CN101870711B - Synthesis method of tris(trimethylsilyl) phosphate - Google Patents
Synthesis method of tris(trimethylsilyl) phosphate Download PDFInfo
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- CN101870711B CN101870711B CN200910111556.7A CN200910111556A CN101870711B CN 101870711 B CN101870711 B CN 101870711B CN 200910111556 A CN200910111556 A CN 200910111556A CN 101870711 B CN101870711 B CN 101870711B
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- phosphoric acid
- acid ester
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- trimethyl silicon
- phosphate
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Abstract
The invention relates to a synthesis method of a tris(trimethylsilyl) phosphate, which comprises the following steps: reacting hexamethyldisilazane with a phosphate for 2 to 5 hours at the temperature of 80 to 160 DEG C so as to form a tris(trimethylsilyl) phosphate and ammonia; then carrying out rectification and purification on the obtained crude product so as to obtain a fine product of the tris(trimethylsilyl) phosphate. The method has the advantages of simple operation, easy-taking raw material and simple post-processing, is suitable for industrial production, and can synthesize high quality product.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to the synthetic method of three (trimethyl silicon based) phosphoric acid ester.Three (trimethyl silicon based) phosphoric acid ester can be used as lithium-ion battery electrolytes additive.
Background technology
Three (trimethyl silicon based) phosphoric acid ester of indication of the present invention has following structure:
Research discovery, three (trimethyl silicon based) phosphoric acid ester can be used as lithium-ion battery electrolytes additive, improves the performance of lithium ion battery.Three (trimethyl silicon based) phosphoric acid ester is used as to the electrolysis additive of power cell in US Patent No. 20080166637A1.In Chinese patent CN1840550A, point out, three (trimethyl silicon based) phosphoric acid ester be a kind of when in charging state storage batteries, can suppress volume lowering for electrolytical composition and polymer electrolyte.High molecular weight electrolyte comprises electrolytic solution and high-molecular weight compounds, described electrolytic solution comprises the compound with P-O-Si key or B-O-Si key, thereby can suppress unreacted polymerizable compound, in electrode, react, can suppress cell resistance increases and can suppress volume lowering.
In Chinese invention patent CN200810001946.4, point out, while containing sultones and three (trimethyl silicon based) phosphate compound with unsaturated alkyl in nonaqueous electrolyte simultaneously, can form low-resistance overlay film and can not make the high-rate performance of battery reduce in negative terminal surface, thereby can suppress significantly the self-discharge of battery, and improve the cycle performance of battery, contain this electrolytical battery and can be used as power cell and be applied on electromobile.About the synthetic method of three (trimethyl silicon based) phosphoric acid ester, bibliographical information mainly contain following several method:
1, hexamethyl two silthianes and P
4o
10reacting by heating 10 hours, yield can reach 85%.Raw material hexamethyl two silthiane toxicity that [Zh.Obshch.Khim., 1985,55 (8): 1674] the method is used are large, there is no industrialization product, another raw material P of use
4o
10danger is also very large, poorly operation, and also temperature of reaction is high, the time is long, so this method is not suitable for suitability for industrialized production.
2, hexamethyldisilazane and P
4o
10reacting by heating 2 hours, but yield is only in 20%, [Zh.Obshch.Khim., 1985,55 (8): 1883], this method has been used the raw material P of dangerous large, bad operation equally
4o
10, and the yield of reaction is extremely low, so this method is not suitable for suitability for industrialized production.
3, J.Org.Chem.1982, introduced another kind of synthetic method at 47 (20): 3966, and hexamethyldisilazane reacts under asccharin or soluble saccharin katalysis with phosphoric acid with high yield and generates three (trimethyl silicon based) phosphoric acid ester.This method phosphoric acid used must be anhydrous, is also 100% phosphoric acid, but pure phosphoric acid preparation difficulty, and also more dangerous in use procedure.This method suitability for industrialized production is difficult.
The method of above bibliographical information exists that material toxicity is large, dangerous, long reaction time or the shortcoming such as product yield is low.So be necessary to find a kind of simple to operate, raw material is easy to get, be suitable for suitability for industrialized production, aftertreatment is simple, the method that can obtain high-quality product.
Summary of the invention
For the problems referred to above, the invention provides the synthetic method of high-quality three (trimethyl silicon based) phosphoric acid ester of a kind of economy.
The synthetic method of three (trimethyl silicon based) phosphoric acid ester comprises the steps: at 80～160 ℃ of temperature, hexamethyldisilazane and phosphate reaction 2～5 hours, generate three (trimethyl silicon based) phosphoric acid ester and ammonias, then crude product carries out rectifying purifying and obtains three (trimethyl silicon based) phosphoric acid ester fine work.
The synthetic method of a kind of three (trimethyl silicon based) phosphoric acid ester is in more detail disclosed: at 80～160 ℃ of temperature, hexamethyldisilazane reacts with primary ammonium phosphate 2～5 hours, generate three (trimethyl silicon based) phosphoric acid ester and ammonias, then crude product carries out rectifying purifying and obtains three (trimethyl silicon based) phosphoric acid ester fine work.
Invention process describes in detail as follows: hexamethyldisilazane and primary ammonium phosphate add in reactor with certain mol ratio, and then heating, stirring reaction, have ammonia and emit in reaction process, and the ammonia water of emitting absorbs.After reaction finishes, adopt the method for fractionation to obtain high-quality product three (trimethyl silicon based) phosphoric acid ester.
In the present invention, use primary ammonium phosphate instead of pure phosphoric acid, not only weigh convenient but also use safety.In reaction process, by product is ammonia, and the ammoniacal liquor after water absorbs can be used as a kind of Fertilizer application, also can be converted at an easy rate ammonium chloride, and realize zero release, has the feature of environmental protection.In building-up process, without catalyzer, can complete fast reaction, and yield is high, good product purity.
In three (trimethyl silicon based) phosphoric acid ester synthetic, the mol ratio of hexamethyldisilazane and primary ammonium phosphate is 1: 1～4: 1, and preferred value is 1.5: 1～1.8: 1.
In three (trimethyl silicon based) phosphoric acid ester synthetic, temperature of reaction is 80～160 ℃, preferably 90～140 ℃.
In three (trimethyl silicon based) phosphoric acid ester synthetic, the reaction times is 2～5 hours.
In three (trimethyl silicon based) phosphoric acid ester synthetic, method that can normal pressure fractionation is refining, also can adopt the method for vacuum fractionation refining, and preferably the method for vacuum fractionation is refining.
Through aforesaid method, synthesize also and can obtain high-quality three (trimethyl silicon based) phosphoric acid ester product after fractionation, can directly be used as lithium-ion battery electrolytes additive.
Compared with prior art, tool of the present invention has the following advantages: 1) security, and materials safety, reaction are easily controlled, and equipment is not corroded, simple to operate; 2) high, the product of reaction yield is easily purified, and purity is high; 3) feature of environmental protection, unique by product ammonia can be recycled, thereby has realized zero release.
Embodiment
Below by specific embodiment, the invention will be further described, but the present invention is not only defined in these examples.
Embodiment 1:
The there-necked flask of 500ml is equipped with electric mixer, reflux condensing tube, thermometer, adds 58g (0.5mol) primary ammonium phosphate, 320ml (1.5mol) hexamethyldisilazane, and at 120 ℃, heated and stirred reaction is 3 hours.After reaction finishes, change reflux into fractionation plant, carry out fractionation purifying, adopt the method for vacuum fractionation, collect the cut of 126～128 ℃/30mmHg, obtain three (trimethyl silicon based) phosphoric acid ester 126g.
Embodiment 2:
The there-necked flask of 1000ml is equipped with electric mixer, reflux condensing tube, thermometer, adds 200g (1.72mol) primary ammonium phosphate, 590ml (1.58mol) hexamethyldisilazane, and at 130 ℃, heated and stirred reaction is 3 hours.After reaction finishes, change reflux into fractionation plant, carry out fractionation purifying, adopt the method for vacuum fractionation, collect the cut of 118～119 ℃/25mmHg, obtain three (trimethyl silicon based) phosphoric acid ester 541g.
Embodiment 3:
The there-necked flask of 5000ml is equipped with electric mixer, reflux condensing tube, thermometer, adds 1000g (8.6mol) primary ammonium phosphate, 2950ml (13.6mol) hexamethyldisilazane, and at 100 ℃, heated and stirred reaction is 5 hours.After reaction finishes, change reflux into fractionation plant, carry out fractionation purifying, adopt the method for vacuum fractionation, collect the cut of 120～121 ℃/27mmHg, obtain three (trimethyl silicon based) phosphoric acid ester 2210g.
Embodiment 4:
The there-necked flask of 1000ml is equipped with electric mixer, reflux condensing tube, thermometer, adds 200g (1.72mol) primary ammonium phosphate, 620ml (1.66mol) hexamethyldisilazane, and at 150 ℃, heated and stirred reaction is 2 hours.After reaction finishes, change reflux into fractionation plant, carry out fractionation purifying, adopt the method for vacuum fractionation, collect the cut of 118～119 ℃/25mmHg, obtain three (trimethyl silicon based) phosphoric acid ester 500g.
Claims (4)
1. the synthetic method of (trimethyl silicon based) phosphoric acid ester, comprise the steps: at 80～160 ℃, hexamethyldisilazane reacts with primary ammonium phosphate 2～5 hours, generate three (trimethyl silicon based) phosphoric acid ester and ammonias, then crude product carries out rectifying purifying and obtains three (trimethyl silicon based) phosphoric acid ester fine work.
2. the synthetic method of three (trimethyl silicon based) as claimed in claim 1 phosphoric acid ester, is characterized in that: described hexamethyldisilazane and the mol ratio of primary ammonium phosphate are 1:1～4:1.
3. the synthetic method of three (trimethyl silicon based) as claimed in claim 2 phosphoric acid ester, is characterized in that: described hexamethyldisilazane and the mol ratio of primary ammonium phosphate are 1.5:1～1.8:1.
4. the synthetic method of three (trimethyl silicon based) as claimed in claim 1 phosphoric acid ester, is characterized in that: described hexamethyldisilazane and primary ammonium phosphate temperature of reaction are 90～140 ℃.
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| CN200910111556.7A CN101870711B (en) | 2009-04-24 | 2009-04-24 | Synthesis method of tris(trimethylsilyl) phosphate |
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| CN101870711B true CN101870711B (en) | 2014-09-17 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675361B (en) * | 2012-05-22 | 2015-08-05 | 江苏华盛精化工股份有限公司 | The method of purification of three (trimethyl silicon based) phosphorous acid esters and three (trimethyl silicon based) phosphoric acid ester |
| CN105949233A (en) * | 2016-05-16 | 2016-09-21 | 江苏长园华盛新能源材料有限公司 | Preparation method of tris(trimethylsilyl) phosphate |
| CN106946929B (en) * | 2017-03-30 | 2019-06-18 | 石家庄圣泰化工有限公司 | Three (trimethyl silicon substrate) phosphate synthesis methods |
| KR20200012886A (en) * | 2017-06-01 | 2020-02-05 | 히타치가세이가부시끼가이샤 | Electrolytes and Electrochemical Devices |
| CN110551151A (en) * | 2018-05-30 | 2019-12-10 | 微宏动力系统（湖州）有限公司 | preparation method of phosphate or phosphite ester, electrolyte and secondary battery |
| CN109503653B (en) * | 2018-12-25 | 2021-08-24 | 苏州祺添新材料有限公司 | Synthesis method of tri (trihydrocarbylsilyl) phosphate |
| CN112375207A (en) * | 2021-01-14 | 2021-02-19 | 东营大莱新材料有限公司 | Preparation method of phosphorus-nitrogen modified isocyanate |
| CN113054258B (en) * | 2021-04-21 | 2023-07-04 | 广州天赐高新材料股份有限公司 | New application of substituted silicon-based phosphate compound, electrolyte and lithium ion battery |
| CN114478619B (en) * | 2022-02-14 | 2023-11-28 | 九江天赐高新材料有限公司 | Silicon-based phosphate and preparation method thereof |
| CN115477288B (en) * | 2022-10-17 | 2024-02-27 | 无锡零一未来新材料技术研究院有限公司 | Phosphoric acid water removal method and preparation method of tris (trimethylsilane) phosphate |
| CN115588779B (en) * | 2022-11-11 | 2023-11-28 | 广州天赐高新材料股份有限公司 | High-temperature non-aqueous electrolyte and secondary battery |
-
2009
- 2009-04-24 CN CN200910111556.7A patent/CN101870711B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| Catalysts for Silylations with 1,1,1,3,3,3-Hexamethyldisilazan;Cornelis A. Bruynes等;《J. Org. Chem.》;19821231;第47卷(第20期);第3966-3969页 * |
| Cornelis A. Bruynes等.Catalysts for Silylations with 1,1,1,3,3,3-Hexamethyldisilazan.《J. Org. Chem.》.1982,第47卷(第20期), |
| Gas Chromatographic Analysis of Aqueous Phosphate by Reaction Gas Chromatography;Patrick M. Wiese等;《ANALYTICAL CHEMISTRY》;19721231;第2393-2394页 * |
| Patrick M. Wiese等.Gas Chromatographic Analysis of Aqueous Phosphate by Reaction Gas Chromatography.《ANALYTICAL CHEMISTRY》.1972, |
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