WO2002018309A1 - Procede de production d'alcools fluores - Google Patents

Procede de production d'alcools fluores Download PDF

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Publication number
WO2002018309A1
WO2002018309A1 PCT/JP2001/006075 JP0106075W WO0218309A1 WO 2002018309 A1 WO2002018309 A1 WO 2002018309A1 JP 0106075 W JP0106075 W JP 0106075W WO 0218309 A1 WO0218309 A1 WO 0218309A1
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WO
WIPO (PCT)
Prior art keywords
methanol
formula
fluorinated alcohol
hcf
tetrafluoroethylene
Prior art date
Application number
PCT/JP2001/006075
Other languages
English (en)
Japanese (ja)
Inventor
Toru Yoshizawa
Shouji Takaki
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2002018309A1 publication Critical patent/WO2002018309A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups

Definitions

  • the present invention relates to a method for producing a fluorine-containing alcohol (
  • a main object of the present invention is to provide a method capable of producing a fluorine-containing alcohol substantially free of impurities by a smooth distillation operation without causing clogging in a pipe or a distillation column.
  • the present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, contacted a reaction crude product obtained by reacting tetrafluoroethylene with methanol with a base, and then formed NaF and the like. Solids and tar from the bottom of the treatment tank, When a component containing a fluorinated alcohol is subjected to a distillation operation, it is possible to produce a fluorinated alcohol substantially free of impurities by a smooth distillation operation without causing clogging in a pipe or a distillation column. This led to the completion of the present invention.
  • the present invention provides the following method for producing a fluorinated alcohol.
  • a method for producing a fluorinated alcohol represented by the following method, comprising the following steps (i) to (iv):
  • reaction crude product is distilled, methanol obtained from the top of the distillation column is returned to the reactor and reused, and the formula (1) obtained as the bottom component is obtained.
  • the method of recovering HCF 2 CF 2 CH 2 OH in the step (vi) is to remove components having a low boiling point by distilling components containing HCF 2 CF 2 CH 2 ⁇ H.
  • first, tetrafluoroethylene and methanol are reacted in the presence of a radical generation source to obtain the following formula (1)
  • n is 1 or 2.
  • the radical generating source at least one selected from the group consisting of a reaction initiator, UV and heat can be used.
  • the radical source is UV, for example, UV from a medium or high pressure mercury lamp can be used.
  • the radical generating source is heat, it may be heated at a temperature of 250 to 30.
  • the reaction initiator a peroxide can be exemplified, and a reaction initiator having a half-life at the reaction temperature of about 10 hours can be preferably exemplified.
  • Preferred initiators include perbutyl D (di-t-butylperoxyside), perbutyl O (t-butylperoxy-2-ethylhexanoethyl), and perbutyl I (t-butylperoxyisopropyl). Carbonate) and the like.
  • the amount of the reaction initiator used is usually about 0.005 to 0.1 mol per 1 mol of tetrafluoroethylene.
  • methanol is used in an excess amount based on tetrafluoroethylene.
  • the reaction temperature may be about 40 to 14 Ot
  • the reaction time may be about 3 to 12 hours
  • the reaction pressure may be about 0.2 to 1.2 MPa.
  • the reaction can be performed, for example, in a high-pressure reactor. It is preferable to replace the inside of the reaction system with an inert gas such as nitrogen or argon.
  • the production reaction of the fluorinated alcohol is preferably performed in the presence of an acid acceptor.
  • Acid acceptors include calcium carbonate, magnesium carbonate, sodium carbonate, and carbonated lithium.
  • the acid acceptor is preferably one that can trap an acid such as HF generated during the reaction without making the reaction system strongly alkaline.
  • the amount of the acid acceptor is not particularly limited, but may be about 0.01 to 0.1 mol per 1 mol of tetrafluoroethylene.
  • reaction crude product After producing the fluorinated alcohol represented by (1), the obtained reaction crude product is brought into contact with a base.
  • a base having a pKb of 2 or less is preferable.
  • bases include, for example, alkali metal alcoholates such as sodium methylate, sodium ethylate, sodium propylate, potassium t-butoxide, lithium ethylate, 7K sodium oxide, potassium hydroxide, lithium hydroxide, etc.
  • alkali metal hydroxide calcium hydroxide, aluminum hydroxide, barium hydroxide, magnesium hydroxide, and soda lime. Of these, alkali metal alcoholates are particularly preferred.
  • the amount of the base used may be about 0.05 to 1.0 mol, preferably about 0.1 to 0.5 mol, per 1 kg of tetrafluoropropanol by weight.
  • the operating conditions for bringing the reaction crude product into contact with the base are not particularly limited, but the reaction may usually be carried out at about 20 to 150 for about 0.5 to 3 hours.
  • the reaction crude product When the reaction crude product is brought into contact with a base in this way, the reaction crude product contains several ppm to several hundred ppm of HF generated by the side reaction, and this is the treatment tank (base treatment tank). Reacts with a base in the reaction to form solids such as NaF and KF and tar. In particular, solids can cause clogging of piping and distillation columns in subsequent processing. For this reason, solids and tar are removed from the bottom of the base treatment tank, and components containing fluorine-containing alcohol are further purified by distillation.
  • the component containing the fluorinated alcohol is distilled, and the fluorinated alcohol is separated and recovered, whereby the fluorinated alcohol represented by the above formula (1) substantially free of evaporation residue can be obtained.
  • the operation of bringing the reaction crude product into contact with the base may be performed after removing excess methanol from the reaction crude product by a method such as distillation.
  • methanol is distilled off from the top of the distillation column, and the fluorinated alcohol is contained in the bottom liquid.
  • the methanol obtained from the top can be used effectively by returning it to the reactor and reusing it.
  • a reaction product of an acid acceptor such as C a F 2 or Na F and an unreacted acid acceptor are obtained from the reaction crude product. Is preferably removed.
  • the operation is not particularly limited, and any method may be used as long as the reaction product of the acid acceptor and the unreacted acid acceptor, which are solid components, can be removed from the crude reaction product.For example, a centrifuge is used. Can be removed efficiently.
  • the base treatment tank In the base treatment tank, alcohol or water is produced as a reaction product depending on the type of the base used, and low boiling components such as the reaction product and alcohol used as a solvent for the base are converted to tetrafluoropropanol. Mixed. Therefore, first, as a first-stage distillation operation, distillation is performed to separate and remove low-boiling components such as alcohol and water from tetrafluoroalcohol, and then, as a second stage, a first-stage distillation is performed. It is preferable to recover the tetrafluoro alcohol by distilling the component containing the tetrafluoro alcohol obtained as the bottom component by the operation. According to such a distillation method, it is possible to obtain tetrafluoropropanol which is substantially free from impurities and contains no alcohol or water.
  • substantially free of impurities means that the evaporation residue of the fluorinated alcohol is 5 Oppm or less, preferably 25 ppm or less, more preferably 10 ppm or less, and
  • the evaporation residue is a fluoroalcohol 40, 5mmH (0. 665 kP a ) the weight of the residue upon concentration was measured, the ma ss against the HCF 2 CF 2 CH 2 OH, p Expressed in pm.
  • the absorbance in methanol is measured using a sample obtained by adding 3 ml of methanol to lm 1 of the fluorinated alcohol of the general formula (1), and using methanol as a reference.
  • the tetrafluoropropanol substantially free of impurities obtained by the method of the present invention can be used, for example, when manufacturing an information recording medium in which a substrate is provided with a laser on which information is written and a Z or readable recording layer is provided. It is suitable as a solvent.
  • An information recording medium provided with a recording layer capable of writing and Z or reading information by a laser on a substrate is a tetrafluoropropanol compound obtained by the method of the present invention.
  • the dye is dissolved in a solvent containing toluene, preferably a fluorine-containing solvent containing tetrafluoropropanol, and the resulting solution is used to record the dye containing the dye by a method such as coating and drying on a substrate according to a conventional method. It can be manufactured by forming a layer.
  • a solvent containing toluene preferably a fluorine-containing solvent containing tetrafluoropropanol
  • the dye examples include a cyanine dye, a phthalocyanine dye, a pyrylium dye, a thiopyrylium dye, a squarylium dye, an azurenium dye, an indophenol dye, an indoline phosphorus dye, a triphenylmethane dye, a quinone dye, Examples include aluminum dyes, diimmonium dyes, and metal complex salt dyes.
  • the substrate include plastics such as polystyrene, polymethyl methacrylate, epoxy resin, amorphous polyolefin, polyester, and polyvinyl chloride, glass, and ceramics.
  • An undercoat layer may be provided between the recording layer and the substrate for the purpose of improving flatness, improving adhesive strength, preventing deterioration of the recording layer, and a protective layer may be provided on the recording layer. .
  • the tetrafluoropropanol separated and recovered from the fluorinated alcohol thus obtained is substantially free of impurities, and has a recording layer on which information can be written by a laser and Z or readable by a laser. It is a suitable solvent for manufacturing the provided information recording media (such as optical discs such as CD-R and DVD-R) and film photoreceptors.
  • FIG. 1 is a flow chart showing a continuous distillation step in Example 1.
  • 1 is a reactor
  • 2 is a centrifugal separator
  • 3 is a first distillation column
  • 4 is a second distillation column
  • 5 is a base treatment tank
  • 6 is an alkaline distillation column
  • 7 is an alkaline distillation column.
  • a high-pressure reactor was charged with methanol (2 liters), perbutyl D (45 g) and calcium carbonate (30 g), and the reactor was purged with nitrogen, and then tetrafluoroethylene was added at an initial rate of 600. Charged at g / hr, controlled at a temperature of 125 and a pressure of 0.8 MPa The reaction was continued for 6 hours.
  • the reaction crude obtained (HF: 1300 mass.ppm, tetrafluoropropanol 27% (GC analysis value), t-butanol: 0.16% (GC analysis value)) is shown in FIG. It was treated in the following manner by the continuous distillation step shown in FIG. First, the reaction crude product was introduced into the centrifugal separator 2 from the reaction vessel 1, and the unreacted acid acceptor and the reaction product of the acid acceptor were removed by a centrifugation method, and then sent to the first distillation column 3. Next, in the first distillation column 3, methanol was distilled off and recycled to the reaction vessel 1.
  • the separated tetrafluoropropanol was sent to the base treatment tank 5, and 30 g of sodium methylate (28% methanol solution) was added to tetrafluoropropanol (l kg), followed by stirring. From the bottom of the base treatment tank 5, solids and evening water were removed, and a component containing tetrafluoropropanol was introduced into the Aryuri distillation column 6.
  • distillation was carried out in an alkali distillation column 6 to distill methanol and water from the top of the column, and the bottom component containing tetrafluoropropanol was sent to the alkali distillation column 7. Then, by distillation in an alkali distillation column 7, tetrafluoropropanol having a purity of 99.9% or more was obtained as a fraction in the middle stage.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'alcools fluorés représentés par la formule générale (1), dans laquelle n est égal à 1 ou 2. Ces alcools fluorés sont produits à partir de tétrafluoroéthylène et de méthanol comme matériaux de départ en présence d'un générateur de radicaux libres. Ce procédé comprend les étapes consistant à (1) faire réagir du tétrafluoroéthylène avec du méthanol ; (ii) à mettre en contact le produit de réaction brut obtenu avec une base puis à retirer les solides et le goudron généré; et (iii) distiller le produit de réaction brut traité dans l'étape (ii) pour récupérer l'alcool fluoré représenté par la formule générale (1). Ainsi, un alcool fluoré ne contenant pratiquement pas d'impuretés peut être produit par une opération de distillation sans colmater les canalisations ni la colonne de distillation.
PCT/JP2001/006075 2000-08-28 2001-07-13 Procede de production d'alcools fluores WO2002018309A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000257848A JP2002069019A (ja) 2000-08-28 2000-08-28 含フッ素アルコールの製造方法
JP2000-257848 2000-08-28

Publications (1)

Publication Number Publication Date
WO2002018309A1 true WO2002018309A1 (fr) 2002-03-07

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Application Number Title Priority Date Filing Date
PCT/JP2001/006075 WO2002018309A1 (fr) 2000-08-28 2001-07-13 Procede de production d'alcools fluores

Country Status (4)

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JP (1) JP2002069019A (fr)
CN (1) CN1242967C (fr)
TW (1) TW572879B (fr)
WO (1) WO2002018309A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718630B (zh) * 2012-06-11 2014-07-02 中昊晨光化工研究院 一种精馏提纯四氟丙醇的方法
CN103694082A (zh) * 2013-11-26 2014-04-02 浙江巨圣氟化学有限公司 一种四氟丙醇的提纯方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH035434A (ja) * 1989-05-13 1991-01-11 Hoechst Ag テロマーアルコールの製造方法
EP0967193A2 (fr) * 1998-12-28 1999-12-29 Daikin Industries, Limited Procédé pour la production de fluoroalcool et son utilisation pour la fabrication d'un médium d'enregistrement d'information
EP0968990A2 (fr) * 1999-03-15 2000-01-05 Daikin Industries, Limited Procédé de préparation d'alcools fluorés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH035434A (ja) * 1989-05-13 1991-01-11 Hoechst Ag テロマーアルコールの製造方法
EP0967193A2 (fr) * 1998-12-28 1999-12-29 Daikin Industries, Limited Procédé pour la production de fluoroalcool et son utilisation pour la fabrication d'un médium d'enregistrement d'information
EP0968990A2 (fr) * 1999-03-15 2000-01-05 Daikin Industries, Limited Procédé de préparation d'alcools fluorés

Also Published As

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TW572879B (en) 2004-01-21
CN1441763A (zh) 2003-09-10
JP2002069019A (ja) 2002-03-08
CN1242967C (zh) 2006-02-22

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