EP0457320B1 - Procédé de déshalogénation électrolytique partielle des acides dichloro-acétiques et solution d'électrolyse - Google Patents

Procédé de déshalogénation électrolytique partielle des acides dichloro-acétiques et solution d'électrolyse Download PDF

Info

Publication number
EP0457320B1
EP0457320B1 EP91107944A EP91107944A EP0457320B1 EP 0457320 B1 EP0457320 B1 EP 0457320B1 EP 91107944 A EP91107944 A EP 91107944A EP 91107944 A EP91107944 A EP 91107944A EP 0457320 B1 EP0457320 B1 EP 0457320B1
Authority
EP
European Patent Office
Prior art keywords
formula
another
alkyl
independently
group
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 - Lifetime
Application number
EP91107944A
Other languages
German (de)
English (en)
Other versions
EP0457320A1 (fr
Inventor
Steffen Dr. Dapperheld
Rudolf Rossmeissl
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of EP0457320A1 publication Critical patent/EP0457320A1/fr
Application granted granted Critical
Publication of EP0457320B1 publication Critical patent/EP0457320B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/01—Products
    • C25B3/11—Halogen containing compounds

Definitions

  • Monochloroacetic acid and its derivatives are important intermediates in industrial organic synthesis. They are used for the production of adhesives, pesticides or pharmaceutical products.
  • the production of monochloroacetic acid by chlorinating acetic acid is always associated with the formation of di- and trichloroacetic acid.
  • electrochemical dehalogenation is also available for removing di- and trichloroacetic acid from the product mixture (EP-B 0 241 685).
  • the latter dehalogenation is carried out using graphite cathodes in the presence of small amounts of metal salts with a hydrogen overvoltage of at least 0.4 V (at a current density of 4000 A / m 2 ), preferably in water-containing, acidic electrolytes.
  • This process has a high selectivity because the thermodynamically favored reduction of protons to hydrogen takes place at the cathode at low concentrations of the partially dehalogenated di- and trichloroacetic acid. In this way, undesired dehalogenation of the monochloroacetic acid is avoided, but the di- and trichloroacetic acid are also dehalogenated only with poor current efficiency.
  • This method is not suitable for dehalogenation down to a very low concentration level of di- and trichloroacetic acid, since an increasing proportion of the electrical charge is used for the reduction of protons to hydrogen.
  • An economical implementation of dehalogenation to monochloroacetic acid at a low concentration of di- and trichloroacetic acid has therefore only been insufficient to date (comparative example).
  • the task was therefore to selectively dehalogenate di- and trichloroacetic acid with very extensive conversion to monochloroacetic acid, that is to say not completely.
  • Nekrasov et al. investigated the dehalogenation of trichloroacetic acid and monochloroacetic acid in the presence of tetramethylammonium or tetraethylammonium salt in a non-protic electrolyte (Nekrasov et al., Elektrokhimiya 1988, 24, 560-563). The effects they observed in no way suggest that ammonium salts in an aqueous electrolyte could inhibit the above-mentioned undesired reduction of protons to hydrogen.
  • di- and trichloroacetic acid can be dehalogenated continuously or discontinuously to form monochloroacetic acid with very extensive conversion in divided electrolysis cells if electrolysis is carried out in aqueous solutions in which, in addition to metal salts, a hydrogen overvoltage of at least 0.4 V (at a Current density of 4000 A / m 2 ) quaternary ammonium and / or phosphonium salts are still dissolved.
  • Another object is an electrolysis solution for the partial dehalogenation of tri- and / or dichloroacetic acid, which contains at least one of these two acids, one or more metal salts with a hydrogen overvoltage of at least 0.4 V (at a current density of at least 4000 A / m 2 ) contains at least one compound selected from the group of compounds of the formula I to V.
  • the compounds of the formulas I to V are used in concentrations of 1 to 5000 ppm, preferably 10 to 1000 ppm, but in particular 50 to 500 ppm.
  • the metal salts with a hydrogen overvoltage of at least 0.4 V are generally the soluble salts of Cu, Zn, Cd, Hg, Sn, Pb, Ti, Bi, V, Ta and / or Ni, preferably the soluble salts of Cu, Zn, Cd, Sn, Hg and Pb.
  • CI-, Br-, SO 4 2- , NO 3 - or CH 3 COO- are preferably used as anions, the anion being chosen so that a soluble metal salt is formed (for example PbN0 3 ).
  • the salts can be added directly to the electrolysis solution or, e.g. by adding oxides or carbonates - or by adding the metals themselves, such as Zn, Cd, Sn, Pb, Ni - in the solution.
  • the salt concentration in the catholyte is expediently set to about 0.1 to 5000 ppm, preferably to about 10 to 1000 ppm.
  • the starting material for the process is di- and / or trichloroacetic acid or mixtures thereof with monochloroacetic acid which are inevitably formed in the acetic acid chlorination.
  • the proportion by weight of di- and trichloroacetic acid in the total amount of chlorinated acetic acids is less than 10% by weight. This proportion by weight can easily be less than 5% by weight, or even less than 2% by weight, which was particularly surprising.
  • the catholyte can also contain mineral acids (eg HCl, H 2 S0 4 etc.).
  • the anolyte is preferably an aqueous mineral acid, in particular an aqueous hydrochloric acid or sulfuric acid.
  • the same material as that for the cathode can generally be used as the anode material.
  • other customary electrode materials which, however, must be inert under the electrolysis conditions, for example titanium, coated with titanium dioxide and doped with a noble metal oxide, such as e.g. Ruthenium dioxide.
  • Cation exchange membranes made of perfluorinated polymers with carboxyl and / or sulfonic acid groups are generally used to divide the cells into the anode and cathode compartments. It is also generally possible to use anion exchange membranes which are stable in the electrolyte, diaphragms made of polymers or inorganic materials.
  • the electrolysis temperature should generally be below 100 ° C, preferably between 10 and 90 ° C.
  • the electrolysis can be carried out either continuously or batchwise.
  • a continuous process is preferred, especially at a low concentration of di- and trichloroacetic acid.
  • chloride is constantly consumed due to the anodic chlorine evolution. In general, the chloride consumption is then compensated for by continuously introducing gaseous HCl or aqueous hydrochloric acid.
  • the electrolysis product is worked up in a known manner, e.g. by distillation.
  • the metal salts and the quaternary ammonium and phosphonium compounds remain in the residue and can be returned to the process.
  • the invention is illustrated by the following examples. Examples 1-9 are followed by a comparative example.
  • the comparative example shows that under the electrolysis conditions of EP-B 0 241 685, when a dichloroacetic acid concentration of 31% (based on the total amount of dissolved acetic acids) is reached, the major part of the electrical charge is used for the reduction of protons to hydrogen .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (22)

1. Procédé de déshalogénation partielle des acides trichloracétique et dichloracétique en acide monochlo- racétique par électrolyse de solutions aqueuses de ces acides dans des cellules divisées en présence d'un ou de plusieurs sels de métaux avec une surtension d'hydrogène d'au moins 0,4 V (à une densité de courant de 4000 A/m2), avec des cathodes en carbone, procédé caractérisé par l'addition d'un ou de plusieurs composés pris parmi les suivants, de formules I à V
Figure imgb0057
Figure imgb0058
Figure imgb0059
Figure imgb0060
Figure imgb0061
formules dans lesquelles
X représente l'azote ou le phosphore,
R1 à R21, qui peuvent être identiques ou différents, représentent indépendamment les uns des autres l'hydrogène, un C1-C18-alkyle linéaire ou ramifié, un C3-C18-cycloalkyle ou un C1-C18-alkyl-aryle dont l'aryle peut avoir de 6 à 12 atomes de carbone, les radicaux R2 à R16 pouvant en outre avoir aussi, indépendamment les uns des autres, les significations suivantes :
R2 un groupe -((CH2)n-O)m-R, les significations de R étant les mêmes que pour R1 mais R et R1 étant indépendants l'un de l'autre, et m et n désignant des entiers de 1 à 12 chacun,
R3 et R4, R5 et R6 et/ou R7 et R8, respectivement, forment ensemble, indépendamment les uns des autres, une chaîne de 2 à 8 groupes CH2 ou un groupe -CH2(Z)CH2- dont Z désigne l'azote, l'oxygène ou le soufre, et
R12 et R13, R13 et R14, R14 et R15 et/ou R15 et R16, respectivement, forment ensemble, indépendamment les uns des autres, un groupe
Figure imgb0062
Y représente un groupe -(CH2)p- ou -CH2-[O-(CH2)p]q-O-(CH2)2-, p étant un entier de 1 à 12 et q un entier de 0 à 6, et
A- l'un des anions OH-, F-, CI-, Br-, I-, SO4 2-, HSO4-, NO3-, CH3COO-, BF4- et CH3OSO3-.
2. Procédé selon la revendication 1, caractérisé par l'addition d'au moins un composé de formule I.
3. Procédé selon la revendication 1, caractérisé par l'addition d'au moins un composé de formule II.
4. Procédé selon la revendication 1, caractérisé par l'addition d'au moins un composé de formule III.
5. Procédé selon la revendication 1, caractérisé par l'addition d'au moins un composé de formule IV.
6. Procédé selon la revendication 1, caractérise, par l'addition d'au moins un composé de formule V.
7. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que dans la formule I les symboles R1 à R4 représentent chacun, indépendamment les uns des autres, l'hydrogène ou des alkyles en C1-C16.
8. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que dans la formule I X désigne l'azote ou le phosphore, R1 un alkyle en C1-C3 et R2 à R4, indépendamment les uns des autres, un alkyle en C1-C4.
9. Procédé selon la revendication 1 ou 3, caractérisé en ce que dans la formule II R5 à R10 représentent, indépendamment l'un de l'autre un alkyle en C4-C6 linéaire ou ramifié, un cyclohexyle ou un alkyle en C8-C16 à chaîne linéaire d'ordre pair.
10. Procédé selon la revendication 1 ou 4, caractérisé en ce que dans la formule III R11 représente, un alkyle en C4-C16 et R12 à R16 indépendamment l'un de l'autre, l'hydrogène ou un alkyle en C4-C16.
11. Procédé selon la revendication 1 ou 4, caractérisé en ce que dans la formule III R11 représente un alkyle en C8-C16 et R12 à R16 chacun l'hydrogène.
12. Procédé selon une ou plusieurs des revendications 1 à 11, caractérisé en ce que les composés de formules I à V sont ajoutés à des concentrations de 1 à 5000 ppm.
13. Procédé selon une ou plusieurs des revendications 1 à 11, caractérisé en ce que les composés de formules I à V sont ajoutés à des concentrations de 10 à 1000 ppm.
14. Procédé selon une ou plusieurs des revendications 1 à 11, caractérisé en ce que les composés de formules I à V sont ajoutés à des concentrations de 50 à 500 ppm.
15. Procédé selon au moins une des revendications 1 à 14, caractérisé en ce qu'on utilise en tant que sels de métaux avec une surtension d'hydrogène d'au moins 0,4 V (à une densité de courant de 4000 A/m2) des sels solubles de Cu, Zn, Cd, Hg, Sn, Pb, Ti, Bi, V, Ta et/ou Ni.
16. Procédé selon au moins une des revendications 1 à 14, caractérisé en ce qu'on utilise en tant que sels de métaux avec une surtension d'hydrogène d'au moins 0,4 V (à une densité de courant de 4000 A/m2) des sels solubles de Cu, Zn, Cd, Hg et Pb.
17. Procédé selon au moins une des revendications 1 à 16, caractérisé en ce que la teneur en sels de métaux de la solution d'électrolyse est de 0,1 à 5000 ppm.
18. Procédé selon au moins une des revendications 1 à 16, caractérisé en ce que la teneur de la solution en sels de métaux est de 10 à 1000 ppm.
19. Procédé selon au moins une des revendications 1 à 18, caractérisé en ce que l'on effectue l'électrolyse en continu.
EP91107944A 1990-05-18 1991-05-16 Procédé de déshalogénation électrolytique partielle des acides dichloro-acétiques et solution d'électrolyse Expired - Lifetime EP0457320B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4016063 1990-05-18
DE4016063A DE4016063A1 (de) 1990-05-18 1990-05-18 Verfahren zur teilweisen elektrolytischen enthalogenierung von di- und trichloressigsaeure sowie elektrolyseloesung

Publications (2)

Publication Number Publication Date
EP0457320A1 EP0457320A1 (fr) 1991-11-21
EP0457320B1 true EP0457320B1 (fr) 1994-12-07

Family

ID=6406747

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91107944A Expired - Lifetime EP0457320B1 (fr) 1990-05-18 1991-05-16 Procédé de déshalogénation électrolytique partielle des acides dichloro-acétiques et solution d'électrolyse

Country Status (7)

Country Link
US (1) US5362367A (fr)
EP (1) EP0457320B1 (fr)
JP (1) JPH0593290A (fr)
BR (1) BR9102050A (fr)
CA (1) CA2042862A1 (fr)
DE (2) DE4016063A1 (fr)
FI (1) FI912381A7 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7083707B2 (en) * 2001-07-27 2006-08-01 Canon Kabushiki Kaisha Decomposition apparatus and decomposition method
US7169287B2 (en) * 2001-07-27 2007-01-30 Canon Kabushiki Kaisha Decomposition apparatus and decomposition method
US7692037B2 (en) 2004-09-02 2010-04-06 Eastman Chemical Company Optimized liquid-phase oxidation
US7910769B2 (en) 2004-09-02 2011-03-22 Eastman Chemical Company Optimized liquid-phase oxidation
US7371894B2 (en) 2004-09-02 2008-05-13 Eastman Chemical Company Optimized liquid-phase oxidation
US7572932B2 (en) 2004-09-02 2009-08-11 Eastman Chemical Company Optimized liquid-phase oxidation
US7741515B2 (en) 2004-09-02 2010-06-22 Eastman Chemical Company Optimized liquid-phase oxidation
US7568361B2 (en) 2004-09-02 2009-08-04 Eastman Chemical Company Optimized liquid-phase oxidation
US7692036B2 (en) 2004-11-29 2010-04-06 Eastman Chemical Company Optimized liquid-phase oxidation
US7381836B2 (en) 2004-09-02 2008-06-03 Eastman Chemical Company Optimized liquid-phase oxidation
US7504535B2 (en) 2004-09-02 2009-03-17 Eastman Chemical Company Optimized liquid-phase oxidation
US7589231B2 (en) 2004-09-02 2009-09-15 Eastman Chemical Company Optimized liquid-phase oxidation
US7572936B2 (en) 2004-09-02 2009-08-11 Eastman Chemical Company Optimized liquid-phase oxidation
US20110237830A1 (en) 2010-03-26 2011-09-29 Dioxide Materials Inc Novel catalyst mixtures
US9815021B2 (en) 2010-03-26 2017-11-14 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion
US9012345B2 (en) 2010-03-26 2015-04-21 Dioxide Materials, Inc. Electrocatalysts for carbon dioxide conversion
US10173169B2 (en) 2010-03-26 2019-01-08 Dioxide Materials, Inc Devices for electrocatalytic conversion of carbon dioxide
US8956990B2 (en) 2010-03-26 2015-02-17 Dioxide Materials, Inc. Catalyst mixtures
US9790161B2 (en) 2010-03-26 2017-10-17 Dioxide Materials, Inc Process for the sustainable production of acrylic acid
US9957624B2 (en) 2010-03-26 2018-05-01 Dioxide Materials, Inc. Electrochemical devices comprising novel catalyst mixtures
US9566574B2 (en) * 2010-07-04 2017-02-14 Dioxide Materials, Inc. Catalyst mixtures
US10647652B2 (en) 2013-02-24 2020-05-12 Dioxide Materials, Inc. Process for the sustainable production of acrylic acid
US10774431B2 (en) 2014-10-21 2020-09-15 Dioxide Materials, Inc. Ion-conducting membranes
US10975480B2 (en) 2015-02-03 2021-04-13 Dioxide Materials, Inc. Electrocatalytic process for carbon dioxide conversion
CN109763138A (zh) * 2017-11-09 2019-05-17 山东润博生物科技有限公司 一种3,6-二氯水杨酸的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5476521A (en) * 1977-11-30 1979-06-19 Chlorine Eng Corp Ltd Preparation of monochloroacetic acid
JPS5724333A (en) * 1980-07-18 1982-02-08 Koei Chem Co Ltd Production of quaternary ammonium acidic sulfate salt
US4707230A (en) * 1985-09-23 1987-11-17 Tracer Technologies, Inc. Electrochemical dehalogenation of organic compounds
DE3607446A1 (de) * 1986-03-07 1987-09-10 Hoechst Ag Verfahren zur enthalogenierung von chlor- und von bromessigsaeuren
US4892944A (en) * 1987-05-13 1990-01-09 Mitsubishi Petrochemical Co., Ltd. Process for producing quaternary salts
DE58904307D1 (de) * 1988-03-19 1993-06-17 Hoechst Ag Verfahren zur herstellung von ungesaettigten halogenierten kohlenwasserstoffen.

Also Published As

Publication number Publication date
DE4016063A1 (de) 1991-11-21
BR9102050A (pt) 1991-12-24
US5362367A (en) 1994-11-08
EP0457320A1 (fr) 1991-11-21
FI912381A0 (fi) 1991-05-16
JPH0593290A (ja) 1993-04-16
CA2042862A1 (fr) 1991-11-19
DE59103750D1 (de) 1995-01-19
FI912381A7 (fi) 1991-11-19

Similar Documents

Publication Publication Date Title
EP0457320B1 (fr) Procédé de déshalogénation électrolytique partielle des acides dichloro-acétiques et solution d'électrolyse
DE2818066C2 (de) Verfahren zum Dehalogenieren halogenierter Kohlenwasserstoffe
EP0627020B1 (fr) Procede electrochimique de preparation d'acide glyoxylique
DE19846636A1 (de) Elektrochemische Synthese von Perfluoralkylfluorophosphoranen
DE2603144A1 (de) Betriebsverfahren fuer eine elektrolytische zelle mit drei abteilungen zur herstellung von alkalimetallhydroxiden
DE2949379C2 (de) Verfahren zur Herstellung von Glyoxalsäure durch Oxidation von Glyoxal
EP0334796B1 (fr) Procédé de préparation d'hydrocarbures halogénés insaturés
EP0308838B1 (fr) Procédé de production d'acides fluorés et leurs dérivés
EP0241685B1 (fr) Procédé de déhalogénation des acides chloro- et bromoacétiques
EP0355726B1 (fr) Procédé pour la décarboxylation électrolytique d'un acide perfluorocarboxylique ou de leurs sels solubles et une dimérisation consécutive ds radicaux ainsi obtenus
DE3420333C2 (fr)
DE3522304C2 (de) Verfahren zur Herstellung von Carbonsäuren durch elektrochemische Reduktion
DE4217338C2 (de) Elektrochemisches Verfahren zur Reduktion von Oxalsäure zu Glyoxylsäure
DE10031565B4 (de) Verfahren zur Herstellung von perfluorierten organischen Verbindungen durch elektrochemische Fluorierung
DE10031563B4 (de) Verfahren zur Herstellung von perfluororganischen Verbindungen durch elektrochemische Fluorierung
EP0326855B1 (fr) Procédé de préparation de l'acide fluoromalonique et de ses dérivés
DE4029068A1 (de) Verfahren zur herstellung von halogenierten acrylsaeuren
DE2701453A1 (de) Verfahren zur elektrolytischen oxydation von dialkyldithiocarbamaten zu tetraalkylthiuramdisulfiden
DE69706668T2 (de) Verfahren zur herstellung von tetraalkyl 1,2,3,4-butantetracarboxylaten
EP0293856B1 (fr) Procédé de préparation d'un éther de vinyle fluoriné
DE102010029272A1 (de) Verfahren zur elektrochemischen Herstellung von Isophoron
DE102009001168A1 (de) Verfahren zur Herstellung von Hypophosphiten und Phosphiten
EP0382106B1 (fr) Procédé de préparation de dérivés de thiophène
DE2725213B2 (de) Verfahren zur Herstellung von perfluorierten organischen Säurefluoriden
DE4205423C1 (de) Elektrochemisches Verfahren zur Herstellung von Glyoxylsäure

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

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT NL

17P Request for examination filed

Effective date: 19920514

17Q First examination report despatched

Effective date: 19930430

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;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.SCRIBED TIME-LIMIT

Effective date: 19941207

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19941207

Ref country code: NL

Effective date: 19941207

Ref country code: BE

Effective date: 19941207

Ref country code: FR

Effective date: 19941207

Ref country code: GB

Effective date: 19941207

REF Corresponds to:

Ref document number: 59103750

Country of ref document: DE

Date of ref document: 19950119

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 19941207

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

Ref country code: DE

Effective date: 19960201