EP0245133B1 - Fonctionnalisation de iodo-polyfluoroalcanes par réduction électrochimique et nouveaux composés fluorés ainsi obtenus - Google Patents

Fonctionnalisation de iodo-polyfluoroalcanes par réduction électrochimique et nouveaux composés fluorés ainsi obtenus Download PDF

Info

Publication number
EP0245133B1
EP0245133B1 EP87400768A EP87400768A EP0245133B1 EP 0245133 B1 EP0245133 B1 EP 0245133B1 EP 87400768 A EP87400768 A EP 87400768A EP 87400768 A EP87400768 A EP 87400768A EP 0245133 B1 EP0245133 B1 EP 0245133B1
Authority
EP
European Patent Office
Prior art keywords
process according
iodo
cooh
water
ppm
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
EP87400768A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0245133A1 (fr
Inventor
Sylvie Résidence Le Prieuré Benefice-Malouet
Patrick Calas
Hubert Blancou
Auguste Commeyras
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
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 Atochem SA, Elf Atochem SA filed Critical Atochem SA
Publication of EP0245133A1 publication Critical patent/EP0245133A1/fr
Application granted granted Critical
Publication of EP0245133B1 publication Critical patent/EP0245133B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the present invention relates to the preparation of compounds containing a perfluorinated chain and at least one acid or alcohol function by electrochemical reduction of iodo-polyfluoralcanes.
  • Polyfluorinated alcohols of type R F CH 2 CH 2 0H where R F denotes a perfluoroalkyl radical are precursors of surface treatment agents and materials and can be prepared from iodo-1 perfluoroalkyl-2 ethanes R F C 2 H 4 1 according to various routes, for example, by the action of an amide in aqueous solution (publication JP 72-37520) or by the action of a sulfuric oleum (US Patent 3,283,012) or also by formation in tributylphosphate an intermediate organozinc which is then oxidized and then hydrolyzed (patent FR 2,521,987).
  • the synthesis of these alcohols by electrochemical reduction of the compounds R F C 2 H 4 1 has not yet been envisaged.
  • the invention now relates to a process for the preparation of compounds containing a perfluorinated chain and at least one acid or alcohol function by electrochemical reduction of iodo-polyfluoroalkanes, characterized in that this reduction is carried out in a solvent of the formamide type on a cathode carbon, possibly in the presence of sulfur dioxide or in the presence of water and sulfur dioxide.
  • the solvent in which the electrochemical reduction according to the invention is carried out may be the formamide itself or an N-substituted derivative of the latter, such as methylformamide or, preferably, dimethylformamide.
  • this solvent can be used in mixture with water, provided that the proportion of water does not exceed 70% by volume and preferably remains less than 30% by volume .
  • the water content of the solvent plays an important role in the nature of the functional fluorinated derivatives formed in accordance with the process according to the invention.
  • the carbon cathode used according to the invention can consist of carbon fibers, woven or nonwoven, or by a glassy carbon plate.
  • an activator chosen from allyl alcohol, propargyl alcohol, iodo -2 perfluoroalkyl-3 propanols (patents FR 2 486 521 and 2 486 522) and the dichloro-1,1 perfluoroalkyl-2 ethylenes (patent FR 2 559 479).
  • the activator concentration can range up to 10% by volume relative to the solvent mixture, but is preferably between 0.02 to 0.2%.
  • the preferred activator is allyl alcohol.
  • the anode is preferably identical to the cathode, but it can also be constituted by any usual material for an electrode, for example, nickel, platinum, gold, lead, etc.
  • the support electrolyte whose role is to ensure the passage of current can be chosen from all the mineral or organic salts known for this purpose (cf. for example "Organic Electrochemistry" by MM BAIZER, 1973, p. 227-230) and, more particularly, among the halides, perchlorates or arylsulfonates of alkali metals (preferably lithium) or of tetraalkylammonium (C 1 -C 4 alkyl radicals).
  • the concentration of support electrolyte can range from 0.01 to 1 mole per liter of solvent mixture.
  • the electrochemical reduction according to the invention can be carried out intensiostatically or potentiostatically in the various usual cell types. Although one can operate in a single compartment cell, it is preferred to conduct the operation in a two compartment cell to avoid free circulation between the cathode and the anode; the separator is generally made of an inert material, for example, porcelain, sintered glass, cellulose, alumina, porous polytetrafluoroethylene or ion exchange membrane.
  • the nature of the functional fluorinated derivatives obtained depends not only on the starting iodo-polyfluoroalkane, but also on the operating conditions used and in particular on the water content of the solvent.
  • perfluoro-carboxylic acid Cn- 1 F 2n-1 -COOH if the formamide contains less than 0.2% by volume of water.
  • a mixture of Cn-1F2n-1-COOH acid and CnF2n + 1-S0 2 H acid is obtained, the proportion of the latter rapidly increasing up to '' to about 95% when the water content reaches 20% by volume.
  • the acid CnF2n + 1-S0 2 H is formed almost exclusively, but the chemical yield then decreases rapidly.
  • a perfluorocarboxylic acid advantageously use a formamide having a water content as low as possible while, to obtain a perfluoro-sulfinic acid, it will advantageously operate in the presence of sulfur dioxide in a formamide with a water content greater than 5% by volume and preferably between 10 and 20%.
  • a separate glass electrochemical cell is used, using a sintered glass of porosity 3 or 4 and of diameter 30 mm, in two anode and cathode compartments with respective capacities 12 and 24 ml.
  • the two electrodes are made of carbon fibers and each consist of 5 cm of wick of 10,000 strands of 3 ⁇ m in diameter.
  • a mixture is introduced into the cell comprising 22.5 ml of dimethylformamide, 2.5 ml of water, 0.1 g of lithium chloride, 5 ⁇ l of allylic alcohol and 4 g of sulfur dioxide.
  • the reduction is carried out intensiostatically.
  • the catholyte is constantly agitated by means of a magnetic bar and a weak current of gaseous sulfur dioxide is maintained in the anode compartment throughout the duration of the electrolysis in order to avoid the diffusion of C 6 F 13 l.
  • the following table indicates the yields of perfluorohexanesulfinic and perfluorohexanoic acids obtained when the water content of the electrolysis medium is varied.
  • the perfluorobutanesulfinic acids C 4 F 9 S O2 H and perfluorobutanoic C 3 F 7 COOH are obtained with respective yields of 95 and 3%.
  • the perfluorooctanesulfinic acids C 8 F 17 SO 2 H and perfluorooctanoic C 7 F 15 COOH are obtained and the same renders ment.
  • a separate glass electrochemical cell is used, by means of a sintered glass of porosity 3 or 4 and of diameter 15 mm, in two anode and cathode compartments with respective capacities 3.5 and 7.5 ml.
  • the two electrodes are made of carbon fibers and each consist of 1.5 cm of wick of 10,000 strands of 3 ⁇ m in diameter.
  • a mixture is introduced into this cell comprising 6.3 ml of dimethylformamide, 0.7 ml of water, 0.03 g of lithium chloride , 1.5 ⁇ l of allylic alcohol and I g of sulfur dioxide.
  • the catholyte is agitated by means of a magnetic bar and a weak current of gaseous sulfur dioxide is maintained in the anode compartment throughout the duration of the electrolysis.
  • Example 2 The same cell and the same electrodes are used as in Example 1 and a mixture comprising 25 ml of dimethylformamide previously dehydrated on calcium hydride (water content ⁇ 0.2% by volume), 0 is introduced into the cell. 1 g of lithium chloride and 5 ⁇ l of allyl alcohol, at a rate of 11 ml in the anode compartment and 14 ml in the cathode compartment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP87400768A 1986-04-17 1987-04-07 Fonctionnalisation de iodo-polyfluoroalcanes par réduction électrochimique et nouveaux composés fluorés ainsi obtenus Expired EP0245133B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8605519A FR2597511B1 (fr) 1986-04-17 1986-04-17 Fonctionnalisation de iodo-polyfluoroalcanes par reduction electrochimique et nouveaux composes fluores ainsi obtenus
FR8605519 1986-04-17

Publications (2)

Publication Number Publication Date
EP0245133A1 EP0245133A1 (fr) 1987-11-11
EP0245133B1 true EP0245133B1 (fr) 1989-10-11

Family

ID=9334336

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87400768A Expired EP0245133B1 (fr) 1986-04-17 1987-04-07 Fonctionnalisation de iodo-polyfluoroalcanes par réduction électrochimique et nouveaux composés fluorés ainsi obtenus

Country Status (17)

Country Link
US (2) US4830715A (no)
EP (1) EP0245133B1 (no)
JP (1) JPS62250191A (no)
AT (1) AT394214B (no)
AU (1) AU587120B2 (no)
CA (1) CA1299191C (no)
DE (1) DE3760742D1 (no)
DK (1) DK195187A (no)
ES (1) ES2005153A6 (no)
FI (1) FI84918C (no)
FR (1) FR2597511B1 (no)
GR (1) GR870612B (no)
IL (1) IL82011A (no)
NO (1) NO169085C (no)
PT (1) PT84706B (no)
TR (1) TR22854A (no)
ZA (1) ZA872754B (no)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5202506A (en) * 1992-04-02 1993-04-13 E. I. Du Pont De Nemours And Company Oxidative drown process for 2-perfluoroalkylethyl alcohols
JPH061472U (ja) * 1992-06-15 1994-01-11 積水化学工業株式会社 洗面台
JP3324273B2 (ja) * 1994-05-16 2002-09-17 松下電器産業株式会社 多チャンネル多重装置
TWI335517B (en) * 2006-08-25 2011-01-01 Via Tech Inc Method of requests access and scheduling and related apparatus thereof
JP5556177B2 (ja) * 2007-09-04 2014-07-23 ダイキン工業株式会社 含フッ素化合物の吸着方法と回収方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2519983A (en) * 1948-11-29 1950-08-22 Minnesota Mining & Mfg Electrochemical process of making fluorine-containing carbon compounds
US2606206A (en) * 1951-02-05 1952-08-05 Minnesota Mining & Mfg Perfluorosebacic acid
US3283012A (en) * 1962-05-29 1966-11-01 Du Pont Process for preparing 2-perfluoroalkylethanol
US3810939A (en) * 1970-03-11 1974-05-14 Nat Starch Chem Corp Fluorocarbon sulfonic acid water and oil repellency agents
FR2342950A1 (fr) * 1976-03-05 1977-09-30 Ugine Kuhlmann Procede de fonctionnalisation de radicaux perfluores
IT1117060B (it) * 1976-03-05 1986-02-10 Ugine Kuhlmann Procedimento per la preparazione di composti perfluorati,particolarmente di acidi perfluorocarbossilici e perfluoroalcan solfinici
FR2374287A1 (fr) * 1976-12-17 1978-07-13 Ugine Kuhlmann Procede de preparation de derives des acides perfluoroalcane-carboxyliques et perfluoroalcane-sulfiniques
DE2903981A1 (de) * 1979-02-02 1980-08-07 Hoechst Ag Rueckgewinnung fluorierter emulgatorsaeuren aus basischen anionenaustauschern
FR2486521A1 (fr) * 1980-07-08 1982-01-15 Ugine Kuhlmann Procede d'addition d'iodoperfluoroalcanes sur des composes ethyleniques ou acetyleniques
US4332954A (en) * 1981-01-30 1982-06-01 Minnesota Mining And Manufacturing Company Cyclic sulfoperfluoroaliphaticcarboxylic acid anhydrides
JPS57164991A (en) * 1981-04-02 1982-10-09 Asahi Chem Ind Co Ltd Production of (omega-fluorosulfonyl)haloaliphatic carboxylic acid fluoride
DE3128118A1 (de) * 1981-07-16 1983-02-03 Hoechst Ag, 6000 Frankfurt "verfahren zur herstellung von (alpha),(omega)-bis-fluorsulfato-perfluoralkanen sowie einige spezielle dieser verbindungen"
FR2521987A1 (fr) * 1982-02-23 1983-08-26 Ugine Kuhlmann Procede de preparation d'alcools polyfluores du type rfch2ch2oh
FR2559479B1 (fr) * 1984-02-14 1986-07-18 Atochem Synthese d'acides perfluoroalcane-carboxyliques
US4647350A (en) * 1985-10-15 1987-03-03 Monsanto Company Electrolytic preparation of perfluoroalkanoic acids, perfluoroalkanols and perfluoroalkyl esters

Also Published As

Publication number Publication date
PT84706B (pt) 1989-11-30
DK195187D0 (da) 1987-04-15
US5023370A (en) 1991-06-11
FI84918B (fi) 1991-10-31
IL82011A (en) 1990-11-29
NO169085B (no) 1992-01-27
FR2597511A1 (fr) 1987-10-23
DE3760742D1 (en) 1989-11-16
FI871680A (fi) 1987-10-18
ATA94987A (de) 1991-08-15
FR2597511B1 (fr) 1990-09-07
JPS62250191A (ja) 1987-10-31
EP0245133A1 (fr) 1987-11-11
JPH0254436B2 (no) 1990-11-21
PT84706A (fr) 1987-05-01
CA1299191C (fr) 1992-04-21
GR870612B (en) 1987-08-12
FI84918C (fi) 1992-02-10
ZA872754B (en) 1987-10-05
AU7174787A (en) 1987-10-22
NO169085C (no) 1992-05-06
US4830715A (en) 1989-05-16
AU587120B2 (en) 1989-08-03
NO871494D0 (no) 1987-04-09
NO871494L (no) 1987-10-19
TR22854A (tr) 1988-09-13
ES2005153A6 (es) 1989-03-01
DK195187A (da) 1987-10-18
FI871680A0 (fi) 1987-04-15
AT394214B (de) 1992-02-25

Similar Documents

Publication Publication Date Title
DE1468149B1 (de) Verfahren zur herstellung von olefinoxiden
FR2530266A1 (fr) Procede de preparation des acides arylacetiques et arylpropioniques
EP0245133B1 (fr) Fonctionnalisation de iodo-polyfluoroalcanes par réduction électrochimique et nouveaux composés fluorés ainsi obtenus
JPS6140040B2 (no)
KR20130138296A (ko) 유기 화합물의 전기화학적 플루오린화 방법
JPH02133591A (ja) フルオロカーボン類の製造法
EP0203851B1 (fr) Procédé électrochimique de préparation de dérivés organiques trifluoro(ou chlorodifluoro ou dichlorofluoro) méthylés
EP0043758B1 (fr) Procédé d'addition d'iodoperfluoroalcanes sur des composés éthyléniques ou acétyléniques
EP0007674B1 (fr) Procédé d'électrolyse d'une solution aqueuse de chlorure de métal alcalin dans une cellule à diaphragme
BE1014628A5 (fr) Procede de preparation de composes perfluoroorganiques par fluoration electrochimique.
BE1014521A3 (fr) Procede de preparation de composes organiques perfluores par fluoration electrochimique.
CH664979A5 (fr) Procede d'electrosynthese d'acides carboxyliques.
CH628883A5 (fr) Procede de fabrication d'un disulfure de tetraalkylthiurame.
EP0179676B1 (fr) Procédé de préparation d'acide glyoxylique par oxydation électrochimique anodique du glyoxal
FR2633948A1 (fr) Synthese de trifluoromethanesulfinates
WO1997024309A1 (fr) Procede de preparation d'acides perfluoroalcanecarboxyliques et perfluoroalcanesulfoniques
US4466926A (en) Process for the preparation of α,ω-bis-fluorosulfatoperfluoroalkanes, and a few special representatives of these compounds
FR2604189A1 (fr) Procede de preparation de derives benzyliques fluores
CH626603A5 (no)
FR2569726A1 (fr) Procede de preparation d'acide glyoxylique par oxydation electrochimique anodique du glyoxal
FR2665715A1 (fr) Procede electrochimique pour la preparation de l'acide 4,4'-dinitrostilbene-2,2'-disulfonique et de ses sels.
Medaghri-Alaoui et al. ELECTROCHEMICAL REDUCTION OF CF2Br2 IN THE PRESENCE OF RICH OR DEFICIENT OLEFINS
FR2462440A1 (fr) Procede pour l'obtention de cetophosphonates et d'aldophosphonates par oxydation catalytique des phosphonates ethyleniques correspondants
FR2728569A1 (fr) Sels liquides hydrophobes, leur preparation et leur application en electrochimie
FR2681866A1 (fr) Procede de synthese d'organosilicies et composes organosilicies.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19870410

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19890203

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI LU NL SE

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3760742

Country of ref document: DE

Date of ref document: 19891116

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19920416

Year of fee payment: 6

Ref country code: CH

Payment date: 19920416

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920430

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19920507

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920604

Year of fee payment: 6

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19930407

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19930430

Ref country code: CH

Effective date: 19930430

Ref country code: BE

Effective date: 19930430

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19930909

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930922

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19930924

Year of fee payment: 7

BERE Be: lapsed

Owner name: ATOCHEM

Effective date: 19930430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19931101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940407

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940407

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19941229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950103

EUG Se: european patent has lapsed

Ref document number: 87400768.5

Effective date: 19931110

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050407