EP0016676A1 - Process for the preparation of magnesium alkyl phenates - Google Patents

Process for the preparation of magnesium alkyl phenates Download PDF

Info

Publication number
EP0016676A1
EP0016676A1 EP80400270A EP80400270A EP0016676A1 EP 0016676 A1 EP0016676 A1 EP 0016676A1 EP 80400270 A EP80400270 A EP 80400270A EP 80400270 A EP80400270 A EP 80400270A EP 0016676 A1 EP0016676 A1 EP 0016676A1
Authority
EP
European Patent Office
Prior art keywords
active
magnesium oxide
weight
moles
phenolic
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.)
Granted
Application number
EP80400270A
Other languages
German (de)
French (fr)
Other versions
EP0016676B1 (en
Inventor
Jean-Pierre Tassara
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 AT80400270T priority Critical patent/ATE1647T1/en
Publication of EP0016676A1 publication Critical patent/EP0016676A1/en
Application granted granted Critical
Publication of EP0016676B1 publication Critical patent/EP0016676B1/en
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
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

Definitions

  • the present invention relates to a process for the preparation of magnesium alkylphenates, the products obtained according to the process and the application of said products as detergent-dispersant additives for lubricating oils.
  • Such a process uses not an alkylphenol alone but an alkylphenol-sulfonic acid mixture which is easier to neutralize and requires the presence of a promoter.
  • the Applicant has found a process making it possible to prepare magnesium alkylphenates using an alkylphenol alone (that is to say not mixed with a sulfonic acid), active magnesia and which does not require the use of a promoter.
  • active magnesium oxide denotes magnesium oxide which can be obtained by gentle calcination of the basic magnesium carbonate, for example at a temperature of the order of 500 to 700 ° C. for at least 3 hours; the specific surface of this type of oxide is greater than 80 m 2 / g and generally greater than 100 m2 / g.
  • alkylphenol denotes both non-alkylphenols sulfurized than sulfurized alkylphenols.
  • alkylphenols which can be used, mention may be made of those bearing 1 or more C 9 -C 15 substituents, in particular nonyl, decyl, dodecyl and tetradecylphenols, optionally sulfurized.
  • paraffinic oils such as 100 Neutral oil
  • naphthenic or mixed oils may also be suitable.
  • heavy alcohols that can be used, mention may preferably be made of isobutanol, hexanol or 2-ethylhexanol.
  • the operation of suspending the “active” magnesium oxide in methanol takes place favorably at ordinary temperature.
  • the contacting and carbonation operations can be carried out at a temperature between 0 and 40 ° C. preferably between 15 and 30 ° C.
  • the operations described above may optionally be followed by a water treatment operation, in particular when a ratio of the number of moles of “active” magnesium oxide / number of phenolic OH units greater than 1 has been set. in use and if one seeks to reduce the viscosity of the product obtained.
  • This water treatment can be carried out in a conventional manner using 1 to 2 moles of water per mole of "active" magnesium oxide employed.
  • the present invention also relates to the magnesium alkylphenates obtained according to the process described above, as well as the application of said alkylphenates as detergent-dispersant additives for lubricating oils.
  • the amount of alkylphenates to be added to petrol engine oils is generally of the order of 1 to 4% by weight; that to be added in diesel engine oils is generally of the order of 1 to 8% by weight.
  • the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as lubricating oils of naphthenic base, of paraffinic base, and of mixed base, of other hydrocarbon lubricants, for example lubricating oils derived from coal products, 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 liquid acids phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenyl ethers, polymers of silicon.
  • lubricating oils such as lubricating oils of naphthenic base, of paraffinic base, and of mixed base, of other hydrocarbon lubricants, for example lubricating oils derived from coal products, and synthetic oils, for example alkylene
  • Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives .
  • the alkylphenol used is presulfurized paradodecyl phenol (A) containing 11.5% of sulfur (obtained by sulfurization with sulfur).
  • the “active” magnesium oxide (B) used has a specific surface of 145 m 2 / g and a purity in MgO of 90%.
  • the phenolic MgO / OH molar ratio used is 0.5.
  • the amount of active MgO is 9% compared to methanol
  • the amount of dilution oil is 68.3% relative to the alkylphenol.
  • a suspension of 11 g of the active magnesium oxide (B) (ie 0.25 mol) in 120 g of methanol is prepared separately and this suspension is added to the preceding mixture.
  • the mixture thus obtained is then carbonated at 20 ° C with stirring by introducing into the reactor carbon dioxide under a pressure of 10 kg / cm 2 for 8 hours.
  • the apparatus is brought back to atmospheric pressure and the methanol is removed by distillation, raising gradually the temperature up to 180 ° C.
  • Example 1 We repeat Example 1 but without first preparing the suspension of magnesium oxide in methanol and by loading all the constituents of the mixture without special precautions.
  • Example 1 The operation described in Example 1 is carried out in the presence of an amount of "active" Mg0 corresponding to 5% by weight of methanol.
  • the suspension of "active" MgO thus consists of 11 g of active MgO (ie 0.25 mole) in 220 g of methanol.
  • a suspension of 22 g of active magnesium oxide (B) (ie 0.5 mole) in 250 g of methanol is prepared and this suspension is added to the preceding mixture.
  • the mixture is carbonated for 10 hours at room temperature under a pressure of 10 kg / cm 2 of carbon dioxide.
  • a suspension of 19 g of active magnesium oxide ( B ) (i.e. 0.425 mole) in 220 g of methanol is prepared and we add this suspension to the preceding mixture.
  • the mixture is carbonated for 10 hours at room temperature under a pressure of 12 kg / cm 2 of carbon dioxide.
  • a suspension of 13 g of active magnesium oxide B (ie 0.3 mole) in 150 g of methanol is prepared and this suspension is added to the preceding mixture.
  • the resulting mixture is carbonated for 8 hours at room temperature under a pressure of 12 kg / cm 2 of carbon dioxide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

A method of preparing magnesium alkylphenates comprising: 1. preparing a suspension of "active" magnesium oxide in methanol; 2. contacting said suspension with a mixture containing (a) an alkylphenol bearing one or more C6-C60 alkyl substituents; (b) a dilution oil; (c) and optionally a heavy alcohol of a boiling point of between 100 DEG and 200 DEG C., the ratio of number of mols of "active" magnesium oxide to number of recurrent phenolic OH units being between about 0.25 and 2; and 3. carbonating the resultant medium under pressure with carbon dioxide. The magnesium alkylphenates thus obtained are suitable detergent-dispersant additives for lubricating oils in amounts of between about 1 and 8 percent of the weight of the oils.

Description

La présente invention a pour objet un procédé de préparation d'alkylphénates de magnésium, les produits obtenus selon le procédé et l'application desdits produits comme additifs détergents-dispersants pour huiles lubrifiantes.The present invention relates to a process for the preparation of magnesium alkylphenates, the products obtained according to the process and the application of said products as detergent-dispersant additives for lubricating oils.

Il est connu d'après les brevets américains n° 3.718.589 et 3.932.289 de préparer des alkylphénates de magnésium à partir d'alkylphénols, en utilisant des alcoolates de magnésium carbonatés comme agents de neutralisation ou de suralcalinisation. De tels procédés sont coûteux et délicats du fait que les alcoolates de magnésium carbonatés sont préparés à partir de magnésium métallique.It is known from US Pat. Nos. 3,718,589 and 3,932,289 to prepare magnesium alkylphenates from alkylphenols, using carbonated magnesium alcoholates as neutralizing or over-alkalizing agents. Such processes are expensive and delicate because the carbonated magnesium alcoholates are prepared from metallic magnesium.

Il est également connu d'après le brevet français n° 2.277.145 de préparer des alkylphénates de magnésium par carbonatation d'un mélange contenant un alkylphénol éventuellement sulfurisé, un acide sulfonique, un alcool, de l'hydroxyde de magnésium ou de la magnésie active ainsi qu'un promoteur du type sel d'ammonium d'acide carboxylique.It is also known from French Patent No. 2,277,145 to prepare magnesium alkylphenates by carbonation of a mixture containing an optionally sulfurized alkylphenol, a sulfonic acid, an alcohol, magnesium hydroxide or magnesia active as well as a promoter of the ammonium salt type of carboxylic acid.

Un tel procédé met en oeuvre non pas un alkylphénol seul mais un mélange alkylphénol-acide sulfonique plus facile à neutraliser et nécessite la présence d'un promoteur.Such a process uses not an alkylphenol alone but an alkylphenol-sulfonic acid mixture which is easier to neutralize and requires the presence of a promoter.

La demanderesse a trouvé un procédé permettant de préparer des alkylphénates de magnésium en utilisant un alkylphénol seul (c'est-à-dire non mélangé à un acide sulfonique), de la magnésie active et ne nécessitant pas l'emploi d'un promoteur.The Applicant has found a process making it possible to prepare magnesium alkylphenates using an alkylphenol alone (that is to say not mixed with a sulfonic acid), active magnesia and which does not require the use of a promoter.

Le procédé de préparation d'alkylphénates de magnésium, faisant l'objet de l'invention, est caractérisé en ce que :

  • 1) On prépare une suspension d'oxyde de magnésium "actif" dans du méthanol, ladite suspension pouvant contenir jusqu'à 10 % en poids d'oxyde de magnésium "actif" par rapport au poids du méthanol,
  • 2) On met en contactt ladite suspension avec un mélange contenant :
    • - un alkylphénol portant un ou plusieurs substituants alkyles en C6-C60,
    • - une huile de dilution,
    • - un alcool lourd de point d'ébullition compris entre 100 et 200°C, le rapport nombre de moles d'oxyde de magnésium "actif"/ nombre de motifs OH phénoliques étant compris entre 0,25 et 2, la quantité d'huile de dilution étant comprise entre 0 et 140 % en poids par rapport au poids d'alkylphénol et le rapport molaire alcool lourd/ oxyde de magnésium "actif" étant compris entre 0 et 4, ledit rapport molaire étant d'au moins 1,2 lorsque le rapport nombre de moles d'oxyde de magnésium "actif"/nombre de motifs 0H phénoliques est supérieur à 0,75.
  • 3) Et on carbonate sous pression le milieu obtenu à l'aide de gaz carbonique.
The process for the preparation of magnesium alkylphenates, which is the subject of the invention, is characterized in that:
  • 1) A suspension of "active" magnesium oxide in methanol is prepared, said suspension possibly containing up to 10% by weight of "active" magnesium oxide relative to the weight of methanol,
  • 2) is contacted with t said slurry a mixture containing:
    • an alkylphenol carrying one or more C 6 -C 60 alkyl substituents,
    • - a dilution oil,
    • a heavy alcohol with a boiling point of between 100 and 200 ° C., the ratio number of moles of "active" magnesium oxide / number of phenolic OH units being between 0.25 and 2, the amount of oil dilution being between 0 and 140% by weight relative to the weight of alkylphenol and the molar ratio heavy alcohol / magnesium oxide "active" being between 0 and 4, said molar ratio being at least 1.2 when the number of moles of "active" magnesium oxide / number of phenolic OH units is greater than 0.75.
  • 3) And the medium obtained is carbonated under pressure using carbon dioxide.

Pour une bonne réalisation du procédé, on mettra en oeuvre préférentiellement :

  • - de 5 à 10 % en poids d'oxyde de magnésium "actif" par rapport au poids de méthanol ;
  • - un rapport nombre de moles d'oxyde de magnésium "actif"/ nombre de motifs OH phénoliques compris entre 0,5 et 1 ;
  • - de 20 à 75 % en poids d'huile de dilution par rapport au poids d'alkylphénol ;
  • - un rapport molaire alcool lourd/oxyde de magnésium "actif" d'au moins 1,5 lorsque le rapport nombre de moles d'oxyde de magnésium "actif"/nombre de motifs OH phénoliques est supérieur à 0,75 ; et on réalisera l'opération de carbonatation pendant au moins 4 heures sous une pression comprise entre 3 et 30 kg/cm2, plus particulièrement entre 5 et 15 kg/cm2, avec une quantité de C02 correspondant, à plus ou moins 30 % en poids près, à celle pouvant être complètement absorbée par le milieu ; en général cette quantité de CO2 correspondra sensiblement à celle pouvant être complètement absorbée.
For a good implementation of the process, preferably:
  • - from 5 to 10% by weight of "active" magnesium oxide relative to the weight of methanol;
  • - A ratio of the number of moles of "active" magnesium oxide / number of phenolic OH units of between 0.5 and 1;
  • - from 20 to 75% by weight of dilution oil relative to the weight of alkylphenol;
  • - A molar ratio of heavy alcohol / "active" magnesium oxide of at least 1.5 when the number of moles of "active" magnesium oxide / number of phenolic OH units is greater than 0.75; and the carbonation operation will be carried out for at least 4 hours under a pressure of between 3 and 30 kg / cm 2 , more particularly between 5 and 15 kg / cm 2 , with an amount of C0 2 corresponding to more or less 30 % by weight, to that which can be completely absorbed by the medium; in general, this quantity of CO 2 will correspond substantially to that which can be completely absorbed.

On désigne par oxyde de magnésium "actif", de l'oxyde de magnésium pouvant être obtenu par calcination douce du carbonate basique de magnésium, par exemple à une température de l'ordre de 500 à 700°C pendant au moins 3 heures ; la surface spécifique de ce type d'oxyde est supérieure à 80 m2/g et généralement supérieure à 100 m2/g.The term “active” magnesium oxide denotes magnesium oxide which can be obtained by gentle calcination of the basic magnesium carbonate, for example at a temperature of the order of 500 to 700 ° C. for at least 3 hours; the specific surface of this type of oxide is greater than 80 m 2 / g and generally greater than 100 m2 / g.

On désigne par alkylphénol aussi bien les alkylphénols non sulfurisés que les alkylphénols sulfurisés. Parmi les alkylphénols pouvant être mis en oeuvre on peut citer ceux portant 1 ou plusieurs substituants en C9-C15, en particulier les nonyl, décyl, dodécyl et tétradécylphénols, éventuellement sulfurisés.The term “alkylphenol” denotes both non-alkylphenols sulfurized than sulfurized alkylphenols. Among the alkylphenols which can be used, mention may be made of those bearing 1 or more C 9 -C 15 substituents, in particular nonyl, decyl, dodecyl and tetradecylphenols, optionally sulfurized.

Parmi les huiles de dilution pouvant être mises en oeuvre, on peut citer de préférence les huiles paraffiniques telles que l'huile 100 Neutral ; les huiles naphténiques ou mixtes peuvent également convenir.Among the dilution oils which can be used, mention may preferably be made of paraffinic oils such as 100 Neutral oil; naphthenic or mixed oils may also be suitable.

Parmi les alcools lourds pouvant être mis en oeuvre on peut citer de préférence l'isobutanol, l'hexanol ou l'éthyl-2 hexanol.Among the heavy alcohols that can be used, mention may preferably be made of isobutanol, hexanol or 2-ethylhexanol.

L'opération de mise en suspension de l'oxyde de magnésium "actif" dans le méthanol se déroule favorablement à température ordinaire. Les opérations de mise en contact et de carbonatation peuvent être réalisées à une température comprise entre 0 et 40°C de préférence entre 15 et 30°C.The operation of suspending the “active” magnesium oxide in methanol takes place favorably at ordinary temperature. The contacting and carbonation operations can be carried out at a temperature between 0 and 40 ° C. preferably between 15 and 30 ° C.

Les opérations ci-dessus décrites peuvent éventuellement être suivies d'une opération de traitement à l'eau, en particulier lorsqu'un rapport nombre de moles d'oxyde de magnésium "actif"/ nombre de motifs OH phénoliques supérieur à 1 a été mis en oeuvre et si l'on cherche à diminuer la viscosité du produit obtenu. Ce traitement à l'eau peut être réalisé d'une manière classique à l'aide de 1 à 2 moles d'eau par mole d'oxyde de magnésium "actif" engagé.The operations described above may optionally be followed by a water treatment operation, in particular when a ratio of the number of moles of “active” magnesium oxide / number of phenolic OH units greater than 1 has been set. in use and if one seeks to reduce the viscosity of the product obtained. This water treatment can be carried out in a conventional manner using 1 to 2 moles of water per mole of "active" magnesium oxide employed.

La présente invention a également pour objet les alkylphénates de magnésium obtenus selon le procédé ci-dessus décrit, ainsi que l'application desdits alkylphénates comme additifs détergents-dispersants pour huiles lubrifiantes. La quantité d'alkylphénates à ajouter dans les huiles pour moteur essence est généralement de l'ordre de 1 à 4 % en poids ; celle à ajouter dans les huiles pour moteur diesel est généralement de l'ordre de 1 à 8 % en poids.The present invention also relates to the magnesium alkylphenates obtained according to the process described above, as well as the application of said alkylphenates as detergent-dispersant additives for lubricating oils. The amount of alkylphenates to be added to petrol engine oils is generally of the order of 1 to 4% by weight; that to be added in diesel engine oils is generally of the order of 1 to 8% by weight.

Les huiles lubrifiantes que l'on peut ainsi améliorer peuvent être choisies parmi des huiles lubrifiantes très variées, comme les huiles lubrifiantes de base naphténique, de base paraffinique, et de base mixte, d'autres lubrifiants hydrocarbonés, par exemple des huiles lubrifiantes dérivées de produits de la houille, et des huiles synthétiques, par exemple des polymères d'alkylène, des polymères du type oxyde d'alkylène et leurs dérivés, y compris les polymères d'oxyde d'alkylène préparés en polymérisant de l'oxyde d'alkylëne en présence d'eau ou d'alcools, par exemple d'alcool éthylique, les esters d'acides dicarboxyliques, des esters liquides d'acides liquides d'acides du phosphore, des alkylbenzènes et des dialkylbenzënes, des polyphényles, des alkylbiphényl éthers, des polymères du silicium.The lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as lubricating oils of naphthenic base, of paraffinic base, and of mixed base, of other hydrocarbon lubricants, for example lubricating oils derived from coal products, 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 liquid acids phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenyl ethers, polymers of silicon.

Des additifs supplémentaires peuvent également être présents dans lesdites huiles lubrifiantes à côté des détergents-dispersants obtenus selon le procédé de l'invention ; on peut citer par exemple des additifs anti-oxydants, anti-corrosion, des additifs dispersants sans cendres.......Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives .......

Les exemples suivants sont donnés à titre indicatif et ne peuvent être considérés comme une limite du domaine et de l'esprit de l'invention.The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention.

EXEMPLE 1EXAMPLE 1

L'alkylphénol utilisé est du paradodécyl phénol présul- furisé (A) contenant 11,5 % de soufre (obtenu par sulfurisation au soufre).The alkylphenol used is presulfurized paradodecyl phenol (A) containing 11.5% of sulfur (obtained by sulfurization with sulfur).

L'oxyde de magnésium "actif" (B) utilisé présente une surface spécifique de 145 m2/g et une pureté en Mg0 de 90 %.The “active” magnesium oxide (B) used has a specific surface of 145 m 2 / g and a purity in MgO of 90%.

Le rapport molaire MgO/OH phénolique utilisé est de 0,5.The phenolic MgO / OH molar ratio used is 0.5.

La quantité de MgO actif est de 9 % par rapport au méthanolThe amount of active MgO is 9% compared to methanol

La quantité d'huile de dilution est de 68,3 % par rapport à l'alkylphénol.The amount of dilution oil is 68.3% relative to the alkylphenol.

Dans un réacteur d'un litre résistant à des pressions de 35 kg/cm2 et équipé d'un système d'agitation, on charge :

  • - 146 g de paradodécyl phénol sulfurisé (A) (soit environ 0,5 mole de OH phénolique)
  • - 100 g d'huile 100 Neutral de dilution.
In a one liter reactor resistant to pressures of 35 kg / cm 2 and equipped with a stirring system, the following are charged:
  • - 146 g of sulfurized paradodecyl phenol (A) (i.e. approximately 0.5 mole of phenolic OH)
  • - 100 g of 100 Neutral dilution oil.

On prépare séparément une suspension de 11 g de l'oxyde de magnésium actif (B) (soit 0,25 mole) dans 120 g de méthanol et on additionne cette suspension au mélange précédent.A suspension of 11 g of the active magnesium oxide (B) (ie 0.25 mol) in 120 g of methanol is prepared separately and this suspension is added to the preceding mixture.

Le mélange ainsi obtenu est alors carbonaté à 20°C sous agitation en introduisant dans le réacteur de l'anhydride carbonique sous une pression de 10 kg/cm2 pendant 8 heures.The mixture thus obtained is then carbonated at 20 ° C with stirring by introducing into the reactor carbon dioxide under a pressure of 10 kg / cm 2 for 8 hours.

Au bout de ce temps l'appareillage est ramené à pression atmosphérique et le méthanol est éliminé par distillation en élevant progressivement la température jusqu'à 180°C.At the end of this time, the apparatus is brought back to atmospheric pressure and the methanol is removed by distillation, raising gradually the temperature up to 180 ° C.

On obtient ainsi 260 g d'un alkylphénate de magnésium exempt de sédiments contenant 2,3 % de magnésium, 2 % de CO2, dont le taux de suralcalinisation apparent est égal à 1 et présentant un TBN de 110 mg KOH/g (Total Basic Number - Norme ASTM D 2896).260 g of a sediment-free magnesium alkylphenate are thus obtained containing 2.3% magnesium, 2% CO 2 , the apparent rate of over-alkalinization is 1 and having a TBN of 110 mg KOH / g (Total Basic Number - Standard ASTM D 2896).

EXEMPLE 2 (Comparatif)EXAMPLE 2 (Comparative)

Nous répétons l'exemple 1 mais sans préparer préalablement la suspension d'oxyde de magnésium dans le méthanol et en chargeant tous les constituants du mélange sans précautions particulières.We repeat Example 1 but without first preparing the suspension of magnesium oxide in methanol and by loading all the constituents of the mixture without special precautions.

Après 8 heures de carbonatation sous 10 kg/cm2 de pression et après élimination du méthanol nous obtenons un mélange contenant encore en suspension la quasi totalité de l'oxyde de magnésium chargé qui rend le produit infiltrable.After 8 hours of carbonation under 10 kg / cm 2 of pressure and after elimination of the methanol we obtain a mixture still containing almost all of the magnesium oxide charged which makes the product infiltrable.

EXEMPLE 3EXAMPLE 3

L'opération décrite à l'exemple 1 est réalisée en présence d'une quantité de Mg0 "actif" correspondant à 5 % en poids du méthanol.The operation described in Example 1 is carried out in the presence of an amount of "active" Mg0 corresponding to 5% by weight of methanol.

La suspension de MgO "actif" est ainsi constituée de 11 g de MgO actif (soit 0,25 mole) dans 220 g de méthanol.The suspension of "active" MgO thus consists of 11 g of active MgO (ie 0.25 mole) in 220 g of methanol.

On obtient 270 g d'alkylphénate sulfurisé de magnésium présentant un TBN de 90 mg, contenant 2 % de magnésium et 1,8 % de CO2.270 g of sulfurized magnesium alkylphenate with a TBN of 90 mg are obtained, containing 2% magnesium and 1.8% CO 2 .

EXEMPLE 4EXAMPLE 4

  • - Rapport molaire MgO actif/OH phénolique utilisé : 1- Active MgO / phenolic OH molar ratio used: 1
  • - quantité de MgO actif : 8,8 % par rapport au poids du méthanol- amount of active MgO: 8.8% relative to the weight of methanol
  • - quantité d'huile de dilution : 68,3 % par rapport à l'alkylphénol- amount of dilution oil: 68.3% compared to the alkylphenol
  • - rapport molaire hexanol/MgO actif : 3- active hexanol / MgO molar ratio: 3

On charge :

  • - 146 g de paradodécyl phénol sulfurisé (A) (soit environ 0,5 mole de OH phénolique) ;
  • - 100 g d'huile 100 Neutral de dilution ;
  • - 150 g de n hexanol.
We charge:
  • - 146 g of sulfurized paradodecyl phenol (A) (or approximately 0.5 mole of phenolic OH);
  • - 100 g of 100 Neutral dilution oil;
  • - 150 g of n hexanol.

On prépare une suspension de 22 g d'oxyde de magnésium actif (B) (soit 0,5 mole) dans 250 g de méthanol et on ajoute cette suspension au mélange précédent.A suspension of 22 g of active magnesium oxide (B) (ie 0.5 mole) in 250 g of methanol is prepared and this suspension is added to the preceding mixture.

Le mélange est carbonaté pendant 10 heures à température ambiante sous une pression de 10 kg/cm2 d'anhydride carbonique.The mixture is carbonated for 10 hours at room temperature under a pressure of 10 kg / cm 2 of carbon dioxide.

Au bout de ce temps le mélange est ramené à pression atmos- phérique et les alcools sont éliminés par distillation en chauffant le produit jusqu'à 180°C sous vide pour bien éliminer l'hexanol.At the end of this time the mixture is brought back to atmospheric pressure. p h e r ic and alcohols are removed by distillation by heating the product to 180 ° C under vacuum to remove well hexanol.

On obtient ainsi 270 g de produit brut que l'on filtre sur 20 g de terre de filtration à l'aide de 20 g d'huile 100 Neutral supplémentaire.270 g of crude product are thus obtained, which is filtered through 20 g of filter earth using 20 g of additional 100 Neutral oil.

On récupère ainsi 270 g de produit fini présentant un TBN de 170 mg et contenant : 3,7 %de magnésium et 3,5 % de CO2 tandis que 20 g de produit brut restent absorbés sur le gâteau de filtration.270 g of finished product are thus recovered, having a TBN of 170 mg and containing: 3.7% of magnesium and 3.5% of CO 2, while 20 g of crude product remain absorbed on the filter cake.

EXEMPLE 5EXAMPLE 5

  • - Rapport molaire Mg0 actif/OH phénolique : 0,85- Active Mg0 / phenolic OH molar ratio: 0.85
  • - Rapport molaire hexanol/Mg0 actif : 1,5- Active hexanol / Mg0 molar ratio: 1.5
  • - Quantité de Mg0 actif : 8,6 % par rapport au poids de méthanol- Quantity of active Mg0: 8.6% relative to the weight of methanol
  • - Quantité d'huile de dilution : 68,3 % par rapport à l'alkylphénol.- Amount of dilution oil: 68.3% compared to the alkylphenol.

On charge :

  • - 146 g du paradodécyl phénol sulfurisé (A) (soit environ 0,5 mole) de 0H phénolique ;
  • - 100 g d'huile 100 Neutral de dilution ;
  • - 65 g de n-hexanol.
We charge:
  • - 146 g of sulfurized paradodecyl phenol (A) (ie approximately 0.5 mol) of phenolic OH;
  • - 100 g of 100 Neutral dilution oil;
  • - 65 g of n-hexanol.

On prépare une suspension de 19 g d'oxyde de magnésium actif (B) (soit 0,425 mole) dans 220 g de méthanol et nous ajoutons cette suspension au mélange précédent.A suspension of 19 g of active magnesium oxide ( B ) (i.e. 0.425 mole) in 220 g of methanol is prepared and we add this suspension to the preceding mixture.

Le mélange est carbonaté pendant 10 heures à température ambiante sous une pression de 12 kg/cm2 d'anhydride carbonique.The mixture is carbonated for 10 hours at room temperature under a pressure of 12 kg / cm 2 of carbon dioxide.

0n revient à pression atmosphérique, on distille les produits volatils en chauffant jusqu'à 180°C sous vide.0n returns to atmospheric pressure, volatile products are distilled by heating to 180 ° C under vacuum.

On récupère 270 g de produit brut que l'on filtre sur 20 g de terre de filtration à l'aide de 20 g d'huile de dilution supplémentaire.270 g of crude product are recovered which are filtered through 20 g of filter earth using 20 g of additional dilution oil.

On obtient ainsi 273 g de produit fini présentant un TBN de 160 mg et contenant 3,4 % de magnésium et 3 % de CO2.273 g of finished product are thus obtained having a TBN of 160 mg and containing 3.4% magnesium and 3% CO 2 .

EXEMPLE 6EXAMPLE 6

  • - Rapport molaire Mg0 actif/OH phénolique : 0,5- Active Mg0 / phenolic OH molar ratio: 0.5
  • - Quantité de Mg0 actif : 8,66 % par rapport au poids de méthanol- Quantity of active Mg0: 8.66% relative to the weight of methanol
  • - Quantité d'huile de dilution : 45,5 % par rapport à l'alkylphénol.- Quantity of dilution oil: 45.5% compared to the alkylphenol.

On charge

  • - 176 g de paradodécyl phénol sulfurisé (A) (soit environ 0,6 mole en OH phénolique) ;
  • - 80 g d'huile 100 Neutral de dilution.
We charge
  • - 176 g of sulfurized paradodecyl phenol (A) (ie approximately 0.6 mole of phenolic OH);
  • - 80 g of 100 Neutral dilution oil.

On prépare une suspension de 13 g d'oxyde de magnésium actif B (soit 0,3 mole) dans 150 g de méthanol et on ajoute cette suspension au mélange précédent.A suspension of 13 g of active magnesium oxide B (ie 0.3 mole) in 150 g of methanol is prepared and this suspension is added to the preceding mixture.

Le mélange résultant est carbonaté pendant 8 heures à température ambiante sous une pression de 12 kg/cm2 d'anhydride carbonique.The resulting mixture is carbonated for 8 hours at room temperature under a pressure of 12 kg / cm 2 of carbon dioxide.

On revient à pression atmosphérique, on distille le méthanol et on récupère ainsi 278 g d'un produit brut que l'on filtré à l'aide de 20 g de terre et 20 g d'huile.Return to atmospheric pressure, distill the methanol and thus recover 278 g of a crude product which is filtered using 20 g of earth and 20 g of oil.

On récupère 276 g d'alkylphénate de magnésium présentant un TBN de 110 mg et contenant 2,3 % de magnésium et 1,9 % de CO2.276 g of magnesium alkylphenate having a TBN of 110 mg and containing 2.3% of magnesium and 1.9% of CO 2 are recovered.

Claims (8)

1) Procédé de préparation d'alkylphénates de magnésium, caractérisé en ce que : a) on prépare une suspension d'oxyde de magnésium "actif" dans du méthanol, ladite suspension contenant jusqu'à 10 % en poids d'oxyde de magnésium "actif" par rapport au poids du méthanol. b) on met en contact ladite suspension avec un mélange contenant : - un alkylphénol portant un ou plusieurs substituants alkyles en C6-C60. - une huile de dilution, - un alcool lourd de point d'ébullition compris entre 100 et 200°C, le rapport nombre de moles d'oxyde de magnésium "actif"/ nombre de motifs OH phénoliques étant compris entre 0,25 et 2, la quantité d'huile de dilution étant comprise entre 0 et 140 % en poids par rapport au poids d'alkylphénol et le rapport molaire alcool lourd/oxyde de magnésium "actif" étant compris entre 0 et 4, ledit rapport molaire étant d'au moins 1,2 lorsque le rapport nombre de moles d'oxyde de magnésium "actif"/nombre de motifs OH phénoliques est supérieur à 0,75. c) et on carbonate sous presiori le milieu obtenu à l'aide de gas carbonique. 1) Process for the preparation of magnesium alkylphenates, characterized in that: a) a suspension of "active" magnesium oxide in methanol is prepared, said suspension containing up to 10% by weight of "active" magnesium oxide relative to the weight of methanol. b) said suspension is brought into contact with a mixture containing: an alkylphenol carrying one or more C 6 -C 60 alkyl substituents. - a dilution oil, a heavy alcohol with a boiling point of between 100 and 200 ° C., the ratio number of moles of "active" magnesium oxide / number of phenolic OH units being between 0.25 and 2, the amount of oil dilution being between 0 and 140% by weight relative to the weight of alkylphenol and the molar ratio heavy alcohol / magnesium oxide "active" being between 0 and 4, said molar ratio being at least 1.2 when the number of moles of "active" magnesium oxide / number of phenolic OH units is greater than 0.75. c) and the medium obtained is carbonated under preiori using carbon dioxide. 2) Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre : - de 5 à 10 % en poids d'oxyde de magnésium "actif" par rapport au poids de méthanol ; - un rapport nombre de moles d'oxyde de magnésium "actif"/nombre de motifs OH phénoliques compris entre 0,5 et 1 ; - de 20 à 75 % en poids d'huile de dilution par rapport au poids d'alkylphénol ; - un rapport molaire alcool lourd/oxyde de magnésium "actif" d'au moins 1,5 lorsque le rapport nombre de moles d'oxyde de magnésium "actif/nombre de motifs OH phénoliques est supérieur à 0,75 ;
et en ce que l'on réalise l'opération de carbonatation avec une quantité de CO2 correspondant, à plus ou moins 30 % en poids près, celle pouvant être complètement absorbée par le milieu.2) Method according to claim 1, characterized in that one implements: - from 5 to 10% by weight of "active" magnesium oxide relative to the weight of methanol; - A ratio of the number of moles of "active" magnesium oxide / number of phenolic OH units of between 0.5 and 1; - from 20 to 75% by weight of dilution oil relative to the weight of alkylphenol; - A molar ratio of heavy alcohol / "active" magnesium oxide of at least 1.5 when the number of moles of "active" magnesium oxide / number of phenolic OH units is greater than 0.75;
and in that the carbonation operation is carried out with an amount of CO 2 corresponding, to within approximately 30% by weight, that which can be completely absorbed by the medium. 3) Procédé selon la revendication 1, ou la revendication 2, caractérisé en ce que l'opération de carbonatation est réalisée pendant au moins 4 heures à une pression comprise entre 3 et 30 kg/cm2 et à une température comprise entre 0 et 40cC.3) Method according to claim 1, or claim 2, characterized in that the carbonation operation is carried out for at least 4 hours at a pressure between 3 and 30 kg / cm 2 and at a temperature between 0 and 40cC. 4) Procédé selon la revendication 3 caractérisé en ce que l'opération de carbonatation est réalisée à une pression comprise entre 5 et 15 kg/cm3, à une température comprise entre 15 et 30°C et avec une quantité de CO2 correspondant sensiblement à celle pouvant être complètement absorbée.4) Method according to claim 3 characterized in that the carbonation operation is carried out at a pressure between 5 and 15 kg / cm 3 , at a temperature between 15 and 30 ° C and with an amount of CO 2 corresponding substantially to that which can be completely absorbed. 5) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que les alkylphénols mis en oeuvre portent un ou plusieurs substituants alkyles en C9-C15 et sont sulfurisés ou non.5) Process according to any one of the preceding claims, characterized in that the alkylphenols used carry one or more C 9 -C 15 alkyl substituents and are sulfurized or not. 6) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'alcool lourd mis en oeuvre est l'isobutanol, l'hexanol ou l'éthyl-2 hexanol.6) Process according to any one of the preceding claims, characterized in that the heavy alcohol used is isobutanol, hexanol or 2-ethylhexanol. 7) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'opération de carbonatation est suivie d'un traitement par 1 à 2 moles d'eau par mole d'oxyde de magnésium "actif" engagé lorsque le rapport nombre de moles d'oxyde de magnésium "actif"/ nombre de motifs OH phénoliques est supérieur à 1.7) Method according to any one of the preceding claims, characterized in that the carbonation operation is followed by a treatment with 1 to 2 moles of water per mole of "active" magnesium oxide engaged when the number of moles of "active" magnesium oxide / number of phenolic OH units is greater than 1. 8) Additifs pour huiles lubrifiantes obtenus selon le procédé faisant l'obiet de l'une quelconque des revendications précédentes.8) Additives for lubricating oils obtained according to the process forming the subject of any one of the preceding claims.
EP80400270A 1979-03-09 1980-02-27 Process for the preparation of magnesium alkyl phenates Expired EP0016676B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80400270T ATE1647T1 (en) 1979-03-09 1980-02-27 PROCESS FOR THE PREPARATION OF MAGNESIUM ALKYLPHENATES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7906060A FR2450868A1 (en) 1979-03-09 1979-03-09 PROCESS FOR THE PREPARATION OF MAGNESIUM ALKYLPHENATES AND APPLICATION OF THE PRODUCTS OBTAINED AS DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS
FR7906060 1979-03-09

Publications (2)

Publication Number Publication Date
EP0016676A1 true EP0016676A1 (en) 1980-10-01
EP0016676B1 EP0016676B1 (en) 1982-10-13

Family

ID=9222946

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80400270A Expired EP0016676B1 (en) 1979-03-09 1980-02-27 Process for the preparation of magnesium alkyl phenates

Country Status (11)

Country Link
US (1) US4382004A (en)
EP (1) EP0016676B1 (en)
JP (1) JPS6011894B2 (en)
AT (1) ATE1647T1 (en)
BR (1) BR8001372A (en)
CA (1) CA1123015A (en)
DE (1) DE3060929D1 (en)
ES (1) ES489289A1 (en)
FR (1) FR2450868A1 (en)
MX (1) MX7049E (en)
ZA (1) ZA801364B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2529225B1 (en) * 1982-06-24 1986-04-25 Orogil NEW HIGH ALKALINITY METAL DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS
FR2529224B1 (en) * 1982-06-24 1986-02-07 Orogil NEW SURALKALINIZED DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS
FR2529226B1 (en) * 1982-06-24 1987-01-16 Orogil PROCESS FOR THE PREPARATION OF SULFURIZED ALKYLPHENATES OF ALKALINE EARTH METALS FOR USE AS ADDITIVES FOR LUBRICATING OILS
JPS60127396A (en) * 1983-12-12 1985-07-08 Cosmo Co Ltd Preparation of detergent of basic alkali earth metal salicylate type
JPS62127886U (en) * 1986-02-06 1987-08-13
JPS62178288U (en) * 1986-05-06 1987-11-12
US4744921A (en) * 1986-10-21 1988-05-17 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
US4971710A (en) * 1986-10-21 1990-11-20 Chevron Research Company Methods for preparing, Group II metal overbased sulfurized alkylphenols
US5024773A (en) * 1986-10-21 1991-06-18 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
GB8730220D0 (en) * 1987-12-29 1988-02-03 Exxon Chemical Patents Inc Detergents
US5292443A (en) * 1992-08-21 1994-03-08 Texaco Inc. Process for producing neutralized sulfurized alkylphenate lubricant detergent additive
US6310009B1 (en) * 2000-04-03 2001-10-30 The Lubrizol Corporation Lubricating oil compositions containing saligenin derivatives

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1194439A (en) * 1960-03-09 1959-11-09 Socony Mobil Oil Co Additives for petroleum oils and spirits and their preparation
US3878116A (en) * 1970-09-09 1975-04-15 Bray Oil Co Overbased sulfonates
US3932289A (en) * 1973-11-09 1976-01-13 Chevron Research Company Preparation of overbased carbonated sulfurized magnesium alkylphenates
FR2277145A1 (en) * 1974-07-05 1976-01-30 Exxon Research Engineering Co DETERGENT BASED ON SUPERBASIC MAGNESIUM AND ITS APPLICATION TO LUBRICATING OILS
US4065396A (en) * 1970-02-09 1977-12-27 Bray Oil Co. Magnesium oxide process
EP0002644A1 (en) * 1977-12-20 1979-06-27 Orogil Basic complex magnesium compounds and their application to the preparation of detergent dispersant additives for lubricating oils

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350310A (en) * 1965-02-08 1967-10-31 Mobil Oil Corp Preparation of overbased calcium alkylphenate sulfides
GB1470338A (en) * 1974-05-17 1977-04-14 Exxon Research Engineering Co Lubricating oil compositions
SU644811A1 (en) * 1975-07-14 1980-02-05 Всесоюзный научно-исследовательский институт по переработке нефти Method of preparing sulfide alkylphenolate additive to lubricating oils
US4010106A (en) * 1976-02-02 1977-03-01 Chevron Research Company Corrosion-retarding functional fluid
US4016093A (en) * 1976-03-19 1977-04-05 Mobil Oil Corporation Metal alkylphenate sulfides of reduced corrosiveness and method of preparing same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1194439A (en) * 1960-03-09 1959-11-09 Socony Mobil Oil Co Additives for petroleum oils and spirits and their preparation
US4065396A (en) * 1970-02-09 1977-12-27 Bray Oil Co. Magnesium oxide process
US3878116A (en) * 1970-09-09 1975-04-15 Bray Oil Co Overbased sulfonates
US3932289A (en) * 1973-11-09 1976-01-13 Chevron Research Company Preparation of overbased carbonated sulfurized magnesium alkylphenates
FR2277145A1 (en) * 1974-07-05 1976-01-30 Exxon Research Engineering Co DETERGENT BASED ON SUPERBASIC MAGNESIUM AND ITS APPLICATION TO LUBRICATING OILS
EP0002644A1 (en) * 1977-12-20 1979-06-27 Orogil Basic complex magnesium compounds and their application to the preparation of detergent dispersant additives for lubricating oils
FR2412607A1 (en) * 1977-12-20 1979-07-20 Orogil NEW BASIC MAGNESIUM COMPLEXES AND THEIR APPLICATION FOR THE MANUFACTURE OF DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS

Also Published As

Publication number Publication date
JPS6011894B2 (en) 1985-03-28
CA1123015A (en) 1982-05-04
US4382004A (en) 1983-05-03
JPS55143923A (en) 1980-11-10
ZA801364B (en) 1981-03-25
DE3060929D1 (en) 1982-11-18
FR2450868A1 (en) 1980-10-03
BR8001372A (en) 1980-11-11
FR2450868B1 (en) 1983-05-20
MX7049E (en) 1987-04-07
ATE1647T1 (en) 1982-10-15
ES489289A1 (en) 1980-08-16
EP0016676B1 (en) 1982-10-13

Similar Documents

Publication Publication Date Title
BE1001979A3 (en) Concentrated and lubricating oil compositions.
EP0003694B1 (en) Method for preparing highly based detergents-dispersants for lubricating oils, and product thus obtained
EP0016676B1 (en) Process for the preparation of magnesium alkyl phenates
EP0164286B1 (en) A process for the production of additives for lubricants with detergent and dispersant properties based on non-foaming alkylarylsulfonates of alkaline-earth metals
EP0133088B1 (en) Process for preparing calcium-based detergent-dispersant additives having a very high alkalinity, and products obtained by this process
EP1562887B1 (en) Method for producing lubricant detergents
EP0007257B1 (en) Process for the preparation of detergent-dispersant agents of high alkali content for lubricating oils and product obtained
FR2631969A1 (en) COMPOSITIONS OF LUBRICATING OILS
FI78683B (en) FOERFARANDE FOER FRAMSTAELLNING AV ETT OEVERBASISKT SVAVELHALTIGT ALKYLFENAT AV EN ALKALISK JORDARTSMETALL.
EP0102255B1 (en) Process for the preparation of sulphurized alkylphenates for use as lubricating oil addtives
EP1236791A1 (en) Overbased detergent additives
EP0007260B1 (en) Process for the preparation of metalliferous detergent-dispersant additives of high alkali content, especially for lubricating oils, and product obtained
EP0102254B1 (en) Superalkalised detergent-dispersant additive for lubricating oils
US20040127743A1 (en) Method for the alkylation of salicylic acid
EP0308445B1 (en) Process for the preparation of a superalkalinized additive containing an inorganic boron derivative, additive produced by said process and lubricating compositions containing said additive
EP0211722B1 (en) Sulfonated and sulfurized detergent dispersant additives for lubricant oils
US4608184A (en) Phenate process and composition improvement
EP0957153A1 (en) Detergents comprising low sulfur, alkaline earth alkyl salicylates and their use in low sulfur lubricating compositions for two-stroke engines
EP0006796B1 (en) Process for the preparation of overbased metalliferous detergent-dispersant agents for lubricating oils and product obtained
EP0219382B1 (en) Superbasic detergent-dispersant additives stable to hydrolysis, and process for their preparation
FR2529225A1 (en) NEW DETERGENT-HIGH ALKALINITE METAL DISPERSANT ADDITIVE FOR LUBRICATING OILS
WO2012167530A1 (en) Cleaning agent for lubricating oil and production process thereof
CA1113680A (en) Basic magnesium complexes and their use in the manufacture of detergent-dispersant additives for lubricating oils
EP0117784B1 (en) Dispersant additive compositions for lubricating oils
GB2114993A (en) Production of "overbased" sulphonates in the presence of 1,3- dioxolane

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 GB IT NL SE

17P Request for examination filed

Effective date: 19801010

ITF It: translation for a ep patent filed

Owner name: D. PERROTTA & C. S.A.S.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

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

REF Corresponds to:

Ref document number: 1647

Country of ref document: AT

Date of ref document: 19821015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3060929

Country of ref document: DE

Date of ref document: 19821118

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

Ref country code: AT

Payment date: 19910114

Year of fee payment: 12

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

Ref country code: GB

Payment date: 19910116

Year of fee payment: 12

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

Ref country code: SE

Payment date: 19910121

Year of fee payment: 12

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

Ref country code: CH

Payment date: 19910122

Year of fee payment: 12

Ref country code: BE

Payment date: 19910122

Year of fee payment: 12

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

Ref country code: DE

Payment date: 19910129

Year of fee payment: 12

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: 19910228

Year of fee payment: 12

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

Ref country code: GB

Effective date: 19920227

Ref country code: AT

Effective date: 19920227

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

Ref country code: SE

Effective date: 19920228

Ref country code: BE

Effective date: 19920228

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

Ref country code: CH

Effective date: 19920229

BERE Be: lapsed

Owner name: OROGIL

Effective date: 19920228

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

Ref country code: NL

Effective date: 19920901

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal 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: 19921103

EUG Se: european patent has lapsed

Ref document number: 80400270.7

Effective date: 19920904

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