CN101870711A - Synthesis method of tris(trimethylsilyl) phosphate - Google Patents
Synthesis method of tris(trimethylsilyl) phosphate Download PDFInfo
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- CN101870711A CN101870711A CN200910111556A CN200910111556A CN101870711A CN 101870711 A CN101870711 A CN 101870711A CN 200910111556 A CN200910111556 A CN 200910111556A CN 200910111556 A CN200910111556 A CN 200910111556A CN 101870711 A CN101870711 A CN 101870711A
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- phosphate
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- trimethyl silicon
- phosphoric acid
- hexamethyldisilazane
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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 three (trimethyl silicon based) synthesis process of phosphate.Three (trimethyl silicon based) phosphoric acid ester can be used as the lithium-ion battery electrolytes additive.
Background technology
Three (trimethyl silicon based) phosphoric acid ester of indication of the present invention has following structure:
Discover that three (trimethyl silicon based) phosphoric acid ester can be used as the lithium-ion battery electrolytes additive, improves the performance of lithium ion battery.In U.S. Pat 20080166637A1, three (trimethyl silicon based) phosphoric acid ester is used as the electrolysis additive of power cell.In Chinese patent CN1840550A, point out, three (trimethyl silicon based) phosphoric acid ester be a kind of can inhibition when in the charging state storage batteries capacity reduce be used 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, react in electrode thereby can suppress unreacted polymerizable compound, can suppress cell resistance increase and the reduction of energy inhibition capacity.
In Chinese invention patent CN200810001946.4, point out, when in nonaqueous electrolyte, containing sultones and three (trimethyl silicon based) phosphate compound simultaneously with unsaturated alkyl, can form low-resistance overlay film and the high-rate performance of battery is reduced in negative terminal surface, thereby can suppress the self-discharge of battery significantly, and improve the cycle performance of battery, contain this electrolytical battery and can be used as power cell and be applied on the electromobile.About three (trimethyl silicon based) synthesis process of phosphate, bibliographical information mainly contain following several method:
1, hexamethyl two silthianes and P
4O
10Reacting by heating 10 hours, yield can reach 85%.The employed raw material hexamethyl two silthiane toxicity of [Zh.Obshch.Khim., 1985,55 (8): 1674] this method are big, do not have industrialization product, another raw material P of use
4O
10Danger is also very big, not so good operation, and also temperature of reaction height, time are long, so this method is not suitable for suitability for industrialized production.
2, hexamethyldisilazane and P
4O
10Reacting by heating 2 hours, but yield only is in 20%, [Zh.Obshch.Khim., 1985,55 (8): 1883], this method has been used the raw material P of dangerous big, 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 promptly hexamethyldisilazane and phosphoric acid react under asccharin or soluble saccharin katalysis with high yield and generate three (trimethyl silicon based) phosphoric acid ester.The used phosphoric acid of this method must be anhydrous, also is 100% phosphoric acid, but pure phosphoric acid preparation difficulty, and also relatively more dangerous in the use.This method suitability for industrialized production is difficult.
Shortcomings such as the method for above bibliographical information exists that material toxicity is big, dangerous, long reaction time or product yield are low.So be necessary to seek 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
At the problems referred to above, the invention provides high-quality three (trimethyl silicon based) synthesis process of phosphate of a kind of economy.
Three (trimethyl silicon based) synthesis process of phosphate comprises the steps: under 80～160 ℃ of temperature, hexamethyldisilazane and phosphate reaction 2～5 hours, generate three (trimethyl silicon based) phosphoric acid ester and ammonias, crude product carries out the rectifying purifying and obtains three (trimethyl silicon based) phosphoric acid ester elaboration then.
A kind of three (trimethyl silicon based) synthesis process of phosphate is in more detail disclosed: under 80～160 ℃ of temperature, hexamethyldisilazane and primary ammonium phosphate reaction 2～5 hours, generate three (trimethyl silicon based) phosphoric acid ester and ammonias, crude product carries out the rectifying purifying and obtains three (trimethyl silicon based) phosphoric acid ester elaboration then.
The invention process is described in detail as follows: hexamethyldisilazane and primary ammonium phosphate add in the reactor with certain molar ratio, and heating, stirring reaction have ammonia and emit in the reaction process then, and the ammonia water of emitting absorbs.Reaction adopts fractionated method to obtain high-quality product three (trimethyl silicon based) phosphoric acid ester after finishing.
In the present invention, use primary ammonium phosphate instead of pure phosphoric acid, not only weighing is convenient but also safe in utilization.By product is an ammonia in the reaction process, and the ammoniacal liquor after water absorbs can be used as a kind of fertilizer and uses, and also can be converted into ammonium chloride at an easy rate, and realizes zero release having the feature of environmental protection.In building-up process, need not catalyzer and can finish reaction fast, and the yield height, 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 ℃, preferred 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, can the fractionated method of normal pressure refining, also can adopt the method for vacuum fractionation refining, the method for preferred vacuum fractionation is refining.
High-quality three (trimethyl silicon based) phosphoric acid ester product can be obtained through aforesaid method after the synthetic and fractionation, the lithium-ion battery electrolytes additive can be directly be used as.
Compared with prior art, the present invention has following advantage: 1) security, and materials safety, reaction control is not easily corroded equipment, and is simple to operate; 2) reaction yield height, product are easily purified, the purity height; 3) feature of environmental protection, the unique side product ammonia can be recycled, thereby has realized zero release.
Embodiment
The invention will be further described below by specific embodiment, but the present invention not only is defined in these examples.
Embodiment 1:
The there-necked flask of 500ml was equipped with electric mixer, reflux condensing tube, thermometer, adds 58g (0.5mol) primary ammonium phosphate, 320ml (1.5mol) hexamethyldisilazane, in 120 ℃ of following heated and stirred reactions 3 hours.Reaction changes reflux into fractionation plant after finishing, and carries out the fractionation purifying, adopts the method for vacuum fractionation, collects the cut of 126～128 ℃/30mmHg, gets three (trimethyl silicon based) phosphoric acid ester 126g.
Embodiment 2:
The there-necked flask of 1000ml was equipped with electric mixer, reflux condensing tube, thermometer, adds 200g (1.72mol) primary ammonium phosphate, 590ml (1.58mol) hexamethyldisilazane, in 130 ℃ of following heated and stirred reactions 3 hours.Reaction changes reflux into fractionation plant after finishing, and carries out the fractionation purifying, adopts the method for vacuum fractionation, collects the cut of 118～119 ℃/25mmHg, gets three (trimethyl silicon based) phosphoric acid ester 541g.
Embodiment 3:
The there-necked flask of 5000ml was equipped with electric mixer, reflux condensing tube, thermometer, adds 1000g (8.6mol) primary ammonium phosphate, 2950ml (13.6mol) hexamethyldisilazane, in 100 ℃ of following heated and stirred reactions 5 hours.Reaction changes reflux into fractionation plant after finishing, and carries out the fractionation purifying, adopts the method for vacuum fractionation, collects the cut of 120～121 ℃/27mmHg, gets three (trimethyl silicon based) phosphoric acid ester 2210g.
Embodiment 4:
The there-necked flask of 1000ml was equipped with electric mixer, reflux condensing tube, thermometer, adds 200g (1.72mol) primary ammonium phosphate, 620ml (1.66mol) hexamethyldisilazane, in 150 ℃ of following heated and stirred reactions 2 hours.Reaction changes reflux into fractionation plant after finishing, and carries out the fractionation purifying, adopts the method for vacuum fractionation, collects the cut of 118～119 ℃/25mmHg, gets three (trimethyl silicon based) phosphoric acid ester 500g.
Claims (6)
1. (trimethyl silicon based) synthesis process of phosphate, comprise the steps: under 80～160 ℃, hexamethyldisilazane and phosphate reaction 2～5 hours, generate three (trimethyl silicon based) phosphoric acid ester and ammonias, crude product carries out the rectifying purifying and obtains three (trimethyl silicon based) phosphoric acid ester elaboration then.
2. three (trimethyl silicon based) as claimed in claim 1 synthesis process of phosphate, it is characterized in that: described phosphoric acid salt is primary ammonium phosphate.
3. three (trimethyl silicon based) as claimed in claim 2 synthesis process of phosphate, it is characterized in that: the mol ratio of described hexamethyldisilazane and primary ammonium phosphate is 1: 1～4: 1.
4. three (trimethyl silicon based) as claimed in claim 2 synthesis process of phosphate, it is characterized in that: the mol ratio of described hexamethyldisilazane and primary ammonium phosphate is 1.5: 1～1.8: 1.
5. three (trimethyl silicon based) as claimed in claim 1 synthesis process of phosphate, it is characterized in that: described hexamethyldisilazane and phosphate reaction temperature are 80～160 ℃.
6. three (trimethyl silicon based) as claimed in claim 1 synthesis process of phosphate, it is characterized in that: described hexamethyldisilazane and phosphate reaction temperature 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 CN101870711B (en) | 2014-09-17 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675361A (en) * | 2012-05-22 | 2012-09-19 | 张家港市华盛化学有限公司 | Purification method of tri (trimethylsililyl) phosphite ester and tri (trimethylsililyl) phosphate 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 |
| CN106946929A (en) * | 2017-03-30 | 2017-07-14 | 石家庄圣泰化工有限公司 | Three（Trimethyl silicon substrate）Phosphate synthesis method |
| CN109503653A (en) * | 2018-12-25 | 2019-03-22 | 常熟市常吉化工有限公司 | A kind of three (trialkyl silicon substrate) phosphate synthesis methods |
| 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 |
| CN110710046A (en) * | 2017-06-01 | 2020-01-17 | 日立化成株式会社 | Electrolyte solution and electrochemical device |
| 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 |
| CN114478619A (en) * | 2022-02-14 | 2022-05-13 | 九江天赐高新材料有限公司 | Silicon-based phosphate and preparation method thereof |
| WO2022222420A1 (en) * | 2021-04-21 | 2022-10-27 | 广州天赐高新材料股份有限公司 | New use of substituted silicon-based phosphate compound, electrolyte, and lithium ion battery |
| CN115477288A (en) * | 2022-10-17 | 2022-12-16 | 无锡零一未来新材料技术研究院有限公司 | Phosphoric acid dehydration method and preparation method of tri (trimethylsilyl) phosphate |
| CN115588779A (en) * | 2022-11-11 | 2023-01-10 | 广州天赐高新材料股份有限公司 | High-temperature nonaqueous electrolyte solution and secondary battery |
| CN116239564A (en) * | 2023-01-09 | 2023-06-09 | 曹文兵 | Preparation method of cyclic sulfite, tri (trimethylsilane) phosphate and cyclic sulfate carbonate solution continuous co-production |
-
2009
- 2009-04-24 CN CN200910111556.7A patent/CN101870711B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| CORNELIS A. BRUYNES等: "Catalysts for Silylations with 1,1,1,3,3,3-Hexamethyldisilazan", 《J. ORG. CHEM.》 * |
| PATRICK M. WIESE等: "Gas Chromatographic Analysis of Aqueous Phosphate by Reaction Gas Chromatography", 《ANALYTICAL CHEMISTRY》 * |
Cited By (19)
| 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 |
| CN102675361A (en) * | 2012-05-22 | 2012-09-19 | 张家港市华盛化学有限公司 | Purification method of tri (trimethylsililyl) phosphite ester and tri (trimethylsililyl) phosphate 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 |
| CN106946929A (en) * | 2017-03-30 | 2017-07-14 | 石家庄圣泰化工有限公司 | Three（Trimethyl silicon substrate）Phosphate synthesis method |
| 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 |
| CN110710046A (en) * | 2017-06-01 | 2020-01-17 | 日立化成株式会社 | Electrolyte solution and electrochemical device |
| 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 |
| CN109503653A (en) * | 2018-12-25 | 2019-03-22 | 常熟市常吉化工有限公司 | A kind of three (trialkyl silicon substrate) phosphate synthesis methods |
| 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 |
| WO2022222420A1 (en) * | 2021-04-21 | 2022-10-27 | 广州天赐高新材料股份有限公司 | New use of substituted silicon-based phosphate compound, electrolyte, and lithium ion battery |
| CN114478619A (en) * | 2022-02-14 | 2022-05-13 | 九江天赐高新材料有限公司 | Silicon-based phosphate and preparation method thereof |
| WO2023151691A1 (en) * | 2022-02-14 | 2023-08-17 | 九江天赐高新材料有限公司 | Silicon-based phosphate and preparation method therefor |
| 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 |
| CN115477288A (en) * | 2022-10-17 | 2022-12-16 | 无锡零一未来新材料技术研究院有限公司 | Phosphoric acid dehydration method and preparation method of tri (trimethylsilyl) phosphate |
| 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 |
| CN115588779A (en) * | 2022-11-11 | 2023-01-10 | 广州天赐高新材料股份有限公司 | High-temperature nonaqueous electrolyte solution and secondary battery |
| 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 |
| CN116239564A (en) * | 2023-01-09 | 2023-06-09 | 曹文兵 | Preparation method of cyclic sulfite, tri (trimethylsilane) phosphate and cyclic sulfate carbonate solution continuous co-production |
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| CN101870711B (en) | 2014-09-17 |
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