CN112521320A - Preparation method of dodecamercapto compound monomer - Google Patents
Preparation method of dodecamercapto compound monomer Download PDFInfo
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- CN112521320A CN112521320A CN202011398641.9A CN202011398641A CN112521320A CN 112521320 A CN112521320 A CN 112521320A CN 202011398641 A CN202011398641 A CN 202011398641A CN 112521320 A CN112521320 A CN 112521320A
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- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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Abstract
The invention relates to a preparation method of a dodecamercapto compound monomer, which comprises the following steps: pentaerythritol tetramercaptoacetate is used as a parent reactant, ethyl acetate is used as a solvent to form a parent reactant solution, the solution is mechanically stirred and heated in an oil bath, and triethylamine is used as a catalyst to carry out Michael nucleophilic addition reaction with pentaerythritol tetraacrylate or di-trimethylolpropane tetraacrylate to prepare the dodecamercapto compound monomer. The preparation method successfully synthesizes the required super-dendritic polythiol compound through one-step reaction, and has the advantages of simple reaction, high efficiency, higher yield, energy conservation and environmental protection.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a dodecamercapto compound monomer.
Background
In organic chemistry, a class of non-aromatic compounds containing a mercapto functional group (-SH) is referred to as thiols, which structurally can be viewed as being formed after the oxygen in a common alcohol is replaced by sulfur. Thiols can be used as drugs, antidotes and rubber vulcanization accelerators.
The traditional method for preparing mercaptan, in particular polythiol, has the disadvantages of long process route, high energy consumption, high pollution, low yield and complex operation. For example, the mercaptan is prepared by a traditional thiourea alkylation hydrolysis method, and the process is mainly carried out in three steps: generating isothiourea salt; adding alkali for hydrolysis; acidification produces thiols.
The synthesis of the multi-sulfhydryl compound needs better optimization, gel appears in the synthesis process and is not converted into a target product, and the gel becomes a common bottleneck for restricting the production of the multi-sulfhydryl compound.
Disclosure of Invention
The invention provides a preparation method of a dodecanethiol compound monomer, solves the technical problems of long process route and complex operation of a polythiol preparation method in the prior art, and realizes the technical effects of simple reaction, high efficiency, high yield, energy conservation and environmental protection.
The invention provides a preparation method of a dodecamercapto compound monomer, which comprises the following steps:
the method comprises the following steps: dissolving pentaerythritol tetramercaptoacetate serving as a parent reactant in an ethyl acetate solvent to form a parent reactant solution;
step two: stirring and heating the parent reactant solution;
step three: after the parent reactant is dissolved, dropwise adding a triethylamine catalyst into the parent reactant solution;
step four: adding pentaerythritol tetraacrylate or di-trimethylolpropane tetraacrylate into the parent reactant, carrying out Michael nucleophilic addition reaction of a thiol-ene system, continuously stirring in the reaction process, and obtaining a reaction product after the reaction is completed;
step five: and after the reaction product is cooled to room temperature, evaporating the ethyl acetate solvent in the reaction product to dryness, and performing vacuum drying to finally obtain the dodecamercapto compound monomer.
Preferably, the chemical structural formula of the dodecamercapto compound monomer is as follows:
preferably, the ratio of the amount of the parent reactant to the amount of the pentaerythritol tetraacrylate or the ditrimethylolpropane tetraacrylate is (4.5 to 5.5): 1.
preferably, the ratio of the parent reactant to the amount of material of the pentaerythritol tetraacrylate or the ditrimethylolpropane tetraacrylate is 5.0: 1.
preferably, the triethylamine catalyst may be replaced with a triethanolamine catalyst.
Preferably, the dosage of the triethylamine catalyst is as follows: the amount ratio of the triethylamine catalyst to the pentaerythritol tetraacrylate or the di-trimethylolpropane tetraacrylate is (0.001-0.2): 1;
the dosage of the triethanolamine catalyst is as follows: the amount ratio of the triethanolamine catalyst to the pentaerythritol tetraacrylate or the di-trimethylolpropane tetraacrylate is (0.001-0.2): 1.
preferably, the heating temperature is controlled to be 50-70 ℃;
the temperature of the vacuum drying is controlled to be 65 ℃;
the time of the Michael nucleophilic addition reaction is controlled to be 0.5-14 h.
Preferably, the preparation method is completed by a three-neck flask with a condenser pipe, a thermometer, a water separator and an oil bath kettle;
the stirring is mechanical stirring;
the heating is carried out by oil bath heating;
the michael nucleophilic addition reaction was confirmed to be complete by thin layer chromatography.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
the traditional method for preparing mercaptan, particularly polythiol, has the advantages of long process route, high energy consumption, high pollution, low yield and complex operation, successfully synthesizes the required super-dendritic polythiol compound by selecting proper mercaptan and olefin compound and utilizing Michael nucleophilic addition reaction mechanism in click reaction of a mercaptan-alkene system through one-step reaction, and has the advantages of simple reaction, high efficiency, high yield, energy conservation and environmental protection.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of a dodecamercapto compound monomer (corresponding to ditrimethylolpropane tetraacrylate as a reactant) provided in the examples herein;
FIG. 2 is an infrared spectrum of a dodecanethiol compound monomer (corresponding to ditrimethylolpropane tetraacrylate as a reactant) provided in an example of the present application;
FIG. 3 is a 1H-NMR spectrum of a dodecamercapto compound monomer (corresponding to ditrimethylolpropane tetraacrylate as a reactant) provided in examples of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The technical scheme adopted by the application is as follows: pentaerythritol tetramercaptoacetate is used as a parent reactant to carry out Michael nucleophilic addition reaction with pentaerythritol tetraacrylate or di-trimethylolpropane tetraacrylate, ethyl acetate is used as a reaction solvent, triethylamine or triethanolamine is used as a catalyst, and the dodecamercapto compound monomer is finally prepared.
The synthesis route of the dodecamercapto compound (corresponding to the reaction product of di-trimethylolpropane tetraacrylate) is shown in figure 1, triethylamine is adopted as a catalyst in the reaction, and the reaction follows the Michael nucleophilic addition reaction mechanism of a mercaptan-alkene system.
The specific process is as follows: adding a set amount of parent reactant pentaerythritol tetramercapto acetate into a three-neck flask with a condenser pipe, a thermometer, a water separator and an oil bath pot, using ethyl acetate as a solvent, mechanically stirring, carrying out oil bath heating according to the temperature set by an orthogonal experiment, dropwise adding a certain amount of triethylamine catalyst into the three-neck flask after the pentaerythritol tetramercapto acetate in the three-neck flask is completely dissolved, measuring a certain amount of pentaerythritol tetraacrylate or di-trimethylolpropane tetraacrylate by using a measuring cylinder, adding the reaction solution, continuously stirring for reaction until TLC (thin layer chromatography) determines that the reaction is complete, and stopping stirring.
Naturally cooling the product to room temperature, evaporating the ethyl acetate solvent by using a rotary evaporator, putting the product into a vacuum drying oven for vacuum drying at 65 ℃ for a period of time until the quality of the product is unchanged, collecting the product inside, calculating the yield, and carrying out infrared and nuclear magnetic treatment on the synthesized dodecathiol compound to determine the structure of the dodecathiol compound. The infrared spectrum of the dodecamercapto compound monomer (corresponding to the reaction product of ditrimethylolpropane tetraacrylate) is shown in figure 2; the 1H-NMR spectrum of dodecamercapto monomer (corresponding to ditrimethylolpropane tetraacrylate as reactant) is shown in FIG. 3.
The preparation of the dodecamercapto monomer of the present application is described in detail by the following specific examples:
example 1
Adding 194.67g of parent reactant 0.45mol of pentaerythritol tetramercaptoacetate into a 500mL three-neck flask with a condenser, a thermometer, a water separator and an oil bath pot, using 300mL of ethyl acetate as a solvent, mechanically stirring, heating by an oil bath at 50 ℃, dropwise adding 0.0035mol of triethylamine catalyst 0.35g after the pentaerythritol tetramercaptoacetate in the three-neck flask is completely dissolved, measuring 35.20g of 0.1mol of pentaerythritol tetraacrylate by using a measuring cylinder, adding the three-neck flask, continuously stirring and reacting for 10 hours until TLC determines that the reaction is complete, and stopping stirring.
Example 2
Adding 216.3g of parent reactant 0.5mol pentaerythritol tetrasulfoacetate into a 500mL three-neck flask with a condenser, a thermometer, a water separator and an oil bath pot, mechanically stirring the mixture by using 300mL ethyl acetate as a solvent, heating the mixture in an oil bath at 60 ℃, dropwise adding 1.06g of triethylamine catalyst 0.0106mol into the mixture after the pentaerythritol tetrasulfoacetate in the three-neck flask is completely dissolved, measuring 35.20g of pentaerythritol tetraacrylate 0.1mol by using a measuring cylinder, adding the mixture into the three-neck flask, continuously stirring the mixture for reaction for 12 hours until the TLC reaction is completely determined, and stopping stirring the mixture.
Example 3
Adding 237.93g of parent reactant pentaerythritol tetrasulfamoacetate into a 500mL three-neck flask with a condenser, a thermometer, a water separator and an oil bath kettle, using 300mL ethyl acetate as a solvent, mechanically stirring, heating in an oil bath at 70 ℃, dropwise adding 1.06g of 0.0106mol triethylamine catalyst into the mixture respectively after the pentaerythritol tetrasulfamoacetate in the three-neck flask is completely dissolved, measuring 35.20g of 0.1mol pentaerythritol tetraacrylate by using a measuring cylinder, adding the mixture into the three-neck flask, continuously stirring and reacting for 14 hours until TLC determines that the reaction is complete, and stopping stirring.
Example 4
Adding 194.67g of parent reactant 0.45mol of pentaerythritol tetramercaptoacetate into a 500mL three-neck flask with a condenser, a thermometer, a water separator and an oil bath pot, using 300mL of ethyl acetate as a solvent, mechanically stirring, heating in an oil bath at 50 ℃, dropwise adding 1.40g of 0.014mol of triethylamine catalyst after the pentaerythritol tetramercaptoacetate in the three-neck flask is completely dissolved, measuring 46.65g of 0.1mol of di-trimethylolpropane tetraacrylate with a measuring cylinder, adding the three-neck flask, continuously stirring and reacting for 10h until TLC determines that the reaction is complete, and stopping stirring.
Example 5
Adding 216.3g of parent reactant 0.50mol of pentaerythritol tetramercaptoacetate into a 500mL three-neck flask with a condenser, a thermometer, a water separator and an oil bath pot, mechanically stirring the mixture by using 300mL of ethyl acetate as a solvent, heating the mixture in an oil bath at 60 ℃, dropwise adding 0.0047mol of triethylamine catalyst into the mixture after the pentaerythritol tetramercaptoacetate in the three-neck flask is completely dissolved, measuring 46.65g of di-trimethylolpropane tetraacrylate 0.1mol by using a measuring cylinder, adding the mixture into the three-neck flask, continuously stirring the mixture for reaction for 12 hours until the TLC determines that the reaction is complete, and stopping stirring the mixture.
Example 6
Adding 237.93g of parent reactant 0.55mol of pentaerythritol tetramercaptoacetate into a 500mL three-neck flask with a condenser, a thermometer, a water separator and an oil bath kettle, using 300mL ethyl acetate as a solvent, mechanically stirring, heating in an oil bath at 50 ℃, dropwise adding 2.33g of 0.0233mol of triethylamine catalyst after the pentaerythritol tetramercaptoacetate in the three-neck flask is completely dissolved, measuring 46.65g of 0.1mol of di-trimethylolpropane tetraacrylate by using a measuring cylinder, adding the three-neck flask, continuously stirring and reacting for 14h until TLC reaction is complete, and stopping stirring.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a dodecamercapto compound monomer is characterized by comprising the following steps:
the method comprises the following steps: dissolving pentaerythritol tetramercaptoacetate serving as a parent reactant in an ethyl acetate solvent to form a parent reactant solution;
step two: stirring and heating the parent reactant solution;
step three: after the parent reactant is dissolved, dropwise adding a triethylamine catalyst into the parent reactant solution;
step four: adding pentaerythritol tetraacrylate or di-trimethylolpropane tetraacrylate into the parent reactant, carrying out Michael nucleophilic addition reaction of a thiol-ene system, continuously stirring in the reaction process, and obtaining a reaction product after the reaction is completed;
step five: and after the reaction product is cooled to room temperature, evaporating the ethyl acetate solvent in the reaction product to dryness, and performing vacuum drying to finally obtain the dodecamercapto compound monomer.
2. The method for producing a dodecamercapto compound monomer according to claim 1,
the chemical structural formula of the dodecamercapto compound monomer is as follows:
3. the method for producing a dodecamercapto compound monomer according to claim 1,
the ratio of the parent reactant to the amount of the pentaerythritol tetraacrylate or the ditrimethylolpropane tetraacrylate is (4.5 to 5.5): 1.
4. the method for producing a dodecamercapto compound monomer according to claim 3,
the ratio of the parent reactant to the amount of material of the pentaerythritol tetraacrylate or the ditrimethylolpropane tetraacrylate is 5.0: 1.
5. the method for producing a dodecamercapto compound monomer according to claim 1,
the triethylamine catalyst can be replaced by a triethanolamine catalyst.
6. The method for producing a dodecamercapto compound monomer according to claim 1,
the dosage of the triethylamine catalyst or the triethanolamine catalyst is as follows: the amount ratio of the triethylamine catalyst or the triethanolamine catalyst to the pentaerythritol tetraacrylate or the ditrimethylolpropane tetraacrylate is (0.001-0.2): 1.
7. the method for producing a dodecamercapto compound monomer according to claim 1,
the heating temperature is controlled to be 50-70 ℃;
the temperature of the vacuum drying is controlled to be 65 ℃;
the time of the Michael nucleophilic addition reaction is controlled to be 0.5-14 h.
8. The method for producing a dodecamercapto compound monomer according to claim 1,
the preparation method is completed by a three-neck flask with a condenser pipe, a thermometer, a water separator and an oil bath pan;
the stirring is mechanical stirring;
the heating is carried out by oil bath heating;
the michael nucleophilic addition reaction was confirmed to be complete by thin layer chromatography.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001064252A (en) * | 1999-08-27 | 2001-03-13 | Nippon Shokubai Co Ltd | Organic sulfide compound, use of the same, polymerization method and polymer using the same |
| CN104109243A (en) * | 2014-07-04 | 2014-10-22 | 深圳职业技术学院 | Synthetic method for optical resin |
| CN110606935A (en) * | 2019-09-29 | 2019-12-24 | 江南大学 | Chain extender and preparation method thereof |
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2020
- 2020-12-02 CN CN202011398641.9A patent/CN112521320A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001064252A (en) * | 1999-08-27 | 2001-03-13 | Nippon Shokubai Co Ltd | Organic sulfide compound, use of the same, polymerization method and polymer using the same |
| CN104109243A (en) * | 2014-07-04 | 2014-10-22 | 深圳职业技术学院 | Synthetic method for optical resin |
| CN110606935A (en) * | 2019-09-29 | 2019-12-24 | 江南大学 | Chain extender and preparation method thereof |
Non-Patent Citations (4)
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| LINGYUN ZHOU ET AL.: "Cross-Linking of Thiolated Paclitaxel–Oligo(p-phenylene vinylene) Conjugates Aggregates inside Tumor Cells Leads to "Chemical Locks" That Increase Drug Efficacy", 《ADVANCED MATERIALS》 * |
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