WO2014026431A1 - 一种三氟甲基直链碳酸酯的制备方法 - Google Patents

一种三氟甲基直链碳酸酯的制备方法 Download PDF

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WO2014026431A1
WO2014026431A1 PCT/CN2012/083285 CN2012083285W WO2014026431A1 WO 2014026431 A1 WO2014026431 A1 WO 2014026431A1 CN 2012083285 W CN2012083285 W CN 2012083285W WO 2014026431 A1 WO2014026431 A1 WO 2014026431A1
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trifluoromethyl
saturated
monohydric alcohol
linear
preparation
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PCT/CN2012/083285
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English (en)
French (fr)
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张先林
杨志勇
张丽亚
吴国栋
陆海媛
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江苏华盛精化工股份有限公司
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Priority to JP2015525706A priority Critical patent/JP2015528434A/ja
Priority to KR1020157003402A priority patent/KR20150036472A/ko
Publication of WO2014026431A1 publication Critical patent/WO2014026431A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids

Definitions

  • the present invention relates to a process for preparing a trifluoromethyl-containing linear carbonate, and more particularly to a saturated monohydric alcohol and a triphosgene from a trifluoromethyl group. Replace the preparation method.
  • a trifluoromethyl-containing linear carbonate is a novel high-voltage lithium battery solvent having an electrochemical window of 5 V or more, and contains a large amount of fluorine in the molecule, and participates in a part of the solvated lithium in the electrochemical field of the lithium battery.
  • the reaction, and participate in the formation of fluorine-containing SEI film enhances the thermal stability of the lithium battery, and then greatly improves the cycle performance of the battery.
  • the application of the new solvent in the dynamic high-voltage lithium battery electrolyte is very broad.
  • the most common preparation method in China is to carry out a transesterification reaction in the presence of a carbonate catalyst using a saturated alcohol containing a trifluoromethyl group and a decyl carbonate.
  • a carbonate catalyst using a saturated alcohol containing a trifluoromethyl group and a decyl carbonate.
  • the activity of the hydroxyl group is greatly reduced, which greatly affects the synthesis yield, and the yield is
  • the main technical problem to be solved by the present invention is to provide a preparation method for preparing a trifluoromethyl-containing linear carbonate by directly substituting a saturated monohydric alcohol containing a trifluoromethyl group with a triphosgene.
  • a method for preparing a trifluoromethyl-containing linear carbonate the steps are as follows:
  • the trifluoromethyl saturated monohydric alcohol and the triphosgene are mixed, and in the presence of an organic amine acid binding agent (chelating hydrogen chloride formed by the reaction to facilitate the reaction), the temperature is adjusted to 25 to 80 ° C, and the reaction is ⁇ 10h, A mixed liquid containing a trifluoromethyl linear carbonate is obtained, which is separated by filtration, and the mixture containing a trifluoromethyl linear carbonate is subjected to distillation and purification to obtain a trifluoromethyl-containing linear carbonate (symmetric structure product) ( I); the structural formula of the trifluoromethyl-containing linear carbonate is: (I)
  • n 0 ⁇ 2
  • n is an integer, which is a methyl group, an ethyl group or a propyl group.
  • the molar ratio of the trifluoromethyl saturated monohydric alcohol to the triphosgene is 6 ⁇ 12:1; the molar ratio of the organic amine acid binding agent to the triphosgene is 6-8:1.
  • n 0 ⁇ 2
  • n is an integer, which is a methyl group, an ethyl group or a propyl group.
  • the molar ratio of the trifluoromethyl saturated monohydric alcohol to the saturated linear monohydric alcohol is 9 to 1: 1, and the molar ratio maximizes the conversion of the reaction raw materials.
  • the molar ratio of the mixture of the trifluoromethyl saturated monohydric alcohol and the saturated linear monohydric alcohol to the triphosgene is 6-12: 1; the molar ratio of the organic amine binding agent to triphosgene is 6-8: 1;
  • the trifluorodecyl alcohol is 2, 2, 2-trifluoroethanol (CF 3 CH 2 OH) and/or 3, 3, 3-trifluoropropanol
  • the saturated linear monohydric alcohol is selected from one or more of the following: methanol, ethanol, propanol.
  • the organic amine acid binding agent is selected from one or more of the following: triethylamine, tributylamine, n-butylamine, dibutylamine.
  • the distillation purification conditions are 70 to 120 ° C / 10 to 100 kPa.
  • the preferred molar ratio of the mixture of the trifluoromethyl saturated monohydric or trifluoromethyl saturated monohydric alcohol to the saturated linear monohydric alcohol to triphosgene is from 8:1 to 12:1.
  • the reaction of the present invention is as follows (organic amine acid scavenger is exemplified by triethylamine): TEAHC1 TEAHC1 TEAHC1
  • the beneficial effects of the present invention are as follows:
  • a trifluoromethyl saturated monohydric alcohol is used as a raw material, and a reaction gas of triphosgene in the presence of an organic amine-binding agent at 25 to 80 ° C to obtain a trifluoromethyl-containing linear carbonic acid is obtained.
  • the ester is further purified by distillation to obtain a trifluoromethyl linear carbonic acid having a purity of 99% or more.
  • the preparation method has the advantages of simple process, high yield (more than 65%) and low cost, and strong stability of triphosgene, and only a small amount of decomposition at a boiling point of 200 ° C, so there is no major safety and environmental protection problems in the preparation process.
  • the chromatographic conditions were Agilent 7890A, split ratio 50:1, inlet temperature 280 °C, detector temperature 300 °C, column HP-5 (30 mX 0.25 mX 0.25 m), temperature program 100 °C ( 2min) - 10 °C /min-250 °C (2min) -15 °C /min-280 °C (5min), standard calibration retention time, area normalization method.
  • the obtained filtrate was subjected to atmospheric pressure reflux control to carry out rectification to recover residual trifluoroethanol and excess trifluoroethanol, and 523.6 g of 112-116 ° C / 100 kPa bistrifluoroethyl carbonate was collected and analyzed by Agilent 7890A. (RT2.525), content: 99.94 Wt.%, yield 77.2%.
  • Example 2 297.0 g (1.0 mol) of triphosgene and 1368.0 g (12.0 mol) of trifluoropropanol were added to a three-necked flask and stirred and mixed, 80 620.0g (6.14moi;) of triethylamine was added dropwise at °C.
  • the content of triethylamine in the sample filtrate was less than 3%.
  • the filtrate was cooled and filtered to obtain 1485.6 filtrate, and the product was analyzed by Agilent 7890A.
  • the content of trifluoropropyl carbonate is 58.6358%
  • the content of triethylamine is 1.2313%
  • trifluoropropanol is 40. 1637%.
  • the obtained filtrate was refluxed under normal pressure to adjust the residual trifluoropropanol and excess triethylamine, and 755.65 g of 75-85 ° C/10 ⁇ 30 kPa di-trifluoropropyl carbonate was collected under reduced pressure.
  • Example 3 297.0 g (1.0 mol) of triphosgene and 400.0 g (4.0 mol) of trifluoroethanol and 96.0 g of methanol (3.0 mol) were added to a three-necked flask, stirred and mixed, and 452.6 g of n-butylamine was added dropwise at 50 ° C ( 6.2mol), after 1 hour of holding after the addition, the content of n-butylamine in the sample filtrate is less than 3%; 565.8g of filtrate is obtained by cooling filtration, and the content of methyl trifluoroethyl carbonate is 72.0718% by Agilent 7890A.
  • the content of butanamine is 1.9256%
  • the content of trifluoroethanol is 18.4679%
  • the content of bistrifluoroethyl carbonate is 4.1135%
  • the content of dimethyl carbonate is 3.4312%.
  • the obtained filtrate was subjected to atmospheric pressure reflux control to carry out distillation to recover residual trifluoroethanol and excess n-butylamine, and collected 385.4 g of 102-106 ° C / 100 kPa trifluoroethyl methyl carbonate, which was detected by Agilent 7890A analysis (RT1). .586), the content is 99.90 Wt.%, and the yield is 67.5%.
  • Example 4 297.0 g (1.0 mol) of triphosgene and 900.0 g (9.0 mol) of trifluoroethanol and 32.0 g of methanol (1.0 mol) were added to a three-necked flask, stirred and mixed, and triethylamine 620.0 g was added dropwise at 70 ° C. (6.14mol), after 8 hours of holding after the addition, the content of triethylamine in the sample filtrate was less than 3%; 975.7g of filtrate was obtained by cooling filtration, and the content of methyl trifluoroethyl carbonate was 15.4051% by Agilent 7890A.
  • the bistrifluoroethyl carbonate contains 45.3257%, the triethylamine content is 1.6231%, the trifluoroethanol is 37.3246%, and the dimethyl carbonate is 0.3215%.
  • the obtained filtrate was subjected to atmospheric pressure reflux control to carry out distillation to recover residual trifluoroethanol and excess triethylamine, and collected 132.6 g of 102-106 ° C / 100 kPa trifluoroethyl methyl carbonate, which was detected by Agilent 7890A analysis (RT1).
  • the content is 99.52 Wt.%; Collecting 384.3g of 112-116°C / lOOkPa bistrifluoroethyl carbonate, detected by Agilent 7890A (RT2.525), the content is 99.95Wt.%, the yield is 84.6 %.
  • 297.0 g (1.0 mol) of triphosgene and 400.0 g (4.0 mol) of trifluoroethanol and 184.0 g of ethanol (4.0 mol) were added to a three-necked flask, stirred and mixed, and tributylamine 1128.5 g (6.1 mol) was added dropwise at 65 °C.
  • the content of tributylamine in the sample filtrate was less than 3%; 582.5 g of filtrate was obtained by cooling filtration, and the content of ethyl trifluoroethyl carbonate was determined by Agilent 7890A, and the content of trifluoroethyl carbonate was 72.8112%.
  • the ethyl carbonate content was 2.9423%, the diethyl carbonate was 2.5613%, the tributylamine content was 2.4352%, the trifluoroethanol was 14.1073%, and the ethanol was 5.1535%.
  • the obtained filtrate was subjected to atmospheric pressure reflux distillation to carry out rectification to recover residual trifluoroethanol and ethanol, and collected 418.3 g of ethyl trifluoroethyl carbonate at 118-120 ° C/100 kPa, which was detected by Agilent 7890A (RT2.096). The content is 99.67 Wt.%, and the yield is 80.8%.
  • Comparative Example 1 90.0 g (1.0 mol) of dimethyl carbonate and 600.0 g (6.0 mol) of trifluoroethanol were placed in a three-necked flask, stirred and mixed, and 10.0 g of potassium carbonate was added thereto, and the mixture was kept at 70 ° C for 10 hours, and then sampled and passed.
  • Agilent 7890A analytical analysis, trifluoroethanol content 73.6811%, methanol 3.7101%, dimethyl carbonate content 7.8211%, trifluoroethyl methyl carbonate content 2.7188%, bistrifluoroethyl carbonate 12.0639%.
  • the obtained filtrate was subjected to atmospheric pressure reflux control to carry out rectification to recover residual trifluoroethanol and excess methanol and raw material dimethyl carbonate, and collected 16.5 g of 102-106 ° C / 100 kPa trifluoroethyl carbonate, through Agilent 7890A
  • the content of analysis and detection was 99.32 Wt.%, and 78.6 g of 112-116 °C/100 kPa bistrifluoroethyl carbonate was collected and analyzed by Agilent 7890A (RT2.525), the content was 99.58 Wt.%, and the yield was 42.08%.
  • Comparative Example 2 90.0 g (1.0 mol) of dimethyl carbonate and 600.0 g (6.0 mol) of trifluoroethanol were added to a three-necked flask, stirred and mixed, and sodium methoxide (10.0 g) was added thereto, and the mixture was kept at 70 ° C for 10 hours, and then sampled and passed.
  • Agilent 7890A, analysis and detection trifluoroethanol content 71.5438%, methanol 4.5613%, dimethyl carbonate content 6.9523%, trifluoroethyl methyl carbonate content 3.8244%, bistrifluoroethyl carbonate 13.1173%.
  • the obtained filtrate was subjected to atmospheric pressure reflux control to carry out rectification to recover residual trifluoroethanol and excess methanol and raw material dimethyl carbonate, and collected 18.2 g of 102-106 ° C / 100 kPa trifluoroethyl methyl carbonate, through Agilent 7890A Analytical test (RT1.586), the content was 99.42 Wt.%, collected 112 ⁇ 116. C/100kPa bistrifluoroethyl carbonate 83.9g, analyzed by Agilent 7890A (RT2.525), the content was 99.61 Wt.%, the yield was 45.18%. It is to be understood that various changes and modifications may be made by those skilled in the art in the ⁇ RTIgt;

Abstract

本发明公开了一种含三氟甲基直链碳酸酯的制备方法，其制备歩骤为：将三氟甲基饱和一元醇或三氟甲基饱和一元醇与饱和直链一元醇的混合物，与三光气混合，在有机胺缚酸剂存在下，调整温度为25~80°C，反应1~10h，得到含三氟甲基直链碳酸酯的混合液，过滤分离，对三氟甲基直链碳酸酯的混合液进行蒸馏提纯，得到含三氟甲基直链碳酸酯。本发明公开工艺制得的三氟甲基直链碳酸，是一种新型动力锂电池高电压型溶剂，对动力锂电池的热稳定性、循环性能以及高电压特性有极大地提升。本制备方法工艺简单、收率高且成本低廉，同时三光气稳定性强，在沸点200°C仅有少量分解，因此制备过程不存在重大安全、环保等问题。

Description

一种三氟甲基直链碳酸酯的制备方法 技术领域 本发明涉及一种含三氟甲基直链碳酸酯的制备方法， 尤其涉及一种由 三氟甲基的饱和一元醇与三光气直接取代制备方法。
背景技术 含三氟甲基直链碳酸酯是一种新型高电压锂电池溶剂， 电化学窗口达 到 5V 以上， 同时分子中含有大量的氟元素， 在锂电池电化学场下参与部 分的溶剂化锂反应， 并参与形成含氟的 SEI膜， 增强了锂电池的热稳定性， 继而大大提高了电池的循环性能， 在动力型高电压锂电池电解液新型溶剂 的应用前景非常广阔。
目前， 国内最常用的制备方法是采用含三氟甲基的饱和醇与碳酸垸基 酯， 在碳酸盐催化剂存在下进行酯交换反应。 但该方法中因三氟甲基的强 拉电子效应， 造成羟基的活性大大降低， 极大地影响了合成收率， 收率为
40-50%, 同时增加了未反应的醇、 碳酸酯以及酯交换产物的分离困难。
发明内容 本发明主要解决的技术问题是： 提供一种由含三氟甲基的饱和一元醇 与三光气直接发生取代制备含三氟甲基直链碳酸酯的制备方法。
为了解决上述技术问题， 本发明的技术方案是： 一种含三氟甲基直链碳 酸酯的制备方法： 其歩骤为：
将三氟甲基饱和一元醇， 及三光气混合， 在有机胺缚酸剂 （对反应生成的 氯化氢进行螯合，有利于反应的进行）存在下，调整温度为 25~80°C，反应 l~10h， 得到含三氟甲基直链碳酸酯的混合液， 过滤分离， 对含三氟甲基直链碳酸酯的 混合液进行蒸馏提纯， 得到含三氟甲基直链碳酸酯 （对称结构产物） （I); 所述含三氟甲基直链碳酸酯结构式为：
Figure imgf000003_0001
(I)
其中， n=0~2， 且 n为整数， 为甲基、 乙基或丙基。
所述三氟甲基饱和一元醇与三光气的摩尔比为 6~12： 1； 所述有机胺缚酸剂 与三光气的摩尔比为 6~8： 1。
将三氟甲基饱和一元醇与饱和直链一元醇的混合物， 与三光气混合， 在有 机胺缚酸剂存在下， 调整温度为 25~80°C， 反应 l~10h， 得到含三氟甲基直链碳 酸酯的混合液， 过滤分离， 对含三氟甲基直链碳酸酯的混合液进行蒸馏提纯， 得到含三氟甲基直链碳酸酯 （非对称结构产物） （II);
所述含三氟甲基直链碳酸酯结构式为：
Figure imgf000003_0002
其中， n=0~2， 且 n为整数， 为甲基、 乙基或丙基。
所述三氟甲基饱和一元醇与饱和直链一元醇混合物中， 三氟甲基饱和一元 醇与饱和直链一元醇的摩尔比为 9~1： 1， 该摩尔比例使反应原料最大程度转化 为结构式 （Π) 表示的含三氟甲基直链碳酸酯。
所述三氟甲基饱和一元醇与饱和直链一元醇的混合物与三光气的摩尔比为 6-12： 1； 所述有机胺缚酸剂与三光气的摩尔比为 6~8： 1；
所述三氟垸基醇为 2， 2， 2-三氟乙醇 （CF3CH2OH) 和 /或 3， 3， 3-三氟丙醇
(CF3 CH2CH2OH)o 所述饱和直链一元醇选自下述物质中的一种或几种： 甲醇、 乙醇、 丙醇。 所述有机胺缚酸剂选自下述物质中的一种或几种： 三乙胺、 三丁胺、 正丁 胺、 二丁胺。
所述的蒸馏提纯条件为 70~120°C/10~100kPa。 所述三氟甲基饱和一元醇或三氟甲基饱和一元醇与饱和直链一元醇的混合 物与三光气的优选摩尔比为 8:1~12: 1。 本发明的反应如下表示 （有机胺缚酸剂以三乙胺为例）： TEAHC1 TEAHC1 TEAHC1
Figure imgf000004_0001
本发明的有益效果是： 本发明中采用三氟甲基饱和一元醇为原料， 与三光 气在有机胺缚酸剂存在下， 于 25~80 °C下反应得到含三氟甲基直链碳酸酯， 再通过蒸馏精制得到纯度 99%以上的三氟甲基直链碳酸。 是一种新型动力锂 电池高电压型溶剂， 对动力锂电池的热稳定性、 循环性能以及高电压特性 有极大地提升。 本制备方法工艺简单、 收率高 （65%以上） 且成本低廉， 同时三光气稳定性强， 在沸点 200 °C仅有少量分解， 因此制备过程不存在 重大安全、 环保等问题。
具体实施方式
结合实施例做进一歩的详细说明，使本发明的优点更为明显。应该理解， 其中的内容只是用作说明， 而绝非对本发明的保护范围构成限制。 下列实 施例中未注明具体条件的实验方法， 通常按照常规条件， 或按照制造厂商 所建议的条件进行。 除非另外说明， 否则所有的份数为质量份， 所有的百 分比为质量百分比。
实施例中色谱检测条件为安捷伦 7890A, 分流比 50: 1,进样口温度 280 °C， 检测器温度 300°C， 色谱柱 HP-5(30mX 0.25mX 0.25 m),升温程序 100 °C (2min)- 10 °C /min-250 °C (2min)-15 °C /min-280 °C (5min),标样校准保留时间， 面积归一法。
实施例 1
将 297.0g(1.0mol)三光气和 600.0g ( 6.0mol) 三氟乙醇加入三口烧瓶中 搅拌混匀， 25°C下滴加三乙胺 620.0g((6.14mol)， 滴加结束后保温 4小时后， 取样滤液中三氟乙醇含量小于 1%; 冷却过滤得到 578.6g 滤液， 通过安捷伦 7890A,分析检测产品双三氟乙基碳酸酯含量 93.6178%,三乙胺含量 2.8156%, 三氟乙醇 0.4679%。 对得到的滤液进行常压带回流调节精馏回收残留的三氟乙 醇和过量的三氟乙醇，收集 112~116°C/100kPa双三氟乙基碳酸酯 523.6g，通过 安捷伦 7890A分析检测 （RT2.525), 含量为 99.94 Wt.%， 收率 77.2%。 实施例 2 将 297.0g(1.0mol)三光气和 1368.0g ( 12.0mol) 三氟丙醇加入三口烧瓶 中搅拌混匀， 80°C下滴加三乙胺 620.0g(6.14moi;)，滴加结束后保温 10小时后， 取样滤液中三乙胺含量小于 3%; 冷却过滤得到 1485.6 滤液， 通过安捷伦 7890A,分析检测产品双三氟丙基碳酸酯含量 58.6358%,三乙胺含量 1.2313%, 三氟丙醇 40.1637%。 对得到的滤液进行常压带回流调节精馏回收残留的三氟 丙醇和过量的三乙胺， 减压收集 75~85°C/10~30kPa双三氟丙基碳酸酯 815.6g， 通过安捷伦 7890A分析检测 （RT5.596) , 含量为 99.91 Wt.%， 收率 95.1%。 实施例 3 将 297.0g(1.0mol)三光气与 400.0g(4.0mol)三氟乙醇和 96.0g 甲醇 (3.0mol)加入三口烧瓶中搅拌混匀， 50°C下滴加正丁胺 452.6g (6.2mol)， 滴 加结束后保温 1 小时后， 取样滤液中正丁胺胺含量小于 3%; 冷却过滤得到 565.8g 滤液， 通过安捷伦 7890A , 分析检测产品三氟乙基碳酸甲酯含量 72.0718%, 正丁胺含量 1.9156%， 三氟乙醇 18.4679%, 双三氟乙基碳酸酯含量 4.1135%, 碳酸二甲酯 3.4312%。 对得到的滤液进行常压带回流调节精馏回收 残留的三氟乙醇和过量的正丁胺， 收集 102~106°C/100kPa三氟乙基碳酸甲酯 385.4g， 通过安捷伦 7890A分析检测 （RT1.586), 含量为 99.90 Wt.%, 收率 67.5%。 实施例 4 将 297.0g(1.0mol)三光气与 900.0g(9.0mol)三氟乙醇和 32.0g 甲醇 (l .Omol)加入三口烧瓶中搅拌混匀， 70°C下滴加三乙胺 620.0g(6.14mol)， 滴加 结束后保温 8小时后， 取样滤液中三乙胺含量小于 3%; 冷却过滤得到 975.7g 滤液， 通过安捷伦 7890A, 分析检测产品三氟乙基碳酸甲酯含量 15.4051%， 双三氟乙基碳酸酯含 45.3257%， 三乙胺含量 1.6231%， 三氟乙醇 37.3246%， 碳酸二甲酯 0.3215%。 对得到的滤液进行常压带回流调节精馏回收残留的三氟 乙醇和过量的三乙胺， 收集 102~106°C/100kPa三氟乙基碳酸甲酯 132.6g， 通 过安捷伦 7890A分析检测 （RT1.586), 含量为 99.52 Wt.%; 收集 112~116°C /lOOkPa双三氟乙基碳酸酯 384.3g， 通过安捷伦 7890A分析检测 （RT2.525), 含量为 99.95Wt.%， 收率 84.6%。 将 297.0g(1.0mol)三光气与 400.0g(4.0mol)三氟乙醇和 184.0g 乙醇 (4.0mol)加入三口烧瓶中搅拌混匀， 65°C下滴加三丁胺 1128.5g (6.1mol)， 滴 加结束后保温 8 小时后， 取样滤液中三丁胺胺含量小于 3%; 冷却过滤得到 582.5g 滤液， 通过安捷伦 7890A , 分析检测产品三氟乙基碳酸乙酯含量 72.8112%, 双三氟乙基碳酸酯含量 2.9432%， 碳酸二乙酯 2.5613%， 三丁胺含 量 2.4352%， 三氟乙醇 14.1073%， 乙醇 5.1535%。 对得到的滤液进行常压带回 流调节精馏回收残留的三氟乙醇和乙醇， 收集 118~120°C/100kPa三氟乙基碳 酸乙酯 418.3g， 通过安捷伦 7890A分析检测， （RT2.096),含量为 99.67 Wt.%， 收率 80.8%。 对比例 1 将 90.0g(1.0mol)碳酸二甲酯和 600.0g ( 6.0mol) 三氟乙醇加入三口烧瓶 中搅拌混匀， 加入碳酸钾 10.0g， 70°C下保温 10 小时后， 取样， 通过安捷伦 7890A, 分析检测， 三氟乙醇含量 73.6811%， 甲醇 3.7101%， 碳酸二甲酯含量 7.8261%, 三氟乙基碳酸甲酯含量 2.7188%， 双三氟乙基碳酸酯 12.0639%。 对 得到的滤液进行常压带回流调节精馏回收残留的三氟乙醇和过量的甲醇以及 原料碳酸二甲酯， 收集 102~106°C/100kPa三氟乙基碳酸甲酯 16.5g， 通过安捷 伦 7890A分析检测含量为 99.32 Wt.%, 收集 112~116°C/100kPa双三氟乙基碳 酸酯 78.6g， 通过安捷伦 7890A分析检测 （RT2.525) , 含量为 99.58 Wt.%， 收 率 42.08%。 对比例 2 将 90.0g(1.0mol)碳酸二甲酯和 600.0g ( 6.0mol) 三氟乙醇加入三口烧瓶 中搅拌混匀， 加入甲醇钠 10.0g， 70°C下保温 10 小时后， 取样， 通过安捷伦 7890A, 分析检测， 三氟乙醇含量 71.5438%， 甲醇 4.5613%， 碳酸二甲酯含量 6.9532%, 三氟乙基碳酸甲酯含量 3.8244%， 双三氟乙基碳酸酯 13.1173%。 对 得到的滤液进行常压带回流调节精馏回收残留的三氟乙醇和过量的甲醇以及 原料碳酸二甲酯， 收集 102~106°C/100kPa三氟乙基碳酸甲酯 18.2g， 通过安捷 伦 7890A分析检测 (RT1.586 ) , 含量为 99.42 Wt.%, 收集 112~116。C/100kPa 双三氟乙基碳酸酯 83.9g，通过安捷伦 7890A分析检测（RT2.525 ) ,含量为 99.61 Wt.%, 收率 45.18%。 应该理解， 在阅读了本发明的上述讲授内容之后， 本领域技术人员可以 对本发明作各种改动或修改， 这些等价形式同样落于本申请所附权利要求 书所限定的范围。

Claims

1. 一种含三氟甲基直链碳酸酯的制备方法， 其制备歩骤为： 将三氟甲基饱 和一元醇或三氟甲基饱和一元醇与饱和直链一元醇的混合物， 与三光气混合， 在有机胺缚酸剂存在下， 调整温度为 25~80°C， 反应 l~10h， 得到含三氟甲基直 链碳酸酯的混合液， 过滤分离， 对含三氟甲基直链碳酸酯的混合液进行蒸馏提 纯， 得到含三氟甲基直链碳酸酯；
所述三氟甲基饱和一元醇与饱和直链一元醇混合物中， 三氟甲基饱和一元 醇与饱和直链一元醇的摩尔比为 9~1： 1；
所述三氟甲基饱和一元醇或三氟甲基饱与一元醇与饱和直链一元醇的混合 物与三光气的摩尔比为 6~12： 1；所述有机胺缚酸剂与三光气的摩尔比为 6~8： 1； 所述含三氟甲基直链碳酸酯结构式
0
Figure imgf000009_0001
其中， n=0~2， 且 n为整数， 为甲基、 乙基或丙基。
2.根据权利要求 1所述一种三氟甲基直链碳酸酯的制备方法， 其特征在于: 所述三氟甲基饱和一元醇为 2， 2， 2-三氟乙醇和 /或 3， 3， 3-三氟丙醇。
3.根据权利要求 1所述一种三氟甲基直链碳酸酯的制备方法， 其特征在于: 所述饱和直链一元醇选自下述物质中的一种或几种： 甲醇、 乙醇、 丙醇。
4.根据权利要求 1所述一种三氟甲基直链碳酸酯的制备方法， 其特征在于: 所述有机胺缚酸剂选自下述物质中的一种或几种： 三乙胺、 三丁胺、 正丁胺- 二丁胺。
：. 根据权利要求 1至 4任意项所述一种三氟甲基直链碳酸酯的制备方法， 其 特征在于： 所述三氟甲基饱和一元醇或三氟甲基饱和一元醇与饱与直链一元醇 的混合物与三光气的优选摩尔比为 8~12: 1。
6. 根据权利要求 1至 4任意项所述一种三氟甲基直链碳酸酯的制备方法， 其 特征在于： 所述的蒸馏提纯条件为 70~120°C/10~100kPa。
7. 根据权利要求 5所述一种三氟甲基直链碳酸酯的制备方法， 其特征在于: 所述的蒸馏提纯条件为 70~120°C/10~100kPa。
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