CN109160890B - Synthetic method of SPE - Google Patents
Synthetic method of SPE Download PDFInfo
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- CN109160890B CN109160890B CN201811228000.1A CN201811228000A CN109160890B CN 109160890 B CN109160890 B CN 109160890B CN 201811228000 A CN201811228000 A CN 201811228000A CN 109160890 B CN109160890 B CN 109160890B
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- solvent
- propane
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- polymerization inhibitor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
Abstract
The invention discloses a synthetic method of SPE, comprising the following steps: uniformly mixing an organic solvent, dimethylaminoethyl methacrylate and a polymerization inhibitor, and dropwise adding 1, 3-propane sultone into the mixed solution for reaction to obtain a target product; the organic solvent is an alcohol solvent and/or a ketone solvent. The synthesis method of the invention selects the alcohol and/or ketone solvent as the reaction solvent, the solvent has low toxicity and harm, and the alcohol and ketone solvent is easy to recycle and reuse, and is safer and more environment-friendly compared with the method using carbon tetrachloride as the solvent; the dimethyl aminoethyl methacrylate and the 1, 3-propane sultone are used as raw materials, and the polymerization inhibitor is added, so that the polymerization of the dimethyl aminoethyl methacrylate can be effectively inhibited, other side reactions in the reaction process can be reduced, the reaction is more sufficient, and the yield and the purity of the product are improved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthetic method of SPE.
Background
SPE, known as 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl]Ammonium salt]Propane-1-sulfonic acid inner salt, the molecular formula is: c11H21NO5S, molecular weight: 279.4, CAS number: 3637-26-1, the pure product is white powder solid, and the melting point is 150-155 ℃. SPE is a sulfonic acid type polyacrylic acid monomer, belongs to sulfobetaine, and the polyacrylate product of the SPE has unique physical properties and chemical properties of sulfonate by adding the SPE, and the SPE is mainly used for producing stable acrylic acid dispersion gel, adhesive and coating.
The synthesis method of SPE has no related patent at present in China for reporting, only part of documents mention the synthesis method of sulfobetaine, at present, the synthesis of sulfobetaine mainly uses carbon tetrachloride as a reaction solvent, the carbon tetrachloride has high toxicity and high harm, the harm is caused to the health of workers in the production process, the subsequent carbon tetrachloride is difficult to recycle, and the synthesis method is not suitable for industrial production at present; other synthesis methods are safer and more environment-friendly, but have more side reactions, and the obtained product has lower content, thus being not suitable for synthesizing SPE. In view of the wide range of applications for which SPE can be used to produce stable acrylic dispersion gels, there is a need to provide a method for synthesizing SPE.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a synthetic method of SPE, which is safe and environment-friendly and has high product content.
In order to achieve the technical purpose, the technical scheme of the invention provides a SPE synthesis method, which comprises the following steps: uniformly mixing an organic solvent, dimethylaminoethyl methacrylate and a polymerization inhibitor, and dropwise adding 1, 3-propane sultone into the mixed solution for reaction to obtain a target product; the organic solvent is an alcohol solvent and/or a ketone solvent.
The reaction principle of the SPE synthesis method provided by the invention is as follows:
compared with the prior art, the invention has the beneficial effects that:
1. according to the method for synthesizing SPE, the alcohol and/or ketone solvent is/are selected as the reaction solvent, the solvent is low in toxicity and harm, and the alcohol and ketone solvent is easy to recycle and reuse, so that compared with the method using carbon tetrachloride as the solvent, the method is safer and more environment-friendly;
2. according to the invention, dimethylaminoethyl methacrylate and 1, 3-propane sultone are used as raw materials, and a polymerization inhibitor is added, so that the polymerization of dimethylaminoethyl methacrylate can be effectively inhibited, other side reactions in the reaction process can be reduced, the dimethylaminoethyl methacrylate and the 1, 3-propane sultone can be fully reacted, and the yield and the purity of the product are improved;
3. the synthesis method disclosed by the invention is simple and feasible, strong in operability, low in cost, safe and environment-friendly, and suitable for industrial production.
Detailed Description
The embodiment provides a SPE synthesis method, which comprises the following steps:
adding an organic solvent, dimethylaminoethyl methacrylate and a polymerization inhibitor into a four-neck flask with a mechanical stirring thermometer, and uniformly stirring and mixing; continuously introducing dry air into the four-neck flask for protection, dropwise adding 1, 3-propane sultone into the mixed solution, controlling the dropwise adding temperature to be 10-50 ℃, preserving the temperature of the mixed solution for 2-5 hours at 30-50 ℃, cooling the temperature of the mixed solution to 10-30 ℃ after finishing preserving the temperature, filtering, drying the solid obtained by filtering to obtain a finished product, and recycling the filtrate for the next batch.
In some preferred embodiments, the molar ratio of dimethylaminoethyl methacrylate to 1, 3-propane sultone is 1:1 to 1.1.
In some preferred embodiments, the volume ratio of the organic solvent to dimethylaminoethyl methacrylate is 3-5: 1.
in some preferred embodiments, the organic solvent is an alcohol and/or ketone solvent, the alcohol solvent is at least one of ethanol, ethylene glycol, and isopropanol, and the ketone solvent is acetone and/or butanone; the solvents can better mix and dissolve dimethylaminoethyl methacrylate, the polymerization inhibitor and the 1, 3-propane sultone, and the solvents have low toxicity and harm and are safer and more environment-friendly.
In some preferred embodiments, the organic solvent is a mixed solvent of ethanol and isopropanol, and the volume ratio of ethanol to isopropanol is 1-2.5: 1; within the dosage range, the activity of polymerization reaction can be improved, the yield and the content of the product are further improved, and the ethanol and the isopropanol are easier to recycle and are more environment-friendly.
In some preferred embodiments, the polymerization inhibitor is one or more of o-sec-butyl-4, 6-dinitrophenol, hydroquinone, p-benzoquinone, p-tert-butyl catechol, and p-hydroxyanisole. Further, the polymerization inhibitor is o-sec-butyl-4, 6-dinitrophenol.
In some preferred embodiments, the molar ratio of polymerization inhibitor to dimethylaminoethyl methacrylate is 0.001-0.01: 1; within the dosage range, the inhibitor has better inhibiting effect on the polymerization of dimethylaminoethyl methacrylate, can reduce side reaction in the reaction process and further improve the content of products.
In some preferred embodiments, the temperature of the dropwise addition of the 1, 3-propane sultone to the mixed solution is 30 to 40 ℃.
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the following describes the SPE synthesis method in further detail with reference to the embodiments. The experimental materials used in the present invention were all purchased from the market unless otherwise specified. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
adding 500ml of mixed solvent of ethanol and glycol into a 1000ml four-neck flask provided with a mechanical stirring thermometer, adding 250ml of ethanol and glycol into the mixed solvent respectively, adding 160g of dimethylamino methacrylate and 0.2g of hydroquinone serving as a polymerization inhibitor into the flask, and stirring and dissolving until the mixture is uniformly mixed; continuously introducing dry air into the four-neck flask for protection, then dropwise adding 125g of 1, 3-propane sultone into the mixed solution, controlling the dropwise adding temperature to be 10-30 ℃, preserving the temperature of the mixed solution for 5 hours at 30-40 ℃ after dropwise adding, cooling the temperature of the mixed solution to 20 ℃ after preserving the temperature, filtering, drying the solid obtained by filtering to obtain a finished product, and recycling the filtrate for the next batch.
253g of white solid is obtained by adopting the method of the embodiment, the content of the product is detected to be 98.13%, the melting point is 149-158 ℃, and the product yield is 88.77%.
Example 2:
adding 500ml of mixed solvent of ethanol and isopropanol into a 1000ml four-neck flask provided with a mechanical stirring thermometer, adding 350ml of ethanol and 150ml of isopropanol in the mixed solvent, adding 160g of dimethylamino methacrylate and 0.32g of polymerization inhibitor o-sec-butyl-4, 6-dinitrophenol into the flask, and stirring and dissolving until the mixture is uniformly mixed; continuously introducing dry air into the four-neck flask for protection, then dropwise adding 125g of 1, 3-propane sultone into the mixed solution, controlling the dropwise adding temperature to be between 40 and 50 ℃, preserving the temperature of the mixed solution for 2 hours at the temperature after dropwise adding, cooling the temperature of the mixed solution to 30 ℃ after preserving the temperature, filtering, drying the solid obtained by filtering to obtain a finished product, and recycling the filtrate for the next batch.
265g of white solid is obtained by adopting the method of the embodiment, the content of the product is detected to be 98.56%, the melting point is 149-155 ℃, and the product yield is 92.98%.
Example 3:
adding 500ml of mixed solvent of ethanol and isopropanol into a 1000ml four-neck flask provided with a mechanical stirring thermometer, adding 250ml of ethanol and isopropanol in the mixed solvent respectively, adding 160g of dimethylamino methacrylate and 0.2g of polymerization inhibitor o-sec-butyl-4, 6-dinitrophenol into the flask, and stirring and dissolving until the mixture is uniformly mixed; continuously introducing dry air into the four-neck flask for protection, then dropwise adding 125g of 1, 3-propane sultone into the mixed solution, controlling the dropwise adding temperature to be 30-40 ℃, preserving the temperature of the mixed solution for 3 hours at the temperature after dropwise adding, cooling the temperature of the mixed solution to 10 ℃ after preserving the temperature, filtering, drying the solid obtained by filtering to obtain a finished product, and recycling the filtrate for the next batch.
273g of white solid is obtained by adopting the method of the embodiment, the content of the product is detected to be 98.88%, the melting point is 150-153 ℃, and the product yield is 95.79%.
Comparative example
SPE was synthesized in the same manner as in example 3, except that no polymerization inhibitor was added during the synthesis.
The solid obtained by the method is light yellow, 191g of light yellow solid is obtained, the content of the product is detected to be 76.27%, the melting point is 146-152 ℃, and the product yield is 51.11%.
In summary, the method for synthesizing SPE provided by the present invention is an effective method. By controlling parameters in the aspects of reaction raw materials, raw material proportion, reaction temperature and the like, the method for synthesizing the SPE is safe and environment-friendly, the yield and the content of the SPE product and the quality of the SPE product are effectively improved, the yield of the synthesized SPE product reaches more than 88.77%, the content of the synthesized SPE product reaches more than 98.13%, the product has good color and luster appearance and stable quality.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. A method for synthesizing 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt is characterized by comprising the following steps: uniformly mixing an organic solvent, dimethylaminoethyl methacrylate and a polymerization inhibitor, and dropwise adding 1, 3-propane sultone into the mixed solution for reaction to obtain a target product; the organic solvent is a mixed solvent of ethanol and isopropanol, and the volume ratio of the ethanol to the isopropanol is (1-2.5): 1; the polymerization inhibitor is o-sec-butyl-4, 6-dinitrophenol.
2. The method of synthesizing 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt according to claim 1, wherein the molar ratio of dimethylaminoethyl methacrylate to 1, 3-propane sultone is 1:1 to 1.1.
3. The method for synthesizing 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt according to claim 1, wherein the molar ratio of the polymerization inhibitor to dimethylaminoethyl methacrylate is 0.001-0.01: 1.
4. The method for synthesizing 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt according to claim 1, wherein the volume ratio of the organic solvent to dimethylaminoethyl methacrylate is 3-5: 1.
5. the method for synthesizing 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt according to claim 1, wherein the method comprises the following steps: uniformly mixing an organic solvent, dimethylaminoethyl methacrylate and a polymerization inhibitor, introducing dry air into the mixed solution to serve as a protective gas, dropwise adding 1, 3-propane sultone into the mixed solution at 10-50 ℃, preserving heat for 2-5 hours at 30-50 ℃, cooling the mixed solution to 10-30 ℃, filtering and drying to obtain a finished product.
6. The method for synthesizing a 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt according to claim 5, wherein 1, 3-propane sultone is added dropwise to the mixed solution at 30 to 40 ℃.
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| CN201811228000.1A CN109160890B (en) | 2018-10-22 | 2018-10-22 | Synthetic method of SPE |
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| CN109160890B true CN109160890B (en) | 2021-07-27 |
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| US4205152A (en) * | 1976-12-09 | 1980-05-27 | Nippon Paint Co., Ltd. | Thermosetting resin and its production |
| KR20140104766A (en) * | 2013-02-21 | 2014-08-29 | 동우 화인켐 주식회사 | Alkali soluble resin and photosensitive resin composition comprising the same |
| CN104211842A (en) * | 2014-08-22 | 2014-12-17 | 中科院广州化学有限公司南雄材料生产基地 | Novel zwitterionic polyelectrolyte dispersing agent as well as method and application thereof |
| CN107814881A (en) * | 2017-11-14 | 2018-03-20 | 西南石油大学 | A kind of quick copolymer gel of temperature sensitive salt and preparation method thereof |
-
2018
- 2018-10-22 CN CN201811228000.1A patent/CN109160890B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4205152A (en) * | 1976-12-09 | 1980-05-27 | Nippon Paint Co., Ltd. | Thermosetting resin and its production |
| KR20140104766A (en) * | 2013-02-21 | 2014-08-29 | 동우 화인켐 주식회사 | Alkali soluble resin and photosensitive resin composition comprising the same |
| CN104211842A (en) * | 2014-08-22 | 2014-12-17 | 中科院广州化学有限公司南雄材料生产基地 | Novel zwitterionic polyelectrolyte dispersing agent as well as method and application thereof |
| CN107814881A (en) * | 2017-11-14 | 2018-03-20 | 西南石油大学 | A kind of quick copolymer gel of temperature sensitive salt and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Synthesis and Characterization of 3-[N-(2-Methacroyloylethyi)-N,N-dimethylamino]propane Sulfonate and its Crystal Structure;Jian xiao et al;《Asian Journal of Chemistry》;20151231;第27卷(第10期);3818-3820 * |
| 磺基甜菜碱型两性离子聚合物的合成;丁伟等;《化工科技》;20101231;第18卷(第5期);15-19 * |
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