WO2013083015A1

WO2013083015A1 - Process for synthesizing pentafluoropropionyl fluoride

Info

Publication number: WO2013083015A1
Application number: PCT/CN2012/085604
Authority: WO
Inventors: 韩国庆; 徐卫国; 盛楠; 陈明炎; 方小青; 肖恒侨; 项文勤
Original assignee: 中化蓝天集团有限公司; 浙江蓝天环保高科技股份有限公司
Priority date: 2011-12-06
Filing date: 2012-11-30
Publication date: 2013-06-13
Also published as: CN103145544A

Abstract

Disclosed is a process for synthesizing pentafluoropropionyl fluoride by using hexafluoropropylene oxide as raw material. In the presence of a catalyst, hexafluoropropylene oxide is isomerized to pentafluoropropionyl fluoride. Said catalyst comprises a main catalyst and a co-catalyst, wherein the main catalyst is organic amine compound, five-membered or six-membered N-containing heterocyclic compound or six-membered condensed ring aryl compound, and the co-catalyst is alkali metal fluoride salt. The mass ratio of the main catalyst and the co-catalyst is 100:1-5:1. The advantages of the process are mild technology, simple operation and high yield of the pentafluoropropionyl fluoride obtained. The pentafluoropropionyl fluoride obtained is suitable for preparing fluoroalkyl vinyl ether, perfluoropropiono peroxide and so on.

Description

说明书五氟丙酰氟的合成方法 Specification for synthesis of pentafluoropropionyl fluoride

技术领域 Technical field

本发明涉及一种五氟丙酰氟的合成方法，尤其是涉及一种以六氟环氧丙烷为原料合成五氟丙酰氟的方法。背景技术 The present invention relates to a process for the synthesis of pentafluoropropionyl fluoride, and more particularly to a process for the synthesis of pentafluoropropionyl fluoride from hexafluoropropylene oxide. Background technique

五氟丙酰氟 (Pentaf luoropropionyl Fluoride) , 分子式： CF₃CF₂C0F； Cas 号： 422-61-7; 分子量 166. 02; 沸点： _28°C ; 常温下是无色气体，呈酸性，易于醇发生酯化反应，遇水生成 HF气体和全氟丙酸。 Pentaf luoropropionyl Fluoride, molecular formula: CF ₃ CF ₂ C0F; Cas number: 422-61-7; molecular weight 166. 02; boiling point: _28 ° C; colorless gas at room temperature, acidic, easy The alcohol undergoes an esterification reaction to form HF gas and perfluoropropionic acid in the presence of water.

五氟丙酰氟作为特殊含氟功能材料的原料和中间体，是非常重要的化合物，如可以制备一系列含氟烷基乙烯基醚，这种化合物是含氟弹性体的改性单体，可以有效地破坏共聚体的结晶度，分子中的 C-0键赋予分子的柔软性，以改善含氟弹性体的某些性能，如：耐低温性能、韧性、耐撕裂性能、与基材的粘结性能等；可以广泛应用于合成含氟弹性体材料。五氟丙酰氟还可以制备全氟丙酰基过氧化物，这种化合物是制备性能优异的高纯级含氟聚合物所必需的一类引发剂，高纯级氟聚合物与普通氟聚合物相比，具有更低的金属等杂质离子析出度，更好的物理、化学稳定性，不会污染所接触的化学物品，广泛用于制造、储存、运输高纯化学品、超纯化学品的容器、管子、泵、阀门等设备的材料。五氟丙酰氟还可以制备全氟酮，全氟酮是一类环境、灭火性能优异的灭火剂，其 0DP=0， GWP=1，灭火性能与哈龙 1211、 1301相当。五氟丙酰氟也可以水解制的五氟丙酸，五氟丙酸可以制备五氟丙酸甲酯或乙酯，可以制备五氟丙酸酐，这些含氟化合物是合成含氟医药和农药的原料。 Pentafluoropropionyl fluoride is a very important compound as a raw material and intermediate for special fluorine-containing functional materials, such as a series of fluorine-containing alkyl vinyl ethers, which are modified monomers of fluoroelastomers. It can effectively destroy the crystallinity of the copolymer. The C-0 bond in the molecule imparts flexibility to the molecule to improve certain properties of the fluoroelastomer, such as: low temperature resistance, toughness, tear resistance, and substrate. Bonding properties, etc.; can be widely used in the synthesis of fluoroelastomer materials. Pentafluoropropionyl fluoride can also be used to prepare perfluoropropionyl peroxide, which is a type of initiator necessary for the preparation of high purity grade fluoropolymers. High purity grade fluoropolymers and common fluoropolymers. Compared with the lower metal and other impurity ion precipitation, better physical and chemical stability, will not pollute the chemicals in contact, widely used in the manufacture, storage, transportation of high-purity chemicals, ultra-pure chemicals Materials for containers, pipes, pumps, valves, etc. Pentafluoropropionyl fluoride can also be used to prepare perfluoroketone. Perfluoroketone is a kind of fire extinguishing agent with excellent environment and fire extinguishing performance. Its 0DP=0, GWP=1, and the fire extinguishing performance is equivalent to that of halon 1211 and 1301. Pentafluoropropionyl fluoride can also be hydrolyzed by pentafluoropropionic acid, pentafluoropropionic acid can be used to prepare methyl or ethyl pentafluoropropionate, and pentafluoropropionic anhydride can be prepared. These fluorine-containing compounds are synthetic fluorine-containing medicines and pesticides. raw material.

现有技术中五氟丙酰氟的制备方法主要有三种原料路线： In the prior art, the preparation method of pentafluoropropionyl fluoride mainly has three raw material routes:

( 1 ) 六氟环氧丙烷为原料 (1) Hexafluoropropylene oxide as raw material

美国专利 US4729856描述了采用封闭的铂管和 Carious管作反应器，在一定反应温度下，以 DMF或醚类等做溶剂，在原料自身压力或加压下，用碱性催化剂 KHF₂、 N¾C0₃、二甲基胺、六亚甲基四胺做催化剂，六氟环氧丙烷异构化成全氟丙酰氟。此反应产品选择性较低，反应器设计复杂，反应压力较高，反应时间长，不利于工业化生产。 U.S. Patent No. 4,729,856 describes the use of a closed platinum tube and a Carious tube as a reactor. At a certain reaction temperature, a solvent such as DMF or ether is used as a solvent under the pressure or pressure of the raw material itself. The agent KHF ₂ , N 3⁄4C0 ₃ , dimethylamine, hexamethylenetetramine is used as a catalyst, and hexafluoropropylene oxide is isomerized to perfluoropropionyl fluoride. The reaction product has low selectivity, complicated reactor design, high reaction pressure and long reaction time, which is not conducive to industrial production.

美国专利 US5684193描述了用衬有 FEP的管式反应器或压力釜反应器，以氟化氢胺络合物做催化剂，在一定温度下将六氟环氧丙烷异构化成全氟丙酰氟，专利推荐使用管式鼓泡反应器，反应的原料转化率和产品选择性较理想，但该技术反应器的设计较复杂，催化剂的制备也较复杂，会用到腐蚀性较强的 HF，不利于工业化生产。 U.S. Patent No. 5,684,193 describes the isomerization of hexafluoropropylene oxide to perfluoropropionyl fluoride at a certain temperature using a tubular reactor or autoclave reactor lined with FEP using a hydrogen fluoride amine complex as a catalyst. The use of tubular bubbling reactors, the conversion of raw materials and product selectivity of the reaction is ideal, but the design of the reactor is complicated, the preparation of the catalyst is complicated, and the corrosive HF is used, which is not conducive to industrialization. produce.

日本专利 JP58038231描述了用 KF 或 CsF做催化剂，以六氟环氧丙烷做原料异构化全氟丙酰氟，反应温度 0°C〜200°C，反应压力 l〜10atm下，以活性炭为载体的 KF 或 CsF催化剂，产品全氟丙酰氟收率达到 71%，原料以气相形式进入反应器。 Japanese Patent JP58038231 describes the use of KF or CsF as a catalyst, hexafluoropropylene oxide as a raw material for isomerization of perfluoropropionyl fluoride, reaction temperature 0 ° C ~ 200 ° C, reaction pressure l ~ 10 atm, with activated carbon as a carrier The KF or CsF catalyst, the product yield of perfluoropropionyl fluoride reached 71%, and the feedstock entered the reactor in the form of a gas phase.

日本专利 JP4134046描述了用三乙胺、二甲基吡啶、甲基喹啉等胺类作溶剂，用六氟环氧丙烷做原料异构化全氟丙酰氟，在 40°C反应温度下，反应 4小时，产品全氟丙酰氟收率 61. 9%，该技术产品收率不高，存在原料六氟环氧丙烷和产品五氟丙酰氟分离困难的不利因素。 Japanese Patent No. 4134046 describes the use of an amine such as triethylamine, lutidine or methylquinoline as a solvent, and isomerization of perfluoropropionyl fluoride with hexafluoropropylene oxide as a raw material at a reaction temperature of 40 ° C. After 4 hours of reaction, the product yield of perfluoropropionyl fluoride was 61.9%. The yield of the technical product was not high, and there was a disadvantage that the separation of the raw material hexafluoropropylene oxide and the product pentafluoropropionyl fluoride was difficult.

( 2) 全氟甲基乙烯基醚为原料 (2) Perfluoromethyl vinyl ether as raw material

Zompatori禾口 V. Tortelli在 Journal of Fluorine Chemistry. 125 ( 2) 199-204, 2004 上报道了以全氟甲基乙烯基醚为原料异构化制备五氟丙酰氟，该路线存在原料昂贵，反应产物选择性差的缺点，不利于规模化制备五氟丙酰氟。 Zompatori and V. Tortelli reported the preparation of pentafluoropropionyl fluoride by isomerization of perfluoromethyl vinyl ether using the perfluoromethyl vinyl ether as a raw material in Journal of Fluorine Chemistry. 125 (2) 199-204, 2004. The disadvantage of poor selectivity of the reaction product is not conducive to the large-scale preparation of pentafluoropropionyl fluoride.

( 3) 四氟乙烯为原料 (3) Tetrafluoroethylene as raw material

美国专利 US5259938 描述了以四氟乙烯为原料和氟光气调聚合成五氟丙酰氟，产品收率达到 68%，该技术路线同样存在原料不易得到，产品收率低，不利于规模化制备五氟丙酰氟的缺点。 U.S. Patent No. 5,259,938 describes the use of tetrafluoroethylene as a raw material and fluorine photopolymerization to form pentafluoropropionyl fluoride, and the product yield reaches 68%. This technical route also has difficulty in obtaining raw materials, and the product yield is low, which is not conducive to large-scale preparation. Disadvantages of pentafluoropropionyl fluoride.

上述五氟丙酰氟合成方法中均存在产品收率低、工业化生产困难的缺点，需要寻找一种高产率的五氟丙酰氟合成方法。发明内容 In the above-mentioned pentafluoropropionyl fluoride synthesis method, there are disadvantages of low product yield and difficulty in industrial production, and it is necessary to find a high-yield synthesis method of pentafluoropropionyl fluoride. Summary of the invention

本发明的目的在于提供一种五氟丙酰氟的制备方法，具有制备工艺温和、操作简单、合成的五氟丙酰氟收率高等优点。 The object of the present invention is to provide a preparation method of pentafluoropropionyl fluoride, which has a mild preparation process and a process It has the advantages of simple, synthetic pentafluoropropionyl fluoride yield.

为达到发明目的本发明采用的技术方案是： The technical solution adopted by the present invention for the purpose of the invention is:

以六氟环氧丙烷为原料，在催化剂作用下异构化合成五氟丙酰氟，该技术路线用反应方程式表示如下：

The hexafluoropropylene oxide is used as a raw material to synthesize pentafluoropropionyl fluoride under the action of a catalyst. The technical route is expressed by the following reaction equation:

F CF ^ 本技术所用原料六氟环氧丙烷，主要是由六氟丙烯氧化法制备。 F CF ^ The raw material hexafluoropropylene oxide used in the present technology is mainly prepared by the hexafluoropropylene oxidation method.

本发明所述的催化剂包括主催化剂和助催化剂，主催化剂为有机胺类化合物、五元或六元含氮类杂环化合物或六元稠环类芳基化合物，助催化剂为提供 F—阴离子的碱金属氟盐。 The catalyst of the present invention comprises a main catalyst and an auxiliary catalyst, and the main catalyst is an organic amine compound, a five- or six-membered nitrogen-containing heterocyclic compound or a six-membered fused-ring aryl compound, and the cocatalyst is provided with an F-anion. Alkali metal fluoride salt.

碱性的有机胺类催化剂位阻较小，可以很好的开环效应。稠环类化合物，含氮杂环类化合物， C上的电子云密度变得很大，使 C带一定量的负电荷，基于相同电荷之间相互排斥作用，就导致其有推电子作用，进攻原料六氟环氧丙烷碳氧键端，使环氧键断裂，形成 C=0羰基。同时，由于氧的电负性较大，并在大 C 基团强拉电子作用下， β位子的 C原子具有得电子特性，碱性无机氟化物的氟化钠、氟化钾、氟化铯等物质提供 F—阴离子，形成 CF3CF2C0F2—负离子化合物。最后， a位的 F—离子就转移至钠、钾、铯等无机正离子基团上，形成 CF3CF2C0F 和无机氟化物。 Alkaline organic amine catalysts have low steric hindrance and good ring opening effect. A fused ring compound, a nitrogen-containing heterocyclic compound, has a large electron cloud density on C, which causes C to carry a certain amount of negative charge, and based on the mutual repulsion between the same charges, it causes a push-electron effect, attacking The raw material hexafluoropropylene oxide carbon-oxygen bond ends, and the epoxy bond is broken to form a C=0 carbonyl group. At the same time, due to the high electronegativity of oxygen and the strong electron pull of the large C group, the C atom of the β position has an electronic property, and the sodium fluoride, potassium fluoride, and cesium fluoride of the basic inorganic fluoride. The substance provides an F-anion to form a CF3CF2C0F2- anion compound. Finally, the F-ion at the a site is transferred to an inorganic cation group such as sodium, potassium or cesium to form CF3CF2C0F and inorganic fluoride.

有机胺类化合物优选自三乙胺、乙二胺、二丙胺、三丙胺、二甲基甲酰胺或四甲基乙二胺中的一种或两种以上组合。六元稠环类芳基化合物优选自喹啉、异喹啉、烷基喹啉中的一种或两种以上组合。所述烷基喹啉优选为甲基喹啉。 The organic amine compound is preferably one or a combination of two or more of triethylamine, ethylenediamine, dipropylamine, tripropylamine, dimethylformamide or tetramethylethylenediamine. The six-membered fused-ring aryl compound is preferably one or a combination of two or more of quinoline, isoquinoline, and alkylquinoline. The alkylquinoline is preferably a methylquinoline.

五元或六元含氮类杂环化合物优选自哌啶、烷基哌啶、吡啶、四氢吡啶、吗啉、烷基吗啉或烷基吡咯烷酮中的一种或两种以上组合。所述烷基哌啶优选为甲基哌啶，烷基吗啉优选为甲基吗啉，烷基吡咯烷酮优选为 N-甲基吡咯烷酮。 The five- or six-membered nitrogen-containing heterocyclic compound is preferably one or a combination of two or more selected from the group consisting of piperidine, alkyl piperidine, pyridine, tetrahydropyridine, morpholine, alkylmorpholine or alkylpyrrolidone. The alkyl piperidine is preferably methyl piperidine, the alkylmorpholine is preferably methylmorpholine, and the alkylpyrrolidone is preferably N-methylpyrrolidone.

本发明所用助催化剂为碱金属氟盐，优选为氟化钠、氟化钾或氟化铯，主催化剂和助催化剂的质量配比为 100： 1〜5 1，较合适的配比是 30： 1〜10： 1。 The cocatalyst used in the present invention is an alkali metal fluoride salt, preferably sodium fluoride, potassium fluoride or cesium fluoride. The mass ratio of the main catalyst to the cocatalyst is 100:1 to 5 1, and a suitable ratio is 30: 1~10: 1.

反应的温度对反应速度影响较大，我们希望反应较快的进行，这就需要提高反应温度，同时该反应是放热的，为了使反应温度在可以控制范围之内，合适反应温度优选为 20°C〜150°C，进一步较优为 70°C〜100°C。 The reaction temperature has a great influence on the reaction rate. We hope that the reaction proceeds faster. This requires an increase in the reaction temperature. At the same time, the reaction is exothermic. In order to make the reaction temperature within the control range, it is appropriate to The temperature should preferably be from 20 ° C to 150 ° C, and more preferably from 70 ° C to 100 ° C.

本发明反应是等摩尔反应，反应压力对反应速度没有影响，较高的压力可以增加反应物的停留时间，可以使反应进行的更加完全，但太高压力对设备和反应 ***要求较高，不适合操作。因此，合适反应压力优选为常压至 l. OMpa, 进一步较优为 0. 2Mpa-0. 6Mpa 。 The reaction of the invention is an equimolar reaction, the reaction pressure has no effect on the reaction rate, the higher pressure can increase the residence time of the reactant, and the reaction can be carried out more completely, but the too high pressure requires high equipment and reaction system, Suitable for operation. 5Mpa。 Thus, the appropriate reaction pressure is preferably from atmospheric pressure to l. OMpa, further preferably 0. 2Mpa-0. 6Mpa.

本发明所述反应既可以间歇操作，也可以连续进行，优选连续反应。本发明反应可以在带压力的釜式反应器中进行，也可以在带压力的管式反应器中进行。较优选得反应器是带压力的管式反应器，这样便于连续反应，但这样要求精确的控制***。 The reaction of the present invention can be carried out either batchwise or continuously, preferably continuously. The reaction of the present invention can be carried out in a pressurized tank reactor or in a pressurized tubular reactor. More preferably, the reactor is a pressurized tubular reactor which facilitates a continuous reaction, but this requires an accurate control system.

本发明使用的反应器材质需要有较好的耐腐蚀性，适应原料、催化剂体系和产品五氟丙酰氟三者的共同作用，一般选择耐腐蚀性较好的含氟树脂，如聚四氟乙烯、聚六氟丙烯、聚偏氟乙烯等高性能材料。为了增加反应进行程度，提高产品收率，应当提高反应压力，这就需要将反应器设计成一定的耐压要求，基于上面两方面的技术要求，可以将反应器设计成衬含氟树脂的钢制压力容器，这样既可以耐腐蚀，又可以耐压力。具体实施方式 The reactor material used in the invention needs to have good corrosion resistance, and is suitable for the joint action of the raw materials, the catalyst system and the product pentafluoropropionyl fluoride, and generally selects a fluorine-containing resin with good corrosion resistance, such as polytetrafluoroethylene. High performance materials such as ethylene, polyhexafluoropropylene, and polyvinylidene fluoride. In order to increase the degree of reaction and increase the yield of the product, the reaction pressure should be increased. This requires that the reactor be designed to have a certain withstand pressure requirement. Based on the above two technical requirements, the reactor can be designed as a steel with fluorine-containing resin. Pressure vessel, which is both corrosion resistant and pressure resistant. detailed description

下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本领域技术人员应该认识到，本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。实施例 1 The invention is further illustrated by the following specific examples, but the invention is not limited to these specific embodiments. Those skilled in the art will recognize that the present invention encompasses all alternatives, modifications, and equivalents that may be included within the scope of the claims. Example 1

在体积为 0. 5L, 内衬聚四氟乙烯，带搅拌器的压力反应釜中，加入 150g乙二胺和 10_gNaF，然后合上反应釜，开搅拌反应，搅拌速度在 300转 /分钟，开加热升高反应釜温度，温度控制在 90 °C，待温度达到后将 200g原料六氟环氧丙烷从液相管分批通入反应釜内，反应压力维持在 0. 6MPa，从气相管将反应物料放出，冷凝收集得到粗品物料 175g，气相分析粗品含量，其中 CF₃CF₂C0F含量为 92%, 产品收率 80. 5%。实施例 2 In a pressure reactor having a volume of 0. 5L, lined with polytetrafluoroethylene, and a stirrer, 150 g of ethylenediamine and 10 _{g of} NaF were added, and then the reaction vessel was closed, and the reaction was stirred, and the stirring speed was 300 rpm. 6MPa, from the gas phase, the reaction pressure is maintained at 0. 6MPa, from the gas phase, the reaction pressure is maintained at 0. 6MPa, from the gas phase, the gas pressure is maintained at 0. 6MPa, from the gas phase The 5%. The yield of the product is 80.5%. The yield of the CF ₃ CF ₂ C0F is 92%, and the product yield is 80.5%. Example 2

在体积为 0. 5L，内衬聚四氟乙烯，带搅拌器的压力反应釜中，加入 180g喹啉和 10_gKF，然后合上反应釜，开搅拌反应，搅拌速度在 300转 /分钟，开反应釜加热升高反应釜温度，温度控制在 100 °C，待温度达到后将 200g原料六氟环氧丙烷从液相管分批通入反应釜内，反应压力维持在 0. 65MPa，从气相管将反应物料放出，冷凝收集得到粗品物料 186g，气相分析粗品含量，其中 CF₃CF₂C0F含量为 91%，产品收率 84. 6%。实施例 3 In a pressure reactor having a volume of 0.5 L, lined with polytetrafluoroethylene and a stirrer, 180 g of quinoline and 10 _{g of} KF were added, and then the reaction vessel was closed, and the reaction was stirred, and the stirring speed was 300 rpm. The singularity of the reactor is maintained at 0. 65MPa, from the reaction temperature is maintained at 0. 65MPa, from the reaction temperature is maintained at 0. 65MPa, from the reaction vessel is heated to a temperature of 100 ° C, after the temperature is reached, 200g of raw material hexafluoropropylene oxide from the liquid phase tube into the reactor, the reaction pressure is maintained at 0. 65MPa, from 6%。 The gas phase tube of the reaction material is discharged, condensed to obtain a crude material 186g, the gas phase analysis of the crude content, wherein the CF ₃ CF ₂ C0F content is 91%, the product yield of 84.6%. Example 3

在体积为 0. 5L, 内衬聚四氟乙烯，带搅拌器的压力反应釜中，加入 160g哌啶和 6gCsF，然后合上反应釜，开搅拌反应，搅拌速度在 300转 /分钟，开反应釜加热升高反应釜温度，温度控制在 90 °C，待温度达到后将 210g原料六氟环氧丙烷从液相管分批通入反应釜内，反应压力维持在 0. 5MPa左右，从气相管将反应物料放出，冷凝收集得到粗品物料 181 g，气相分析粗品含量，其中 CF₃CF₂C0F含量为 93. 5%，产品收率 81%。实施例 4 In a pressure reactor having a volume of 0. 5L, lined with polytetrafluoroethylene and a stirrer, 160 g of piperidine and 6 g of CsF were added, and then the reaction vessel was closed, and the reaction was stirred, stirring at 300 rpm, and the reaction was started. 5 左右左右,左右之间。 From the gas phase, the gas pressure is maintained at 0. 5MPa or so, from the gas phase. The product was discharged from the tube, and condensed to obtain a crude material of 181 g, which was analyzed by gas phase analysis, wherein the CF ₃ CF ₂ C0F content was 93.5%, and the product yield was 81%. Example 4

在体积为 1L，内衬聚全氟乙丙烯（简称 "F46")，带搅拌器的压力反应釜中，加入 300gN-甲基吡咯烷酮和 20gKF混合催化剂，然后合上反应釜，开搅拌，搅拌速度在 250转 /分钟，开加热升高反应釜温度，温度控制在 95 °C，待温度达到后将 420g原料六氟环氧丙烷从液相管分批通入反应釜内，反应压力维持在 0. 6MPa左右，从气相管将反应物料放出，冷凝收集得到粗品物料 365g，其中 CF₃CF₂C0F含量为 90. 5%, 产品收率 78. 6%。实施例 5 In a pressure reactor with a volume of 1 L, lined with polyfluoroethylene propylene ("F46"), with a stirrer, add 300g of N-methylpyrrolidone and 20g of KF mixed catalyst, then close the reaction vessel, stir, stir speed At 250 rpm, the temperature of the reactor was raised by heating, and the temperature was controlled at 95 ° C. After the temperature was reached, 420 g of the raw material hexafluoropropylene oxide was introduced into the reactor from the liquid phase tube in batches, and the reaction pressure was maintained at 0. The 5%, the product yield is 78.6%. The product is discharged from the gas phase tube, and the condensed material is condensed to obtain a crude material of 365 g, wherein the CF ₃ CF ₂ C0F content is 90.5%, and the product yield is 78.6%. Example 5

在体积为 1L，内衬 F46，带搅拌器的压力反应釜中，加入 320g四甲基乙二胺和 20gNaF混合催化剂，然后合上反应釜，开搅拌，搅拌速度在 250转 /分钟，开加热升高反应釜温度，温度控制在 100 °C，待温度达到后将 400g原料六氟环氧丙烷从液相管分批通入反应釜内，反应压力维持在 0. 6MPa左右，从气相管将反应物料放出，冷凝收集得到粗品物料 360g，其中 CF₃CF₂C0F含量为 89. 7%，产品收率 80. 7%。实施例 6 In a pressure reactor with a volume of 1 L, lined with F46, and a stirrer, add 320 g of tetramethylethylenediamine and 20 g of NaF mixed catalyst, then close the reaction vessel, stir, stir at 250 rpm, and heat on. 5MPa左右,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The reaction mass from the gas discharge pipe, the condensate was collected to give 360 g of crude material, wherein the CF ₃ CF ₂ C0F content of 89.7%, 80.7% yield of product. Example 6

在带有恒温加热套，内衬聚四氟乙烯，直径是 32mm，高度是 lm管式反应器中，加入 100g甲基喹啉和 5gNaF，然后合上反应器，开加热套升高反应温度，当反应温度到 70°C时停止升温，保持这一反应温度。然后将原料六氟环氧丙烷以 20ml/min匀速通入反应器底部，随后反应产物从反应器顶部进入到产品收集器中，反应压力维持在 0. 3MPa，通过气相色谱来检测反应效果，原料转化率 96%，产品五氟丙酰氟含量 92%以上，分析数据如下表。 In a reactor with a constant temperature heating jacket, lined with polytetrafluoroethylene, 32 mm in diameter and height is lm tube reactor, add 100 g of methylquinoline and 5 g of NaF, then close the reactor, and open the heating jacket to raise the reaction temperature. When the reaction temperature reached 70 ° C, the temperature was stopped and the reaction temperature was maintained. The raw material hexafluoropropylene oxide was introduced into the bottom of the reactor at a constant rate of 20 ml/min, and then the reaction product was passed from the top of the reactor to the product collector. The reaction pressure was maintained at 0.3 MPa, and the reaction was detected by gas chromatography. The conversion rate was 96%, and the product pentafluoropropionyl fluoride content was over 92%. The analytical data are shown in the following table.

实施例 7

Example 7

在带有恒温加热套，内衬聚四氟乙烯，直径是 32mm，高度是 lm的管式反应器中，加入 110g吡啶和 8gKF，然后合上反应器，开加热套升高反应温度，当反应温度升到 80°C，恒定反应温度，然后将原料六氟环氧丙烷以 30ml/min 匀速通入反应器底部，反应产物从反应器顶部进入到产品收集器中，反应压力维持在 0. 2MPa，通过气相色谱来检测反应效果，分析数据如下表；原料转化率接近 92%，产品五氟丙酰氟含量 90%以上。 In a tubular reactor with a constant temperature heating jacket, PTFE, 32 mm diameter and lm height, add 110 g pyridine and 8 g KF, then close the reactor, open the heating jacket to raise the reaction temperature, when the reaction 2MPa, The reaction pressure is maintained at 0. 2MPa. The pressure is maintained at 0. 2MPa. The pressure is maintained at 0. 2MPa The reaction effect was detected by gas chromatography, and the analysis data was as follows; the conversion rate of the raw material was close to 92%, and the fluorine content of the product pentafluoropropionyl fluoride was over 90%.

名称 a 里 Name a

6. 7% 6. 7%

CF3CFCF2 CF3CF2COF 90. 1% CF3CFCF2 CF3CF2COF 90. 1%

CF3CF=CF2 0. 8% CF3CF=CF2 0. 8%

CF3CF2CF20CFCOF 1. 3% CF3CF2CF20CFCOF 1. 3%

CF₃ CF ₃

其它 1. 0% 实施例 8 Other 1. 0% Example 8

在带有恒温加热套，内衬聚四氟乙烯，直径是 32mm，高度是 lm的管式反应器中，加入 100g甲基吗啉和 6gNaF，然后合上反应器，开加热套升高反应器温度，待反应温度到 70 °C时恒定该温度，然后将原料六氟环氧丙烷以 25ml/min 匀速通入反应器底部，反应产物从反应器顶部进入到产品收集器中，反应压力维持在 0. 2MPa，通过气相色谱来检测反应效果，显示反应原料几乎没有了，转化率大于 99%，产品五氟丙酰氟含量 94%以上。 In a tubular reactor with a constant temperature heating jacket, lined with polytetrafluoroethylene, 32 mm in diameter and lm in height, add 100 g of methylmorpholine and 6 g of NaF, then close the reactor and open the heating jacket to raise the reactor. Temperature, when the reaction temperature is 70 ° C, the temperature is constant, then the raw material hexafluoropropylene oxide is introduced into the bottom of the reactor at a constant rate of 25 ml / min, and the reaction product enters the product collector from the top of the reactor, and the reaction pressure is maintained at 0. 2MPa, the reaction effect was detected by gas chromatography, showing that there was almost no reaction raw material, the conversion rate was more than 99%, and the product pentafluoropropionyl fluoride content was 94% or more.

实施例 9

Example 9

在带有恒温加热套，内衬聚四氟乙烯，直径是 32mm，高度是 lm的管式反应器中，加入 90g三丙胺和 4gCsF，然后合上反应器，开加热套升高反应器温度，待反应温度在 85 °C后恒温，然后将原料六氟环氧丙烷以 20ml/min匀速通入反应器底部，反应产物从反应器顶部进入到产品收集器中，反应压力维持在 0. 3MPa,通过气相色谱来检测反应收集产物，分析数据显示反应原料含量较低，转化率大于 99%，产品五氟丙酰氟含量 93%以上。 l≡3 In a tubular reactor with a constant temperature heating jacket, PTFE, 32 mm diameter and lm height, add 90 g of tripropylamine and 4 g of CsF, then close the reactor and open the heating jacket to raise the reactor temperature. 3MPa,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The reaction collected product was detected by gas chromatography, and the analysis data showed that the content of the reaction raw material was low, the conversion rate was more than 99%, and the product pentafluoropropionyl fluoride content was 93% or more. L≡3

名称 a 里 Name a

0. 3% 0. 3%

CF3CFCF2 CF3CFCF2

CF3CF2COF 93. 3% CF3CF2COF 93. 3%

CF3CF=CF2 1. 0% CF3CF=CF2 1. 0%

CF3CF2CF20CFCOF 1. 9% CF3CF2CF20CFCOF 1. 9%

CF₃ CF ₃

其它 3. 5% 实施例 10 Other 3. 5% Example 10

在带有恒温加热套，内衬聚四氟乙烯，直径是 32mm，高度是 lm的管式反应器中，加入 105g甲基哌啶和 6gKF，然后合上反应器，开加热套升高反应器温度，待反应温度在 85 °C后恒温，然后将原料六氟环氧丙烷以 30ml/min匀速通入反应器底部，反应产物从反应器顶部进入到产品收集器中，反应压力维持在 0. 3MPa,通过气相色谱来检测反应收集产物，分析数据显示反应原料含量较低，转化率大于 99%，产品五氟丙酰氟含量 92%以上。 In a tubular reactor with a constant temperature heating jacket, lined with polytetrafluoroethylene, 32 mm in diameter and lm in height, add 105 g of methylpiperidine and 6 g of KF, then close the reactor and open the heating jacket to raise the reactor. Temperature, the reaction temperature was kept at a temperature of 85 ° C, then the raw material hexafluoropropylene oxide was introduced into the bottom of the reactor at a constant rate of 30 ml / min, and the reaction product entered the product collector from the top of the reactor, and the reaction pressure was maintained at 0. 3MPa, the product collected by the reaction was detected by gas chromatography. The analysis data showed that the content of the reaction raw material was low, the conversion rate was more than 99%, and the content of pentafluoropropionyl fluoride was over 92%.

|≡3 |≡3

名称 a 里 Name a

0. 8% 0. 8%

CF3CFCF2 CF3CFCF2

CF3CF2COF 92. 4% CF3CF2COF 92. 4%

CF3CF=CF2 1. 0% CF3CF=CF2 1. 0%

CF3CF2CF20CFCOF 2. 2% CF3CF2CF20CFCOF 2. 2%

CF₃ CF ₃

其它 3. 6% Other 3. 6%

Claims

权利要求书 Claim

1. 一种以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于，在催化剂作用下六氟环氧丙烷发生异构化反应生成五氟丙酰氟，所述催化剂包括主催化剂和助催化剂，其中： A method for synthesizing pentafluoropropionyl fluoride using hexafluoropropylene oxide as a raw material, characterized in that hexafluoropropylene oxide is isomerized to form pentafluoropropionyl fluoride under the action of a catalyst, and the catalyst comprises a main catalyst and a cocatalyst, wherein:

主催化剂为有机胺类化合物、五元或六元含氮类杂环化合物或六元稠环类芳基化合物； The main catalyst is an organic amine compound, a five- or six-membered nitrogen-containing heterocyclic compound or a six-membered fused-ring aryl compound;

助催化剂为碱金属氟盐； The cocatalyst is an alkali metal fluoride salt;

主催化剂和助催化剂的质量配比为 100： 1〜5： 1。 The mass ratio of the main catalyst to the cocatalyst is 100: 1 to 5: 1.

2. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述有机胺类化合物选自三乙胺、乙二胺、二丙胺、三丙胺、二甲基甲酰胺或四甲基乙二胺中的一种或两种以上组合。 2. The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the organic amine compound is selected from the group consisting of triethylamine, ethylenediamine, dipropylamine, and tripropylamine. One or a combination of two or more of dimethylformamide or tetramethylethylenediamine.

3. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述六元稠环类芳基化合物选自喹啉、异喹啉、烷基喹啉中的一种或两种以上组合。 The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the six-membered fused ring-based aryl compound is selected from the group consisting of quinoline, isoquinoline, and alkyl group. One or a combination of two or more of quinolines.

4. 按照权利要求 3所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述烷基喹啉为甲基喹啉。 The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 3, wherein the alkylquinoline is methylquinoline.

5. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述五元或六元含氮类杂环化合物选自哌啶、烷基哌啶、吡啶、四氢吡啶、吗啉、烷基吗啉或烷基吡咯烷酮中的一种或两种以上组合。 The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the five- or six-membered nitrogen-containing heterocyclic compound is selected from the group consisting of piperidine and alkyl piperazine. One or a combination of two or more of pyridine, pyridine, tetrahydropyridine, morpholine, alkylmorpholine or alkylpyrrolidone.

6. 按照权利要求 5所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述烷基哌啶为甲基哌啶，烷基吗啉为甲基吗啉，烷基吡咯烷酮为 N-甲基吡咯烷酮。 The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 5, wherein the alkyl piperidine is methyl piperidine, and the alkylmorpholine is methylmorpholine. , alkyl pyrrolidone is N-methylpyrrolidone.

7. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述碱金属氟盐为氟化钠、氟化钾或氟化铯。 The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the alkali metal fluoride salt is sodium fluoride, potassium fluoride or cesium fluoride.

8. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述六氟环氧丙烷与催化剂的质量配比为 1： 1〜100： 1。 The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the mass ratio of the hexafluoropropylene oxide to the catalyst is 1: 1 to 100: 1 .

9. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于所述主催化剂和助催化剂的配比为 30： 1〜10： 1。 9. The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the ratio of the main catalyst to the cocatalyst is from 30:1 to 10:1.

10. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于反应温度为 20°C〜150°C，反应压力为常压至 1. OMpao 10. The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the reaction temperature is from 20 ° C to 150 ° C, and the reaction pressure is from atmospheric pressure to 1. OMpao

11. 按照权利要求 8所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于反应温度为 70°C〜100°C，反应压力为 0. 2Mpa〜0. 6Mpa。 2Mpa〜0. 6Mpa. The reaction temperature is 0. 2Mpa~0. 6Mpa. The method is as follows: The reaction temperature is 0. 2Mpa~0. 6Mpa .

12. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于反应器为带压力的釜式反应器或管式反应器，内衬含氟树脂，所述含氟树脂为聚四氟乙烯、聚六氟丙烯或聚偏氟乙烯。 12. The method for synthesizing pentafluoropropionyl fluoride from hexafluoropropylene oxide according to claim 1, wherein the reactor is a pressurized tank reactor or a tubular reactor, and is lined with a fluorine resin. The fluorine-containing resin is polytetrafluoroethylene, polyhexafluoropropylene or polyvinylidene fluoride.

13. 按照权利要求 1所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于反应连续进行，反应压力为 0. lMpa〜0. 5Mpa，反应温度为 70°C〜 90°C。 The reaction temperature is 70 ° C, the reaction temperature is 0. lMpa~0. 5Mpa, the reaction temperature is 70 ° C, the reaction is carried out continuously, the reaction pressure is 0. lMpa~0. 5Mpa, the reaction temperature is 70 ° C ~ 90 ° C.

14. 按照权利要求 13 所述的以六氟环氧丙烷为原料合成五氟丙酰氟的方法，其特征在于反应在带压力的管式反应器中进行，所述带压力的管式反应器内衬含氟树脂，所述含氟树脂为聚四氟乙烯、聚六氟丙烯或聚偏氟乙烯。 14. Process for the synthesis of pentafluoropropionyl fluoride starting from hexafluoropropylene oxide according to claim 13, wherein the reaction is carried out in a pressurized tubular reactor, said pressurized tubular reactor The fluorine-containing resin is lined, and the fluorine-containing resin is polytetrafluoroethylene, polyhexafluoropropylene or polyvinylidene fluoride.