WO2003091187A1 - Procede de production de telomere d'iodure d'alkyle entierement halogene - Google Patents

Procede de production de telomere d'iodure d'alkyle entierement halogene Download PDF

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Publication number
WO2003091187A1
WO2003091187A1 PCT/JP2003/004877 JP0304877W WO03091187A1 WO 2003091187 A1 WO2003091187 A1 WO 2003091187A1 JP 0304877 W JP0304877 W JP 0304877W WO 03091187 A1 WO03091187 A1 WO 03091187A1
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WIPO (PCT)
Prior art keywords
formula
compound
column
rectification
general formula
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PCT/JP2003/004877
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English (en)
Japanese (ja)
Inventor
Jun Miki
Yoshito Tanaka
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Daikin Industries, Ltd.
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Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO2003091187A1 publication Critical patent/WO2003091187A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons

Definitions

  • the present invention relates to a method of producing a perhalogenated alkyl iodide telomer and a high-purity perhalogenated alkyl iodide telomer.
  • the perhalogenated alkyl iodide telomer of the present invention is particularly useful when used as a pharmaceutical intermediate, an optical functional material intermediate, or a polymer raw material.
  • an optical functional material the presence of a hydrogen-containing compound as an impurity is extremely useful because optical characteristics are impaired.
  • Rf represents a perhalogenated alkyl group.
  • the purpose can be achieved with a mixture having an average n number of about 3.5.
  • high purity is required as a single component. Therefore, it was important how to efficiently purify compounds having a specific n number.
  • Rf— (CF 2 CF 2 ) n —H was a problem as an impurity.
  • a hydrogen-containing compound deteriorated the optical characteristics, and was deteriorated.
  • the purpose is to provide the law.
  • Another object of the present invention is to provide a perhalogenated alkyl iodide telomer having a low impurity content. It is a further object of the present invention to provide an optically functional material and an intermediate of Z or an optically functional material using them. Disclosure of the invention
  • the compound of formula (I), which is a starting material, is reacted with tetrafluoroethylene, the reaction mixture is introduced into a distillation column, and the overhead is reduced by distilling off a fraction mainly composed of the raw material compound of formula (I). It has been found that a highly pure compound of the general formula (II) can be efficiently produced by introducing the bottom liquid to the next rectification step.
  • the invention relates to a process for preparing a compound of the general formula (I):
  • X 1 represents F, C, I
  • X 2 represents F, C, CF 3.
  • a step of introducing the bottom liquid of the distillation column to a rectification step to purify the compound of formula (II) (n 2 to 5) with high purity.
  • the present invention is to provide a method for producing a compound represented by the general formula (II) which comprises a can, as an impurity, the general formula (III):
  • the present invention also relates to a perhalogenated alkyl iodide telomer characterized in that the content of the compound represented by the following formula (hereinafter abbreviated as Rf-H) is 50 ppm or less.
  • the perhalodialkyl alkyl iodide telomer according to the present invention is particularly useful when used as a pharmaceutical intermediate, an intermediate of an optically functional material, or a polymer raw material.
  • the optical functional material is, for example, an organic material for optical communication, such as an optical waveguide material, an optical switch, a modulator, a filter, an optical cross connect, an optical amplifier, a multiplexer / demultiplexer, a wavelength converter, 0ADM, a photonic crystal, and a non-linear type.
  • optical materials include optical recording materials such as holographic materials, photochromic materials, photorefractive materials, and liquid crystal materials.
  • display materials include organic EL materials, liquid crystal materials, and LEDs.
  • the obtained perhalogenated alkyl iodide telomer can be reacted with phosphorus to synthesize high-purity alkyl perphosphoric acid and / or bis-perhalogenated alkyl phosphoric acid.
  • These high-purity fluorinated phosphoric acids are extremely useful as intermediates for optically functional materials.
  • these fluorinated phosphoric acid and rare earth metal ions such as erbium (Er) ion, thulium (Tm) ion, praseodymium (Pr) ion, holmium (Ho) ion, neodymium (Nd) ion, europium ( Complexes with Eu) ions, cerium (Ce) ions, samarium (Sm) ions, dysprosium (Dy) ions, and terbium (Tb) ions can be expected as highly efficient light-emitting materials and optical amplification materials. .
  • C1CF 2 CF 2 I, ICF 2 CF 2 I, C1CF 2 CFC1I, (CF 3 ) 2 CFI are preferably exemplified CF 3 CFC1 I, ICF 2 CFC1I, C1CF 2 CF (CF 3 ) I, ICF 2 CF ( CF 3 ) I can also be used.
  • metal catalysts As the catalyst used for the telomerization reaction, known catalysts, in particular, metal catalysts can be widely used. 10 Examples of the metal type of the metal catalyst include copper, tin, zinc, magnesium, vanadium, renium, rhodium, ruthenium, platinum, silver, alloys of these metals, and mixtures of these metals. Alternatively, an alloy obtained by adding a small amount of a transition metal to these metals can be used. As the transition metal, it is possible to use a metal which does not show a catalytic action itself or a catalyst having a very small catalytic action, such as iron, nickel, chromium, molybdenum, tungsten,
  • Titanium etc. can be used.
  • tin using copper as a cocatalyst when copper, tin, or tin using copper as a cocatalyst is used as a catalyst, the catalytic activity and the selectivity of the medium-chain telomer are improved.
  • tin using copper as a cocatalyst a mixture of tin powder and copper powder, a tin-copper alloy, or the like can be used. Since both tin and copper can be used as catalysts for the telomerization reaction, the ratio of both can be arbitrarily determined. For example, if the ratio of tin is 0.
  • the size of tin powder, copper powder, tin-copper alloy powder, etc. used as a catalyst is not particularly limited, but may be, for example, 0.1 ⁇ m or more: about Lmm, preferably 20 ⁇ m to 0.3 mm. Particle size of about 20 ⁇ ! About 200 ⁇ m, preferably 45 to 100 ⁇ m
  • the reaction can be carried out batchwise or continuously.
  • the reaction When the reaction is carried out in a continuous manner, for example, a tubular reactor filled with a catalyst metal composed of spherical metal powder or sintered metal is used as the reactor, and the raw material of the formula (I) and tetrafluoride are added to the reactor.
  • the telomerization reaction can be carried out by continuously supplying ethylene to the mouth.
  • the amount of the catalyst used is not particularly limited, but is preferably about 0.2 to 50 raass% based on the weight of the compound of the formula (I) as the raw material. If the amount of the catalyst used is too large, it is uneconomical, and if the amount is too small, the reaction speed is undesirably slow.
  • These catalysts may be used in the form of a catalyst metal supported on a carrier such as alumina or zeolite.
  • the compound of the formula ( ⁇ ) wherein n is 2 or more is present under such conditions that 0.1 to 10 mol%, preferably 0.3 to 5 mol% is present (the compound of the formula (I) as a raw material and
  • the reaction is preferably carried out under the following conditions: ethylene ratio, pressure, temperature, time, type and amount of catalyst.
  • eta 5 mol% of the total product the production of 6 or more compounds or less, preferably 2 mol 0/0 or less, more preferably 0 - 5 mole 0/0 or less, in particular can be suppressed to 0.1 mole 0/0, it is possible to manufacture various telomers of interest efficiently.
  • the reaction temperature is usually about 60 to 200 ° C, preferably about 60 to 160 ° C, and more preferably about 100 to 140 ° C.
  • the pressure during the reaction is preferably about 0.1 to 5 MPa (gauge pressure).
  • the reaction proceeds at a pressure lower than this, which is not preferable because the space time yield decreases. If the reaction pressure is higher than the above range, the telomerization reaction proceeds, but safety risks and costs are increased.
  • the reactor is, for example, a reactor having a pressurized temperature control device so that the compound of the formula (I) can exist in a liquid phase, and having a stirring device,
  • the internal pressure is increased from 0.5 to 1.5M so that tetrafluoroethylene, the compound of formula (I), can exist mainly as a liquid
  • a tank reactor that can be adjusted within the range of Pa (gauge pressure) is suitable.
  • the telomerization reaction can be performed by introducing tetrafluoroethylene in a gas phase into a device in which a liquid phase containing the raw material of the formula (I) is stirred.
  • the reaction may be carried out by dissolving tetrafluoroethylene in the raw material of the formula (I), and then supplying this solution from a reactor introduced into the reactor.
  • a reactor equipped with a pressure controller at the outlet and having a temperature controller is suitable.
  • the internal pressure is about 0.5 to 3 MPa (gauge pressure) so that tetrafluoroethylene, which is a taxogen, is dissolved in telogen, for example, parafluoroethyl iodide, and can remain as a liquid. It is preferable to adjust in the range of.
  • the reaction mixture obtained by the above reaction is supplied to a distillation column to distill a fraction containing the i-adduct of the formula (I), which is a starting material at the top, as a main component.
  • the reaction mixture contains the compound represented by the formula (II)!
  • the reaction may be terminated in a state where the conversion is low and led to a distillation column.
  • the bottom liquid is guided to the next rectification step and further purified.
  • purification by a distillation column is exemplified.
  • the distillation column may be a single distillation column or may be purified using two or more distillation columns.
  • the bottom liquid may contain a small proportion of V as a raw material.
  • the distillation may be carried out under the conditions of the number of theoretical plates, temperature and pressure necessary to obtain the compound of the formula (II) of the formula (1) as a top distillate.
  • What is necessary is just to separate and collect.
  • the rectification step can be performed by the following steps (i) to (iii):
  • the present invention also has a feature that Rf-IH, which is an impurity contained in the conventional method for producing a telomer, is 50 ppm or less.
  • Rf-H of 50 ppm or less is determined by gas chromatography with FID detection.
  • telomer of the present invention the properties of the optical functional material can be improved.
  • the telomeri-dani reaction was performed at a supply rate of 9. OmlZ.
  • the reaction temperature was 60 to 120 ° C.
  • the reaction solution flowing out of the stainless tube was cooled, and the composition was analyzed by gas chromatography. The results are shown in Table 1 below.
  • the top fraction of the first distillation column was returned to the reactor and reused.

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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

Procédé de production d'un composé représenté par la formule générale (II) : X1-CF2CFX2-(CF2CF2)n-I [dans laquelle X1 représente fluor, chlore ou iode ; X2 représente fluor, chlore ou CF3 ; et n représente a ou b (a et b représentant chacun un nombre entier compris entre 1 et 5, à condition que a≤b)]. Le procédé consiste à faire réagir un composé représenté par la formule générale (I) X1-CF2CFX2-I (dans laquelle X1 et X2 sont tels que définis plus haut) avec du tétrafluoroéthylène dans un réacteur en présence d'un catalyseur, et est caractérisé en ce qu'il comporte : une étape dans laquelle la réaction est mise en oeuvre dans des conditions permettant de former des produits de réaction contenant comme constituant principal un composé représenté par la formule (II), dans laquelle n=1, et un mélange réactionnel liquide contenant la matière première représentée par la formule (I) comme ingrédient principal est introduit dans une colonne de distillation ; une étape dans laquelle une fraction, constituée principalement de la matière première représentée par la formule générale (I), est extraite du sommet de la colonne par distillation et est réinjectée dans le réacteur pour être réutilisée ; et une étape dans laquelle le fond de la colonne de distillation est introduit dans un étage de rectification à des fins de purification, pour produire un composé très pur représenté par la formule (II). L'invention concerne aussi un télomère d'iodure d'alkyle entièrement halogéné, produit par la mise en oeuvre des étapes mentionnées et qui est représenté par la formule (III) : X1-CF2CFX2-(CF2CF2)n-H [dans laquelle X1 et X2 sont tels que définis plus haut ; et n représente c ou d (c et d représentant chacun un nombre entier compris entre 2 et 6, à condition que c≤d], ledit télomère présentant une teneur en impuretés égale ou inférieure à 50 ppm. L'invention concerne de plus une matière fonctionnelle optique et/ou un produit intermédiaire pour matières fonctionnelles optiques, obtenus à partir du télomère ou contenant celui-ci.
PCT/JP2003/004877 2002-04-24 2003-04-17 Procede de production de telomere d'iodure d'alkyle entierement halogene WO2003091187A1 (fr)

Applications Claiming Priority (2)

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JP2002123086 2002-04-24
JP2002-123086 2002-04-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7888538B1 (en) 2009-11-04 2011-02-15 E.I. Du Pont De Nemours And Company Catalyzed olefin insertion
US7951983B2 (en) 2009-11-04 2011-05-31 E.I. Du Pont De Nemours And Company Catalyzed olefin insertion
CN109988058A (zh) * 2017-12-29 2019-07-09 山东东岳高分子材料有限公司 一种较短链长全氟烷基碘调聚物的合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1535408A (en) * 1975-09-24 1978-12-13 Hoechst Ag Process for the preparation of perfluoroalkyl iodide telomers
US5068471A (en) * 1989-12-21 1991-11-26 Hoechst Aktiengesellschaft Continuous telomerization process
US5073651A (en) * 1989-11-11 1991-12-17 Hoechst Aktiengesellschaft Process for the preparation of extensively fluorinated alkyl bromides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1535408A (en) * 1975-09-24 1978-12-13 Hoechst Ag Process for the preparation of perfluoroalkyl iodide telomers
US5073651A (en) * 1989-11-11 1991-12-17 Hoechst Aktiengesellschaft Process for the preparation of extensively fluorinated alkyl bromides
US5068471A (en) * 1989-12-21 1991-11-26 Hoechst Aktiengesellschaft Continuous telomerization process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7888538B1 (en) 2009-11-04 2011-02-15 E.I. Du Pont De Nemours And Company Catalyzed olefin insertion
US7951983B2 (en) 2009-11-04 2011-05-31 E.I. Du Pont De Nemours And Company Catalyzed olefin insertion
CN109988058A (zh) * 2017-12-29 2019-07-09 山东东岳高分子材料有限公司 一种较短链长全氟烷基碘调聚物的合成方法
CN109988058B (zh) * 2017-12-29 2021-07-20 山东东岳高分子材料有限公司 一种较短链长全氟烷基碘调聚物的合成方法

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