EP0102254B1 - Nouvel additif détergent-dispersant suralcalinisé pour huiles lubrifiantes - Google Patents

Nouvel additif détergent-dispersant suralcalinisé pour huiles lubrifiantes Download PDF

Info

Publication number
EP0102254B1
EP0102254B1 EP83401254A EP83401254A EP0102254B1 EP 0102254 B1 EP0102254 B1 EP 0102254B1 EP 83401254 A EP83401254 A EP 83401254A EP 83401254 A EP83401254 A EP 83401254A EP 0102254 B1 EP0102254 B1 EP 0102254B1
Authority
EP
European Patent Office
Prior art keywords
amount
amine
moles
alkylphenol
ratio
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
EP83401254A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0102254A1 (fr
Inventor
Jean-Louis Le Coent
Bernard Demoures
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.)
Orogil SA
Original Assignee
Orogil 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 Orogil SA filed Critical Orogil SA
Priority to AT83401254T priority Critical patent/ATE24545T1/de
Publication of EP0102254A1 publication Critical patent/EP0102254A1/fr
Application granted granted Critical
Publication of EP0102254B1 publication Critical patent/EP0102254B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts

Definitions

  • the present invention relates to a new additive based on calcium and magnesium salts improving the detergency and dispersion properties of lubricating oils.
  • the Applicant has in fact found a detergent-dispersant additive having a TBN of at least 225, containing more than 3.8% by weight of magnesium and, generally, of the order of 2 to 3% by weight of calcium, this which gives said additive, in addition to the detergency and dispersion characteristics, a good activity as anti-wear.
  • magnesium alkylbenzenesulfonate denotes any solution containing from 25 to 80% by weight, preferably from 30 to 70% by weight of a magnesium alkylbenzenesulfonate in a dilution oil which may or may not be the same as that implemented to prepare the new additive.
  • magnesium alkylbenzenesulfonates which can be used, mention may be made of the magnesium salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from C 15 -C 30 olefin polymers.
  • the amount of dilution oil that can be used is such that the amount of oil contained in the final product (including that from the starting magnesium alkylbenzenesulfonate) represents from 20 to 60% by weight of said product, preferably from 25 to 55% and very particularly from 30 to 45% by weight of said product.
  • a simplified representation of the said mixture constituting the “sulfurized alkylphenol may be the following average formula: where x 'varies from 1 to 3 and generally from 1.4 to 2.5.
  • active magnesium oxide denotes magnesium oxide MgO with a specific surface greater than or equal to 80 m 2 / g, for example between 100 and 170 m 2 / g.
  • Maglite DF with a specific surface area close to 140 m 2 / g marketed by Merck
  • Ferumag with a specific surface area close to 160 m 2 / g and marketed by Rhône-Poulenc.
  • polyalkyleneamines such as polyethyleneamines and very particularly ethylenediamine
  • etheramines and most particularly tris (3-oxa-6-amino hexyl) amine.
  • the amine used may be present in the “milk of magnesia from the start of the Fe carbonation operation or during it.
  • the first carbonation operation is favorably carried out at a temperature which can range from 90 to 140 ° C. and preferably from 110 to 140 ° C., in one or more stages with the introduction of “milk of magnesia into the medium containing the magnesium alkylbenzenesulfonate , the sulfurized alkylphenol and the dilution oil in one or more stages, each stage of introduction of "milk of magnesia being followed by a stage of carbonation. It has been found that it is advantageous to carry out the first carbonation operation in two stages, the first stage in the presence of approximately 2/3 of the total quantity of milk of magnesia, then a second stage by adding the remaining quantity of "Milk of magnesia". It has also been found that the addition of an amount of water corresponding to a H 2 O / MgO weight ratio of between 0.1 and 0.9 towards the end of the carbonation is favorable for the smooth running of the process.
  • the neutralization-over-alkalization operation of the alkylphenol sulfurized by lime is favorably carried out at a temperature between 110 and 145 ° C, and preferably between 120 and 140 ° C.
  • the possible second carbonation operation is favorably carried out at a temperature between 120 and 170 ° C, and preferably between 130 and 150 ° C, using a slight excess of CO 2 .
  • the new additive which is the subject of the present invention has the advantage of being perfectly compatible with viscous oils, of containing a low level of sediment and of being slightly viscous.
  • the present invention also relates to the use of the new additive to improve the detergent, dispersing and anti-wear properties of lubricating oils.
  • the amount of additive to be used depends on the future use of said oils. Thus for a gasoline engine oil, the amount of additive to be added is generally between 1 and 3.5%; for a diesel engine oil it is generally between 1.8 and 5%, for a marine engine oil, this can go up to 25%.
  • the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal. and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylphenylethers, polymers of silicon.
  • lubricating oils such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal. and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including al
  • Additional additives may also be present in said lubricating oils alongside the new additive of the invention; mention may, for example, be made of antioxidant additives. anti-corrosion, ashless dispersant additives ...
  • the reaction medium is heated for 30 minutes at 110 ° C at atmospheric pressure. then 30 minutes under vacuum so as to distill the reaction water.
  • Milk of magnesia is prepared in a beaker by mixing, with stirring, active magnesium oxide, glycol and polyamine, milk which is added to the medium to be carbonated.
  • C0 2 is introduced at 110-120 ° C, then after 3 hours of carbonation at 135 ° C, water is introduced and the carbonation is continued for 1 hour 30 minutes.
  • the carbonated medium is placed under vacuum for 30 minutes.
  • the slaked lime is introduced at 120 ° C and then the medium is gradually placed under vacuum (120 102 Pa) and the mixture is heated to 130 ° C.
  • the vacuum is broken and then heated to 145 ° C.
  • the mixture obtained is carbonated for 2 hours at 145 ° C.
  • This test is carried out by adding 10% by weight of product to be tested to an SAE 30 mineral oil. Storage of the solution obtained for 1 month at 20 ° C. and study of the appearance of the solution as a function of time.
  • the finished product is added to an SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 millimoles of calcium + magnesium.
  • Example 3 The various steps described in Example 3 are carried out by replacing the ethylenediamine with an equivalent amount of tris (3-oxa-6-amino-hexyl) amine called “TOA”.
  • The% of sediments obtained before neutralization cannot be lower than 5 and 4 respectively even by increasing the duration of carbonation.
  • the vacuum is tightened to the maximum and heated to 130 ° C.
  • the vacuum is broken, 411 g of a sulfurized dodecylphenol containing approximately 11% sulfur are loaded, then the remaining 496 g of MgO + glycol mixture.
  • the carbonated medium is placed under vacuum.
  • the vacuum is broken and 100 g of slaked lime are loaded.
  • the flask is brought to 115 ° C under 346 10 2 Pa, then heated for 1 hour at 140 ° C under 346 10 2 Pa.
  • the glycol is distilled for 2 hours at 190 ° C under 66.5 10 2 Pa.
  • The% of raw sediment is 0.8.
  • Example 13 The operations described in Example 13 are carried out by however introducing the 19 g of ethylenediamine into the 496 g of MgO + glycol mixture.
  • the “milk of magnesia thus obtained is introduced in 3 times into the medium to be carbonated. each introduction being followed by a carbonation step, the interval between each introduction being approximately 1 hour.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP83401254A 1982-06-24 1983-06-17 Nouvel additif détergent-dispersant suralcalinisé pour huiles lubrifiantes Expired EP0102254B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83401254T ATE24545T1 (de) 1982-06-24 1983-06-17 Ueberalkalisierter detergens-dispergierzusatz fuer schmieroele.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8211058 1982-06-24
FR8211058A FR2529224B1 (fr) 1982-06-24 1982-06-24 Nouvel additif detergent-dispersant suralcalinise pour huiles lubrifiantes

Publications (2)

Publication Number Publication Date
EP0102254A1 EP0102254A1 (fr) 1984-03-07
EP0102254B1 true EP0102254B1 (fr) 1986-12-30

Family

ID=9275355

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83401254A Expired EP0102254B1 (fr) 1982-06-24 1983-06-17 Nouvel additif détergent-dispersant suralcalinisé pour huiles lubrifiantes

Country Status (17)

Country Link
US (1) US4464289A (2)
EP (1) EP0102254B1 (2)
JP (1) JPS6025078B2 (2)
AT (1) ATE24545T1 (2)
AU (1) AU559590B2 (2)
BR (1) BR8303302A (2)
CA (1) CA1182626A (2)
DE (1) DE3368679D1 (2)
DK (1) DK289783A (2)
EG (1) EG15959A (2)
ES (1) ES8403962A1 (2)
FR (1) FR2529224B1 (2)
GB (1) GB2123021B (2)
GR (1) GR78594B (2)
PH (1) PH19613A (2)
PT (1) PT76928B (2)
ZA (1) ZA834556B (2)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2564830B1 (fr) * 1984-05-25 1986-09-19 Orogil Procede de preparation d'alkylaryl sulfonates de metaux alcalino-terreux a partir d'acides alkylaryl sulfoniques lineaires et additifs detergents-dispersants pour huiles lubrifiantes ainsi obtenus
FR2588269B1 (fr) * 1985-10-03 1988-02-05 Elf France Procede de preparation d'additifs surbases tres fluides et a basicite elevee et composition contenant lesdits additifs
JPS6281291U (2) * 1985-11-08 1987-05-23
DE3708339A1 (de) * 1987-03-14 1988-09-22 Wintershall Ag Verfahren zur herstellung von basischen magnesiumdialkylbenzolsulfonaten
US5032299A (en) * 1987-07-30 1991-07-16 The Lubrizol Corporation Magnesium overbasing process
US4775490A (en) * 1987-07-30 1988-10-04 The Lubrizol Corporation Magnesium overbasing process
GB8723909D0 (en) * 1987-10-12 1987-11-18 Exxon Chemical Patents Inc Lubricant oil additive
JPH0398821A (ja) * 1989-09-01 1991-04-24 Sanyo Electric Co Ltd 薬剤供給器
GB9611424D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
US5759966A (en) * 1996-10-01 1998-06-02 Chevron Chemical Company High overbased metal sulfurized alkyphenates
US7084092B2 (en) * 2003-08-25 2006-08-01 M-I L.L.C. Shale hydration inhibition agent and method of use
US20080139430A1 (en) * 2006-12-08 2008-06-12 Lam William Y Additives and lubricant formulations for improved antiwear properties

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282835A (en) * 1963-02-12 1966-11-01 Lubrizol Corp Carbonated bright stock sulfonates and lubricants containing them
GB1144084A (en) * 1966-08-24 1969-03-05 Orobis Ltd Improvements in or relating to lubricant additives
US3464970A (en) * 1967-03-13 1969-09-02 Maruzen Oil Co Ltd Process for preparing over-based sulfurized calcium phenates
GB1280749A (en) * 1970-06-18 1972-07-05 Maruzen Oil Company Ltd Process for preparation of over-based sulphurized phenates
GB1399092A (en) * 1971-05-27 1975-06-25 Cooper & Co Ltd Edwin Lubricant additives
US3936480A (en) * 1971-07-08 1976-02-03 Rhone-Progil Additives for improving the dispersing properties of lubricating oil
BE786032A (fr) * 1971-07-08 1973-01-08 Rhone Progil Nouveaux additifs pour huiles lubrifiantes
GB1470338A (en) * 1974-05-17 1977-04-14 Exxon Research Engineering Co Lubricating oil compositions
GB1469289A (en) * 1974-07-05 1977-04-06 Exxon Research Engineering Co Detergent additives
FR2300793A1 (fr) * 1975-02-17 1976-09-10 Orogil Nouvelles compositions lubrifiantes
US4016093A (en) * 1976-03-19 1977-04-05 Mobil Oil Corporation Metal alkylphenate sulfides of reduced corrosiveness and method of preparing same
FR2416942A1 (fr) * 1978-02-08 1979-09-07 Orogil Procede de preparation de detergents-dispersants de haute alcalinite pour huiles lubrifiantes
US4222882A (en) * 1978-02-08 1980-09-16 Rhone-Poulenc Industries Polymers bearing groups derived from N-substituted lactams and their use as lubricating oil additives
US4229308A (en) * 1978-02-08 1980-10-21 Rhone-Poulenc Industries Polymer lubricating oil additives bearing nitrogen groups and their use as additives for lubricating oils
FR2429832A1 (fr) * 1978-06-26 1980-01-25 Orogil Procede perfectionne de preparation d'additifs detergents-dispersants, metalliques de haute alcalinite notamment pour huiles lubrifiantes
FR2429831A2 (fr) * 1978-06-26 1980-01-25 Orogil Nouveau procede de preparation de detergents-dispersants de haute alcalinite pour huiles lubrifiantes
FR2450868A1 (fr) * 1979-03-09 1980-10-03 Orogil Procede de preparation d'alkylphenates de magnesium et application des produits obtenus comme additifs detergents-dispersants pour huiles lubrifiantes

Also Published As

Publication number Publication date
GR78594B (2) 1984-09-27
GB2123021B (en) 1985-06-05
CA1182626A (fr) 1985-02-19
FR2529224A1 (fr) 1983-12-30
ZA834556B (en) 1984-03-28
DK289783D0 (da) 1983-06-23
EG15959A (en) 1987-07-30
PT76928A (fr) 1983-07-01
GB8317021D0 (en) 1983-07-27
DE3368679D1 (en) 1987-02-05
JPS5951997A (ja) 1984-03-26
ES523538A0 (es) 1984-04-01
FR2529224B1 (fr) 1986-02-07
AU1612683A (en) 1984-01-05
DK289783A (da) 1983-12-25
AU559590B2 (en) 1987-03-12
BR8303302A (pt) 1984-02-07
ES8403962A1 (es) 1984-04-01
EP0102254A1 (fr) 1984-03-07
US4464289A (en) 1984-08-07
JPS6025078B2 (ja) 1985-06-15
PH19613A (en) 1986-05-30
PT76928B (fr) 1986-01-24
GB2123021A (en) 1984-01-25
ATE24545T1 (de) 1987-01-15

Similar Documents

Publication Publication Date Title
EP0133088B1 (fr) Procédé de préparation d'additifs détergents-dispersants de très haute alcalinité à base de calcium et produits ainsi obtenus
EP0164286B1 (fr) Procédé de préparation d'additifs détergents-dispersants pour huiles lubrifiantes à base d'alkylarylsulfonates de métaux alcalino-terreux ne moussant pas
EP0007257B1 (fr) Procédé de préparation de détergents-dispersants de haute alcalinité pour huiles lubrifiantes et produit obtenu
EP0102255B1 (fr) Procédé de préparation d'alkylphénates sulfurisés de métaux alcalino-terreux utilisables comme additifs pour huiles lubrifiantes
EP0102254B1 (fr) Nouvel additif détergent-dispersant suralcalinisé pour huiles lubrifiantes
FR2605329A1 (fr) Procede de preparation de derives de metal du groupe 2 d'alkylphenols sulfures rendus surbasiques.
EP0003694B1 (fr) Procédé de préparation de détergents-dispersants de haute alcalinité pour huiles lubrifiantes et produit obtenu
FR2917421A1 (fr) Additifs et formulations de lubrifiants pour ameliorer les proprietes antiusure.
EP0007260B1 (fr) Procédé perfectionné de préparation d'additifs détergents dispersants métalliques de haute alcalinité notamment pour huiles lubrifiantes et produit obtenu
EP0101334B1 (fr) Nouvel additif détergent-dispersant métallique de haute alcalinité pour huiles lubrifiantes
EP0812313B1 (en) Low base number sulphonates
EP0812314B1 (en) Magnesium low base number sulphonates
EP0006796B1 (fr) Procédé de préparation de détergents-dispersants métalliques suralcalinisés pour huiles lubrifiantes et produits obtenus
EP0308445B1 (fr) Procede de preparation d'un additif suralcanilise renfermant un derive inorganique du bore, l'additif ainsi obtenu et compositions lubrifiantes renfermant ledit additif
FR2909684A1 (fr) Additifs et formulations de lubrifiants utilises pour obtenir des proprietes antiusure ameliorees
JP2598489B2 (ja) 過塩基マグネシウムスルホン酸塩組成物
CA1269973A (fr) Additifs detergents-dispersants sulfones et sulfurises pour huiles lubrifiantes
JPH0292993A (ja) 過塩基化アルカリ金属スルホネート

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

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

17P Request for examination filed

Effective date: 19840322

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 24545

Country of ref document: AT

Date of ref document: 19870115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3368679

Country of ref document: DE

Date of ref document: 19870205

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

Ref country code: AT

Payment date: 19910610

Year of fee payment: 9

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

Ref country code: SE

Payment date: 19910614

Year of fee payment: 9

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

Ref country code: CH

Payment date: 19910619

Year of fee payment: 9

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

Ref country code: BE

Payment date: 19910624

Year of fee payment: 9

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

Ref country code: DE

Payment date: 19910628

Year of fee payment: 9

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: NL

Payment date: 19910630

Year of fee payment: 9

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

Ref country code: AT

Effective date: 19920617

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

Ref country code: SE

Effective date: 19920618

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

Ref country code: LI

Effective date: 19920630

Ref country code: CH

Effective date: 19920630

Ref country code: BE

Effective date: 19920630

BERE Be: lapsed

Owner name: OROGIL

Effective date: 19920630

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

Ref country code: NL

Effective date: 19930101

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: DE

Effective date: 19930302

EUG Se: european patent has lapsed

Ref document number: 83401254.4

Effective date: 19930109

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

Ref country code: FR

Payment date: 20020605

Year of fee payment: 20