio (2-mercapto) -1-propanethiol into a four-neck round-bottom flask with stirring, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping the temperature for 10min, stopping heating, and separating to obtain crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the obtained crude product B into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 2, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product C;
repeating the washing process after the alkali washing for 2 times to obtain a crude product C, and separating liquid to obtain a crude product D;
and adding the crude product D into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of a system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the steam consumption is observed to be 4 times of the mass of the crude product subjected to steam stripping, cooling, separating liquid to obtain crude product subjected to steam stripping, and performing rotary steaming to obtain 141.6g of tasteless fine product, wherein the yield is 94.4%.
Example 11
Adding 150g of crude 2, 3-dithio (2-mercapto) -1-propanethiol into a four-neck round-bottom flask with stirring, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping the temperature for 10min, stopping heating, and separating to obtain crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 105 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the amount of the steam is observed to be 1 time of the mass of the steam stripping crude product, cooling, and separating liquid to obtain a steam-stripped crude product C;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding 1.62g of hydrochloric acid (37 w%) of the mass of the crude product, diluting uniformly by using water of which the mass is 1 time that of the crude product, adjusting the PH to be 2, heating to 40 ℃, keeping for 30min, stopping heating, and separating to obtain an acid-washing crude product D;
and repeating the washing process after alkaline washing for 2 times to obtain the acid-washed crude product D, separating liquid to obtain crude product, and performing rotary evaporation to obtain odorless fine product 142g with the yield of 94.7%.
Example 12
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (which is cut out by a production process and is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 30g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of a system to be 60 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the water washing step for 1 time, and separating liquid to obtain a water-washed crude product B;
adding the crude product B into a four-mouth round-bottom flask with a stirring paddle for steam stripping, controlling the temperature of the system to be 130 ℃, inserting a steam inlet pipe orifice into or at least contacting the liquid level of the product, starting stirring, keeping the steam stripping steam to stably circulate, stopping ventilation when the amount of the steam is observed to be 4 times of the mass of the steam stripping crude product, cooling, and separating liquid to obtain a steam-stripped crude product C;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product D;
and repeating the washing process after alkaline washing for 2 times to obtain the acid-washed crude product D, separating liquid to obtain the crude product, and performing rotary evaporation to obtain an odorless fine product 139.4g, wherein the yield is 92.9%.
Comparative example 1
Adding 150g of pentaerythritol tetra (3-mercaptopropionate) crude product (which is cut by a production process and is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with a stirring paddle, adding 6g of sodium sulfite into the flask, immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of a system to be 50 ℃, keeping the temperature for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
the washing steps are repeated for 2 times, crude product B is obtained by liquid separation, and 145.5g of tasteless fine product is obtained by rotary evaporation, with the yield of 97%.
Comparative example 2
Adding 150g of pentaerythritol tetra (3-mercaptopropionate) crude product (which is cut by a production process and is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with a stirring paddle, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the system temperature to be 50 ℃, keeping the temperature for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the washing steps for 2 times, and separating liquid to obtain a washing crude product B
Adding the obtained crude product B into a four-neck round-bottom flask with a stirring paddle, adding hydrochloric acid (37 w%) with the mass of 1.62g of the crude product, diluting uniformly with water with the mass of 1 time that of the crude product, adjusting the pH to 2, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain acid-washed crude product C;
the washing steps are repeated for 2 times, crude product D is obtained by liquid separation, tasteless fine product 143.1g is obtained by rotary evaporation, and the yield is 95.4%.
Comparative example 3
150g of a 2, 3-dithio (2-mercapto) -1-propanethiol crude product (a crude product cut by a production process is only subjected to liquid cutting treatment) is added into a four-neck round-bottom flask with a stirring paddle, 9g of ammonia water (25 w%) is added into the flask, 150g of distilled water is added for dilution, the mixture is uniformly stirred, the temperature of the system is controlled to be 50 ℃, the mixture is kept for 10min, heating is stopped, and liquid separation is carried out to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
the washing steps are repeated for 2 times, crude product B is obtained by liquid separation, tasteless fine product 143.5g is obtained by rotary evaporation, and the yield is 95.6%.
Comparative example 4
Adding 150g of pentaerythritol tetrakis (3-mercaptopropionate) crude product (the crude product cut by the production process is only subjected to liquid cutting treatment) into a four-neck round-bottom flask with stirring, adding 9g of ammonia water (25 w%), immediately adding 150g of distilled water for dilution, uniformly stirring, controlling the temperature of the system to be 50 ℃, keeping for 10min, stopping heating, and separating liquid to obtain a crude product A;
adding the obtained crude product A into a four-neck round-bottom flask with a stirring paddle, simultaneously adding three-stage distilled water with the same mass as the crude product, stirring, heating to 50 ℃, keeping for 10min, stopping reaction, and separating liquid to obtain a primary water-washing crude product;
repeating the washing steps for 1 time, and separating liquid to obtain a washing crude product B;
adding the crude product B into a four-neck round-bottom flask with a stirring paddle for N 2 Purging with atmosphere, controlling the temperature of the system at 105 ℃, inserting or at least contacting the liquid level of the product in a nitrogen inlet pipe orifice, starting stirring, keeping the nitrogen flow in stable circulation, continuously purging for 2h, stopping ventilation, and separating liquid after cooling to obtain a crude product C;
adding the obtained crude product C into a four-neck round-bottom flask with a stirring paddle, adding 1.62g of hydrochloric acid (37 w%) of the mass of the crude product, diluting uniformly by using water of which the mass is 1 time that of the crude product, adjusting the pH to 3, heating to 50 ℃, keeping for 10min, stopping heating, and separating to obtain an acid-washing crude product D;
and repeating the process of washing with water after the alkaline washing for 2 times to obtain crude product D, and performing rotary evaporation to obtain a tasteless fine product 141.7g with a yield of 94.5%.
The polymercaptocarboxylic esters prepared in examples 1-12 of the present application and comparative examples 1-4 were subjected to odor testing and the results are shown in Table 1. The odor determination method comprises the following steps: and 5 evaluators are used for evaluating the odor, and the average value of the obtained results is the odor value of the corresponding product. The odor rating values are between 1 and 6: 0-1 is no detectable odor; 1-2 are slightly noticeable but not disturbing; 2-3 means that the smell is obviously perceived but is not interfered; 3-4 are odor forming interferences; 4-5 are strong odor interferences; 5-6 are results of odor intolerance, and the final average value is taken as the odor grade judgment.
TABLE 1 odor test results for polymercaptocarboxylic esters prepared in examples 1-12 and comparative examples 1-3 of the present application
As is clear from the above examples and comparative examples, the odor of the polythiol compound prepared by the present invention is significantly reduced as compared with the conventional techniques.
The above description of the embodiments is only for the purpose of helping understanding the method of the present invention and the core idea thereof, and it should be noted that, for those skilled in the art, many modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments should also be regarded as the protection scope of the present invention.
Claims (10)
1. A process for reducing the odor of polymercapto compounds, characterized in that the process comprises alkaline washing or/and acid washing and stripping, and the sequence of each process is adjustable.
2. The method of claim 1, wherein the process comprises alkaline washing, acid washing and stripping, and the sequence of the processes is adjustable.
3. A method for reducing the odor of a polymercapto compound according to claim 1 or 2, wherein the alkaline washing process uses a weak base.
4. A method according to claim 3, wherein the weak base is selected from one or more of sodium carbonate, sodium bicarbonate, sodium sulfite, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium bisulfite, and ammonia water.
5. The method of claim 3, wherein the weak base is added in an amount of 1.5-10% based on the mass of the polythiol compound in the alkaline washing process.
6. A method for reducing the odor of a polymercapto compound according to claim 1 or 2, wherein the alkaline washing process is diluted with 0.5 to 2 equivalents of polymercapto compound of water.
7. The method of claim 1 or 2, wherein the stripping process temperature is 80-135 ℃, and the stripping process uses 1-4 times the amount of the polythiol compound as steam.
8. A method of reducing the odor of a polymercapto compound according to claim 1 or 2, wherein the temperature of said stripping process is 100-110 ℃.
9. The method of claim 1 or 2, wherein the acid of the acid washing process is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, maleic acid, and citric acid; the pH value of the reaction liquid of the acid washing process is controlled to be 2-5.
10. The method according to claim 1 or 2, wherein the temperature of the acid washing process is 30-60 ℃, and the temperature of the alkali washing process is 30-60 ℃; the acid washing process time is preferably 5-30min, and the alkali washing process time is preferably 5-30min.
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| JPH09263575A (en) * | 1996-03-28 | 1997-10-07 | Sumitomo Seika Chem Co Ltd | Mercapto compounds, production of the same, tetraol compound and production of the same |
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| CN110872246A (en) * | 2019-12-02 | 2020-03-10 | 山东益丰生化环保股份有限公司 | Preparation method of high-content pentaerythritol tetra (3-mercaptopropionate) |
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| JPH09263575A (en) * | 1996-03-28 | 1997-10-07 | Sumitomo Seika Chem Co Ltd | Mercapto compounds, production of the same, tetraol compound and production of the same |
| JPH1180117A (en) * | 1997-09-04 | 1999-03-26 | Asahi Denka Kogyo Kk | Production of mercaptocarboxylic acid ester |
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