WO2013083015A1 - Procédé pour la synthèse de fluorure de pentafluoropropionyle - Google Patents

Procédé pour la synthèse de fluorure de pentafluoropropionyle Download PDF

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Publication number
WO2013083015A1
WO2013083015A1 PCT/CN2012/085604 CN2012085604W WO2013083015A1 WO 2013083015 A1 WO2013083015 A1 WO 2013083015A1 CN 2012085604 W CN2012085604 W CN 2012085604W WO 2013083015 A1 WO2013083015 A1 WO 2013083015A1
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WO
WIPO (PCT)
Prior art keywords
fluoride
hexafluoropropylene oxide
pentafluoropropionyl
synthesizing
reaction
Prior art date
Application number
PCT/CN2012/085604
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English (en)
Chinese (zh)
Inventor
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
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Application filed by 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 filed Critical 中化蓝天集团有限公司
Publication of WO2013083015A1 publication Critical patent/WO2013083015A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides

Definitions

  • 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
  • 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.
  • 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.
  • 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.
  • the preparation method of pentafluoropropionyl fluoride mainly has three raw material routes:
  • U.S. Patent No. 4,729,856 describes the use of a closed platinum tube and a Carious tube as a reactor.
  • a solvent such as DMF or ether is used as a solvent under the pressure or pressure of the raw material itself.
  • the reaction product has low selectivity, complicated reactor design, high reaction pressure and long reaction time, which is not conducive to industrial production.
  • 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.
  • 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
  • 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.
  • an amine such as triethylamine, lutidine or methylquinoline
  • 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.
  • 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.
  • 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:
  • the raw material hexafluoropropylene oxide used in the present technology is mainly prepared by the hexafluoropropylene oxidation method.
  • 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 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.
  • Alkaline organic amine catalysts have low steric hindrance and good ring opening effect.
  • the C atom of the ⁇ 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.
  • 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.
  • 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.
  • 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
  • the alkylpyrrolidone is preferably N-methylpyrrolidone.
  • 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.
  • 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.
  • 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 ⁇
  • the appropriate reaction pressure is preferably from atmospheric pressure to l. OMpa, further preferably 0. 2Mpa-0. 6Mpa.
  • 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.
  • 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.
  • a fluorine-containing resin with good corrosion resistance such as polytetrafluoroethylene.
  • High performance materials such as ethylene, polyhexafluoropropylene, and polyvinylidene fluoride.
  • 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
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé pour la synthèse de fluorure de pentafluoropropionyle à l'aide d'oxyde d'hexafluoropropylène utilisé comme matière première. En présence d'un catalyseur, l'oxyde d'hexafluoropropylène est isomérisé en fluorure de pentafluoropropionyle. Ledit catalyseur comprend un catalyseur principal et un cocatalyseur, le catalyseur principal étant un composé amine organique, un composé hétérocyclique azoté à cinq ou six chaînons ou un composé arylique cyclique condensé à six chaînons et le cocatalyseur étant un sel fluorure de métal alcalin. Le rapport massique du catalyseur principal au cocatalyseur est de 100:1-5:1. Les avantages du procédé sont une technologie douce, une mise en œuvre simple et un rendement de production du fluorure de pentafluoropropionyle élevé. Le fluorure de pentafluoropropionyle obtenu est approprié pour la préparation d'éther de fluoroalkyle et de vinyle, de peroxyde de perfluoropropionyle et ainsi de suite.
PCT/CN2012/085604 2011-12-06 2012-11-30 Procédé pour la synthèse de fluorure de pentafluoropropionyle WO2013083015A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110400059.6 2011-12-06
CN2011104000596A CN103145544A (zh) 2011-12-06 2011-12-06 五氟丙酰氟的合成方法

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WO2013083015A1 true WO2013083015A1 (fr) 2013-06-13

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Publication number Priority date Publication date Assignee Title
CN104016848B (zh) * 2014-06-30 2016-06-01 黄辉 一种五氟丙酰氟的制备方法
CN105315150A (zh) * 2014-08-04 2016-02-10 天津市长芦盐业总公司化工新材料工程技术中心 六氟环氧丙烷低聚物制备全氟丙酰氟的方法
CN105541606A (zh) * 2015-12-29 2016-05-04 天津市长芦化工新材料有限公司 全氟丙酰氟的合成方法及用于该反应的催化剂制备方法
CN106631770B (zh) * 2016-12-14 2019-11-22 天津市长芦化工新材料有限公司 一种β-卤素四氟丙酰氟的合成方法
CN114014782B (zh) * 2021-10-20 2023-10-27 化学与精细化工广东省实验室 胺化-脱水一锅法气相连续制备七氟异丁腈的方法
CN114773239B (zh) * 2022-05-09 2024-02-27 浙江巨化技术中心有限公司 一种全氟(4-甲基-3,6-二氧杂-7-辛烯)磺酰氟及其制备方法
CN115368232A (zh) * 2022-08-02 2022-11-22 浙江诺亚氟化工有限公司 一种全氟代酰氟的合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5838231A (ja) * 1981-08-31 1983-03-05 Daikin Ind Ltd ペンタフルオロプロピオニルフルオライドの製法
JPH04134046A (ja) * 1990-09-21 1992-05-07 Nippon Mektron Ltd パーフルオロプロピオン酸フロリドの製造法
US5684193A (en) * 1995-11-13 1997-11-04 Hoechst Aktiengesellschaft Process for the preparation of perfluoropropionyl fluoride

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5838231A (ja) * 1981-08-31 1983-03-05 Daikin Ind Ltd ペンタフルオロプロピオニルフルオライドの製法
JPH04134046A (ja) * 1990-09-21 1992-05-07 Nippon Mektron Ltd パーフルオロプロピオン酸フロリドの製造法
US5684193A (en) * 1995-11-13 1997-11-04 Hoechst Aktiengesellschaft Process for the preparation of perfluoropropionyl fluoride

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