EP0190553A1 - Process to improve the viscosity of mineral oils and of the distillates of mineral oils - Google Patents

Process to improve the viscosity of mineral oils and of the distillates of mineral oils Download PDF

Info

Publication number
EP0190553A1
EP0190553A1 EP86100143A EP86100143A EP0190553A1 EP 0190553 A1 EP0190553 A1 EP 0190553A1 EP 86100143 A EP86100143 A EP 86100143A EP 86100143 A EP86100143 A EP 86100143A EP 0190553 A1 EP0190553 A1 EP 0190553A1
Authority
EP
European Patent Office
Prior art keywords
vinyl acetate
ethylene
propene
mineral oils
process according
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
EP86100143A
Other languages
German (de)
French (fr)
Other versions
EP0190553B1 (en
Inventor
Wolfgang Dr. Dipl.Chem. Payer
Ludger Dr. Dipl.Chem. Bexten
Hans-Albert Lümmen
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.)
Ruhrchemie AG
Original Assignee
Ruhrchemie 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6260051&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0190553(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ruhrchemie AG filed Critical Ruhrchemie AG
Publication of EP0190553A1 publication Critical patent/EP0190553A1/en
Application granted granted Critical
Publication of EP0190553B1 publication Critical patent/EP0190553B1/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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/08—Pipe-line systems for liquids or viscous products
    • F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
    • F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting

Definitions

  • the present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of ethylene-vinyl acetate copolymers and ethylene-propene-vinyl acetate terpolymers.
  • Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. For example, the ability of crude oil production and transport facilities to function until their complete failure are impaired. In diesel engines and combustion plants, the filters can become clogged, which ultimately results in an interruption in the fuel or heating medium supply.
  • additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.
  • Copoly has the greatest importance as pour point depressants and flow improvers for crude oils and middle distillates merisate of ethylene with carboxylic acid esters of vinyl alcohol.
  • ethylene-vinyl acetate copolymers have proven particularly useful.
  • Such copolymers and their use are described for example in DE-PS 1 914 756. They are generally prepared by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C. and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.
  • Ethylene-vinyl acetate copolymers are generally commercially available as solutions in hydrocarbons. For economic reasons, these solutions should contain the active ingredient in the highest possible concentration and be easy to handle.
  • the object was therefore to develop flow improvers for mineral oils which, at the same concentration in the mineral oil, are at least as effective as ethylene-vinyl acetate copolymers, but have a significantly better solubility in hydrocarbons or hydrocarbon mixtures than these.
  • the invention consists in a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that a mixture of an ethylene-vinyl acetate copolymer and an ethylene-propene-vinyl acetate terpolymer is added to the mineral oils or mineral oil distillates.
  • the ethylene-vinyl acetate copolymers used according to the invention contain 20 to 40% by weight of vinyl acetate. Copolymers with 25 to 35% by weight of vinyl acetate (based in each case on the copolymer) have proven particularly useful. Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, measured at 140 ° C. in each case and they have 2 to 10, in particular 3 to 7, CH 3 groups per 100 CH 2 groups.
  • the production of the ethylene-vinyl acetate copolymers is known. It is carried out by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in an organic solvent as the reaction medium. However, the polymerization at pressures above 50 MPa and temperatures between 120 and 300 ° C in absentia is preferred - made uniform organic solvents.
  • the ethylene-propene-vinyl acetate terpolymers of the new process contain 20 to 40% by weight, in particular 25 to 35% by weight, of vinyl acetate (in each case based on the terpolymer).
  • Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C.
  • Each 100 CH 2 groups have 8 to 25, in particular 12 to 20 CH 3 groups, which do not result from the acetate residue of the vinyl acetate.
  • the preparation of the terpolymers is also described.
  • Mixtures of ethylene, propene and vinyl acetate are used, which are polymerized in the presence of free radical initiators at pressures above 50 mPa and at temperatures from 150 to 350 ° C. in the absence of organic solvents.
  • the molecular weight of the terpolymers is preferably adjusted by the propene, which also acts as a molecular weight regulator.
  • other molecular weight regulators such as hydrocarbons, aldehydes, ketones can also be used.
  • Monomer mixtures containing 30 to 60% by weight of ethylene, 20 to 50% by weight of propene and 15 to 35% by weight of vinyl acetate are used for the polymerization.
  • the mineral oils and mineral oil distillates produced by the process according to the invention to improve their flowability are added to polymer mixtures which contain ethylene-vinyl acetate copolymer and ethylene-propene-vinyl acetate terpolymer in a weight ratio of 0.5 to 1 to 20 to 1. Mixtures containing the copolymer and Contain terpolymer in a weight ratio of 2 to 1 to 10 to 1. It is advisable to use copolymers and terpolymers in the polymer mixture whose vinyl acetate content (in% by weight) is approximately the same and in particular does not deviate from one another by more than 3% by weight.
  • the viscosity of the polymers contained in the mixture should also be as equal as possible, and the deviations should in particular not be greater than 200 mPa.s, measured at 140 ° C.
  • the mixtures of the polymers are added to the mineral oils or the mineral oil fractions in the form of 40 to 60% by weight solutions in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture.
  • an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture For example, Kerosene.
  • the amount of polymer, based on mineral oil or mineral oil fraction, should be 0.001 to 2, preferably 0.005 to 0.5,% by weight.
  • the polymer mixtures can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, corrosion inhibitors, antioxidants or sludge inhibitors.
  • Examples AF relate to the preparation of the ethylene-propene-vinyl acetate terpolymers
  • examples G-I relate to the production of the ethylene-vinyl acetate copolymers.
  • Examples 10-18 describe the flow behavior of middle distillates after the addition of copolymer-terpolymer mixtures according to the inventive method.
  • Ethylene, propene and vinyl acetate are continuously polymerized in an autoclave.
  • the monomer mixture is fed into the autoclave at the reaction pressure after the for the maintenance of the polymerization required amount of peroxide has been added as a solution in a gasoline fraction.
  • the dwell time is about 80 seconds.
  • the vinyl acetate content in the polymers is determined using the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask at 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The acetic acid formed is reacted with a NaJ / KJ0 3 solution and the released iodine is titrated with Na 2 S 2 0 3 solution.
  • the degree of branching of the polymers is determined by H-NMR spectroscopy.
  • the degree of branching is understood to mean the number of CH 3 groups per 100 CH 2 groups with the exception of the CH 3 groups, which originate from the acetate residue.
  • the monomer mixture consisting of ethylene and vinyl acetate is polymerized in a tubular reactor at 150 MPa pressure in the absence of substantial amounts of a solvent.
  • Organic peroxides are used as initiators.
  • the vinyl acetate content and the degree of branching are determined by the methods given for the ethylene-propene-vinyl acetate terpolymers.

Abstract

1. A process to improve the flowability of mineral oils and mineral oil distillates, characterized in that a mixture of an ethylene-vinylacetate copolymer and an ethylene-propene-vinylacetate terpolymer is added to the mineral oils and mineral oil distillates.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten durch Zusatz von Mischungen aus Ethylen-Vinylacetat-Copolymerisaten und Ethylen-Propen-Vinylacetat-Terpolymerisaten.The present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of ethylene-vinyl acetate copolymers and ethylene-propene-vinyl acetate terpolymers.

Mineralöle wie Rohöl, Dieselkraftstoff oder Heizöl enthalten Paraffin gelöst, das bei niedrigen Temperaturen auskriatallisiert. Diese Feststoffablagerungen führen häufig zu Störungen bei der Gewinnung und beim Einsatz von Mineralölen. So kann z.B. die Arbeitsfähigkeit von Förder- und Transporteinrichtungen für Rohöl bis zu deren völligem Ausfall beeinträchtigt werden. Bei Dieselmotoren und Feuerungsanlagen können Verstopfungen der Filter auftreten, die schließlich in einer Unterbrechung der Kraftstoff- bzw. Heizmittelzufuhr reaultieren.Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. For example, the ability of crude oil production and transport facilities to function until their complete failure are impaired. In diesel engines and combustion plants, the filters can become clogged, which ultimately results in an interruption in the fuel or heating medium supply.

Um diese unerwünschte Feststoffbildung zu vermeiden, setzt man Mineralölen Additive zu, die der Entstehung von Paraffinkristallen entgegenwirken. Dadurch wird ein Anstieg der Viskosität der Öle verhindert und ihr Stockpunkt gesenkt.In order to avoid this undesirable solid formation, additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.

Die größte Bedeutung als Stockpunktserniedriger und Fließverbesserer für Rohöle und Mitteldestillate haben Copolymerisate des Ethylens mit Carbonsäureestern des Vinylalkohols erlangt. Besonders bewährt haben sich unter ihnen Ethylen-Vinylacetat-Copolymerisate. Solche Mischpolymerisate und ihre Verwendung sind z.B. in der DE-PS 1 914 756 beschrieben. Ihre Herstellung erfolgt im allgemeinen durch Copolymerisation der Monomeren in Autoklaven bei Temperaturen von 80 bis 150°C und Drücken von 5 bis 15 MPa in Gegenwart von Peroxiden als Initiatoren und organischen Lösungsmittels als Reaktionsmedium.Copoly has the greatest importance as pour point depressants and flow improvers for crude oils and middle distillates merisate of ethylene with carboxylic acid esters of vinyl alcohol. Among them, ethylene-vinyl acetate copolymers have proven particularly useful. Such copolymers and their use are described for example in DE-PS 1 914 756. They are generally prepared by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C. and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.

Ethylen-Vinylacetat-Copolymerisate kommen im allgemeinen als Lösungen in Kohlenwasserstoffen in den Handel. Diese Lösungen sollen aus wirtschaftlichen Gründen den Wirkstoff in möglichst hoher Konzentration enthalten und leicht handhabbar sein.Ethylene-vinyl acetate copolymers are generally commercially available as solutions in hydrocarbons. For economic reasons, these solutions should contain the active ingredient in the highest possible concentration and be easy to handle.

Es ist ein Nachteil der als Fließverbesserer hervorragend geeigneten Ethylen-Vinylacetat-Copolymerisate, daß ihre Lösungen in den verschiedensten Lösungsmitteln, z.B. in Kerosin, relativ hohe Stock- bzw. Fließtemperaturen besitzen, wodurch ihre Anwendbarkeit erschwert Wird.It is a disadvantage of the ethylene-vinyl acetate copolymers which are outstandingly suitable as flow improvers that their solutions are present in a wide variety of solvents, e.g. in kerosene, have relatively high stock or flow temperatures, which makes their applicability more difficult.

Es bestand daher die Aufgabe, Fließverbesserer für Mineralöle zu entwickeln, die bei gleicher Konzentration im Mineralöl mindestens ebenso wirksam sind wie Ethylen-Vinylacetat-Copolymerisate, gegenüber diesen jedoch eine wesentlich bessere Löslichkeit in Kohlenwasserstoffen bzw. Kohlenwasserstoffgemischen aufweisen.The object was therefore to develop flow improvers for mineral oils which, at the same concentration in the mineral oil, are at least as effective as ethylene-vinyl acetate copolymers, but have a significantly better solubility in hydrocarbons or hydrocarbon mixtures than these.

Die Erfindung besteht in einem Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten. Es ist dadurch gekennzeichnet, daß man den Mineralölen bzw. Mineralöldestillaten eine Mischung aus einem Ethylen-Vinylacetat-Copolymerisat und einem Ethylen-Propen-Vinylacetat-Terpolymerisat zusetzt.The invention consists in a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that a mixture of an ethylene-vinyl acetate copolymer and an ethylene-propene-vinyl acetate terpolymer is added to the mineral oils or mineral oil distillates.

Es ist überraschend, daß die gestellte Aufgabe durch die erfindungsgemäße Arbeitsweise gelöst wird. Denn es war nicht vorauszusehen, daß Ethylen-Propen-Vinylacetat-Terpolymerisatc die Löslichkeit von Ethylen-Vinylacetat-Copolymerisaten in Kohlenwasserstoffen oder Kohlenwasserstoffgemischen beeinflußt. Ebenso wenig war zu erwarten, daß Gemische aus Ethylen-Propen-Vinylacetat-Terpolymerisaten mit Ethylen-Vinylacetat-Copolymerisatcn mindestens gleich geeignete Fließverbesserer sind wie die Copolymerisate allein, denn Ethylen-Propen-Vinylacetat-Terpolymerisate für sich wirken nicht oder nur in geringem Maße als Fließverbesserer für Mineralöle und Mineralöldestillate.It is surprising that the task is solved by the procedure according to the invention. Because it could not have been foreseen that ethylene-propene-vinyl acetate terpolymers would influence the solubility of ethylene-vinyl acetate copolymers in hydrocarbons or hydrocarbon mixtures. Likewise, it was not to be expected that mixtures of ethylene-propene-vinyl acetate terpolymers with ethylene-vinyl acetate copolymers would be at least as suitable flow improvers as the copolymers alone, because ethylene-propene-vinyl acetate terpolymers do not work per se or only to a small extent as Flow improver for mineral oils and mineral oil distillates.

Die erfindungsgemäß eingesetzten Ethylen-Vinylacetat-Copolymerisate enthalten 20 bis 40 Gew.% Vinylacetat. Besonders bewährt haben sich Copolymerisate mit 25 bis 35 Gew.% Vinylacetat (jeweils bezogen auf das Copolymerisat). Ihre Viskosität beträgt 100 bis 5000 mPa.s, insbesondere 200 bis 1500 mPa.s, jeweils gemessen bei 140°C und sie weisen je 100 CH2-Gruppen 2 bis 10, insbesondere 3 bis 7 CH3-Gruppen auf.The ethylene-vinyl acetate copolymers used according to the invention contain 20 to 40% by weight of vinyl acetate. Copolymers with 25 to 35% by weight of vinyl acetate (based in each case on the copolymer) have proven particularly useful. Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, measured at 140 ° C. in each case and they have 2 to 10, in particular 3 to 7, CH 3 groups per 100 CH 2 groups.

Die Herstellung der Ethylen-Vinylacetat-Copolymerisate ist bekannt. Sie erfolgt durch Polymerisation des Monomerengemisches bei Drücken von 5 bis 15 MPa und Temperaturen von 70 bis 150°C in einem organischen Lösungsmittel als Reaktionsmedium. Bevorzugt wird jedoch die Polymerisation bei Drücken oberhalb 50 MPa und Temperaturen zwischen 120 und 300°C in Abwesen- heit organischer Lösungsmittel durchgeführt.The production of the ethylene-vinyl acetate copolymers is known. It is carried out by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in an organic solvent as the reaction medium. However, the polymerization at pressures above 50 MPa and temperatures between 120 and 300 ° C in absentia is preferred - made uniform organic solvents.

Die Ethylen-Propen-Vinylacetat-Terpolymerisate des neuen Verfahrens enthalten 20 bis 40 Gew.%, insbesondere 25 bis 35 Gew.% Vinylacetat (jeweils bezogen auf das Terpolymerisat).The ethylene-propene-vinyl acetate terpolymers of the new process contain 20 to 40% by weight, in particular 25 to 35% by weight, of vinyl acetate (in each case based on the terpolymer).

Ihre Viskosität beträgt 100 bis 5000 mPa.s, insbesondere 200 bis 1500 mPa.s, jeweils gemessen bei 140°C. Je 100 CH2-Gruppen weisen sie 8 bis 25, insbesondere 12 bis 20 CH3-Gruppen auf, die nicht aus dem Acetatrest des Vinylacetats herrühren.Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C. Each 100 CH 2 groups have 8 to 25, in particular 12 to 20 CH 3 groups, which do not result from the acetate residue of the vinyl acetate.

Auch die Herstellung der Terpolymerisate ist vorbeschrieben. Man geht von Gemischen aus Ethylen, Propen und Vinylacetat aus, die in Gegenwart Radikale bildender Initiatoren bei Drücken oberhalb 50 mPa und bei Temperaturen von 150 bis 350°C in Abwesenheit von organischen Lösungsmitteln polymerisiert werden. Das Molekulargewicht der Terpolymerisate wird vorzugsweise durch das auch als Molekulargewichtsregler wirkende Propen eingestellt. Andere Molekulargewichtsregler wie Kohlenwasserstoffe, Aldehyde, Ketone können jedoch zusätzlich verwendet werden. Zur Polymerisation werden Monomerengemische eingesetzt, die 30 bis 60 Gew.% Ethylen, 20 bis 50 Gew.% Propen und 15 bis 35 Gew.% Vinylacetat enthalten.The preparation of the terpolymers is also described. Mixtures of ethylene, propene and vinyl acetate are used, which are polymerized in the presence of free radical initiators at pressures above 50 mPa and at temperatures from 150 to 350 ° C. in the absence of organic solvents. The molecular weight of the terpolymers is preferably adjusted by the propene, which also acts as a molecular weight regulator. However, other molecular weight regulators such as hydrocarbons, aldehydes, ketones can also be used. Monomer mixtures containing 30 to 60% by weight of ethylene, 20 to 50% by weight of propene and 15 to 35% by weight of vinyl acetate are used for the polymerization.

Die nach dem erfindungsgemäßen Verfahren hergestellten Mineralöle und Mineralöldestillate zur Verbesserung ihrer Fließfähigkeit zugesetzten Polymermischungen enthalten Ethylen-Vinylacetat-Copolymerisat und Ethylen-Propen-Vinylacetat-Terpolymerisat in einem Gewichtsverhältnis von 0,5 zu 1 bis 20 zu 1. Bevorzugt werden Mischungen, die Copolymerisat und Terpolymerisat im Gewichtsverhältnis von 2 zu 1 bis 10 zu 1 enthalten. Es empfiehlt sich, in der Polymerenmischung Copolymerisate und Terpolymerisate zu verwenden, deren Vinylacetatgehalt (in Gew.%) annähernd gleich ist und insbesondere nicht mehr als 3 Gew.% absolut voneinander abweicht. Auch die Viskosität der in der Mischung enthaltenen Polymeren soll möglichst gleich sein, die Abweichungen sollen insbesondere nicht größer als 200 mPa.s, gemessen bei 140°C, betragen.The mineral oils and mineral oil distillates produced by the process according to the invention to improve their flowability are added to polymer mixtures which contain ethylene-vinyl acetate copolymer and ethylene-propene-vinyl acetate terpolymer in a weight ratio of 0.5 to 1 to 20 to 1. Mixtures containing the copolymer and Contain terpolymer in a weight ratio of 2 to 1 to 10 to 1. It is advisable to use copolymers and terpolymers in the polymer mixture whose vinyl acetate content (in% by weight) is approximately the same and in particular does not deviate from one another by more than 3% by weight. The viscosity of the polymers contained in the mixture should also be as equal as possible, and the deviations should in particular not be greater than 200 mPa.s, measured at 140 ° C.

Im allgemeinen setzt man die Mischungen der Polymeren den Mineralölen bzw. den Mineralölfraktionen in Form von 40 bis 60 Gew.%igen Lösungen in einem aliphatischen oder aromatischen Kohlenwasserstoff oder in einem Kohlenwasserstoffgemisch zu. Besonders geeignet ist z.B. Kerosin. Die Polymerisatmenge, bezogen auf Mineralöl bzw. Mineralölfraktion, soll 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.% betragen. Die Polymergemische können allein oder auch zusammen mit anderen Additiven verwendet werden, beispielsweise mit anderen Stockpunkterniedrigern oder Entwachsungshilfsmitteln, Korrosionsinhibitoren, Antioxidantien oder Schlamminhibitoren.In general, the mixtures of the polymers are added to the mineral oils or the mineral oil fractions in the form of 40 to 60% by weight solutions in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture. For example, Kerosene. The amount of polymer, based on mineral oil or mineral oil fraction, should be 0.001 to 2, preferably 0.005 to 0.5,% by weight. The polymer mixtures can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, corrosion inhibitors, antioxidants or sludge inhibitors.

Das erfindungsgemäße Verfahren wird durch die nachfolgenden Beispiele näher erläutert.The process according to the invention is explained in more detail by the following examples.

Die Beispiele A - F betreffen die Herstellung der Ethylen-Propen-Vinylacetat-Terpolymerisate, die Beispiele G - I die Herstellung der Ethylen-Vinylacetat-Copolymerisate.Examples AF relate to the preparation of the ethylene-propene-vinyl acetate terpolymers, examples G-I relate to the production of the ethylene-vinyl acetate copolymers.

In den Beispielen 1 - 6 ist die Wirksamkeit der Terpolymerisate, in den Beispielen 7 - 9 die Wirksamkeit der Copolymeri- 3ate als Fließverbesserer zusammengestellt.In Examples 1-6, the effectiveness of the terpolymers in Examples 7-9, the effectiveness of the copolymerization 3 ate collected as flow improvers.

Die Beispiele 10 - 18 beschreiben das Fließverhalten von Mitteldestillaten nach Zusatz von Copolymerisat-Terpolymerisat-Mischungen entsprechend dem erfindungsgemäßen Verfahren.Examples 10-18 describe the flow behavior of middle distillates after the addition of copolymer-terpolymer mixtures according to the inventive method.

Beispiele A - F: Herstellung von Ethylen-Propen-Vinylacetat-TerpolymerisatenExamples A - F: Preparation of ethylene-propene-vinyl acetate terpolymers

Ethylen, Propen und Vinylacetat werden kontinuierlich in einem Autoklaven polymerisiert. Das Monomerengemisch wird beim Reaktionsdruck in den Autoklaven eingespeist, nachdem die für die Aufrechterhaltung der Polymerisation erforderliche Menge Peroxid als Lösung in einer Benzinfraktion zugesetzt worden ist. Die Verweilzeit beträgt etwa 80 sec.Ethylene, propene and vinyl acetate are continuously polymerized in an autoclave. The monomer mixture is fed into the autoclave at the reaction pressure after the for the maintenance of the polymerization required amount of peroxide has been added as a solution in a gasoline fraction. The dwell time is about 80 seconds.

Die jeweiligen Polymerisationsbedingungen und die für die erhaltenen Polymere charakteristischen Eigenschaftswerte sind in Tabelle 1 zusammengestellt.The respective polymerization conditions and the property values characteristic of the polymers obtained are summarized in Table 1.

Der Vinylacetatgehalt in den Polymeren wird nach der Pyrolysemethode bestimmt. Hierzu werden 200 mg des Polymeren mit 300 mg reinem Polyethylen in einem Pyrolysekolben 5 Minuten auf 450°C erhitzt und die Spaltgase in einem 250 ml-Rundkolben aufgefangen. Die gebildete Essigsäure wird mit einer NaJ/KJ03-Lösung umgesetzt und mit Na2S203-Lösung das freiwerdende Jod titriert.The vinyl acetate content in the polymers is determined using the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask at 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The acetic acid formed is reacted with a NaJ / KJ0 3 solution and the released iodine is titrated with Na 2 S 2 0 3 solution.

Die Bestimmung des Verzweigungsgrades der Polymeren erfolgt durch H-NMR-Spektroskopie. Unter Verzweigungsgrad versteht man die Anzahl CH3-Gruppen je 100 CH2-Gruppen mit Ausnahme der CH3-Gruppen, die aus dem Acetatrest stammen.

Figure imgb0001
The degree of branching of the polymers is determined by H-NMR spectroscopy. The degree of branching is understood to mean the number of CH 3 groups per 100 CH 2 groups with the exception of the CH 3 groups, which originate from the acetate residue.
Figure imgb0001

Beispiele G - I: Herstellung von Ethylen-Vinylacetat-CopolymerisatenExamples G - I: Preparation of ethylene-vinyl acetate copolymers

Die Polymerisation des aus Ethylen und Vinylacetat bestehenden Monomerengemisches erfolgt in einem Rohrreaktor bei 150 MPa Druck in Abwesenheit wesentlicher Mengen eines Lösungsmittels. Als Initiatoren finden organische Peroxide Anwendung.The monomer mixture consisting of ethylene and vinyl acetate is polymerized in a tubular reactor at 150 MPa pressure in the absence of substantial amounts of a solvent. Organic peroxides are used as initiators.

Die jeweiligen Polymerisationsbedingungen und für die erhaltenen Polymere charakteristischen Eigenschaftswerte sind in Tabelle 2 zusammengestellt.The respective polymerization conditions and property values characteristic of the polymers obtained are summarized in Table 2.

Die Bestimmung des Vinylacetatgehaltes und des Verzweigungsgrades erfolgt nach den für die Ethylen-Propen-Vinylacetat-Terpolymerisaten angegebenen Verfahren.

Figure imgb0002
The vinyl acetate content and the degree of branching are determined by the methods given for the ethylene-propene-vinyl acetate terpolymers.
Figure imgb0002

Beispiel 1 - 18Example 1-18

In den folgenden Beispielen 1 - 18 wird die Wirksamkeit von Ethylen-Propen-Vinylacetat-Terpolymerisaten, Ethylen-Vinylacetat-Copolymerisaten und Gemischen aus Copolymerisat und Terpolymerisat als Fließverbesserer an Hand des "Kalt-Filter-Verstopfungspunkt-Test" (CFPP-Test) beschrieben. Die Durchführung des Tests erfolgt nach DIN 51428, sie ist auch in J. of the Inst. of Petr., Bd. 52, Juni 1966, S. 173 bis 185 publiziert.In the following Examples 1-18, the effectiveness of ethylene-propene-vinyl acetate terpolymers, ethylene-vinyl acetate copolymers and mixtures of copolymer and terpolymer as a flow improver is described using the "cold filter clogging point test" (CFPP test) . The test is carried out in accordance with DIN 51428, and is also published in J. of the Inst. Of Petr., Vol. 52, June 1966, pp. 173 to 185.

Zur Prüfung werden drei Mitteldestillate Ml, M2 und M3 eingesetzt, die durch die in Tabelle 3 zusammengestellten Eigenschaftswerte gekennzeichnet sind.

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
 Three middle distillates Ml, M2 and M3 are used for the test, which are characterized by the property values compiled in Table 3.
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007

Claims (10)

1.) Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten, dadurch gekennzeichnet, daß man den Mineralölen bzw. Mineralöldestillaten eine Mischung ajs einem Ethylen-Vinylacetat-Copolymerisat und einem Ethylen-Propen-Vinylacetat-Terpolymerisat zusetzt.1.) Process for improving the flowability of mineral oils and mineral oil distillates, characterized in that a mixture ajs an ethylene-vinyl acetate copolymer and an ethylene-propene-vinyl acetate terpolymer is added to the mineral oils or mineral oil distillates. 2.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Ethylen-Vinylacetat-Copolymerisat 20 bis 40 Gew.%, insbesondere 25 bis 35 Gew.% Vinylacetat enthält.2.) Process according to claim 1, characterized in that the ethylene-vinyl acetate copolymer contains 20 to 40% by weight, in particular 25 to 35% by weight, of vinyl acetate. 3.) Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß das Vinylacetatcopolymerisat eine Viskosität von 100 bis 5000 mPa.s, insbesondere 200 bis 1500 mPa.s, jeweils gemessen bei 140°C, besitzt.3.) Process according to claim 1 and 2, characterized in that the vinyl acetate copolymer has a viscosity of 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C. 4.) Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß das Vinylacetatcopolymerisat je 100 CH2-Gruppen 2 bis 10, insbesondere 3 bis 7 CH3-Gruppen, die nicht aus dem Acetatrest des Vinylacetats stammen, aufweist.4.) Process according to claim 1 to 3, characterized in that the vinyl acetate copolymer has 100 CH 2 groups 2 to 10, in particular 3 to 7 CH 3 groups, which do not originate from the acetate residue of the vinyl acetate. 5.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Ethylen-Propen-Vinylacetat-Terpolymerisat 20 bis 40, insbesondere 25 bis 35 Gew.% Vinylacetat enthält.5.) Process according to claim 1, characterized in that the ethylene-propene-vinyl acetate terpolymer contains 20 to 40, in particular 25 to 35% by weight of vinyl acetate. 6.) Verfahren nach Anspruch 1 und 5, dadurch gekennzeichnet, daß die Viskosität des Ethylen-Propen-Vinylacetat-Terpolymerisats 100 bis 5000 mPa.s, insbesondere 200 bis 1500 mPa.s, jeweils gemessen bei 140°C, beträgt.6.) Process according to claim 1 and 5, characterized in that the viscosity of the ethylene-propene-vinyl acetate terpoly merisats 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C. 7.) Verfahren nach Anspruch 1, 5 und 6, dadurch gekennzeichnet, daß das Ethylen-Propen-Vinylacetat-Terpolymerisat je 100 CH2-Gruppen 8 bis 25, insbesondere 12 bis 20 CH3-Gruppen, die nicht aus dem Acetatrest des Vinylacetats herrühren, aufweist.7.) Process according to claim 1, 5 and 6, characterized in that the ethylene-propene-vinyl acetate terpolymer per 100 CH 2 groups 8 to 25, in particular 12 to 20 CH 3 groups, which are not from the acetate residue of the vinyl acetate originate, has. 8.) Verfahren nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß die Polymermischung Ethylen-Vinylacetat-Copolymerisat und Ethylen-Propen-Vinylacetat-Terpolymerisat in einem Gewichtsverhältnis von 0,5 : 1 bis 20 : 1, insbesondere 2 : 1 bis 10 : 1 enthält.8.) Method according to claim 1 to 7, characterized in that the polymer mixture ethylene-vinyl acetate copolymer and ethylene-propene-vinyl acetate terpolymer in a weight ratio of 0.5: 1 to 20: 1, in particular 2: 1 to 10: 1 contains. 9.) Verfahren nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß der Vinylacetatgehalt von Copolymerisat und Terpolymerisat in der Polymermischung nicht mehr als 3 Gew.% absolut voneinander abweicht.9.) Process according to claim 1 to 8, characterized in that the vinyl acetate content of the copolymer and terpolymer in the polymer mixture does not deviate from one another by more than 3% by weight. 10.) Verfahren nach Anspruch 1 bis 9, dadurch gekennzeichnet, daß dieViskositäten der in der Mischung enthaltenen Copolymerisate nicht mehr als 200 mPa.s, gemessen bei 140°C, voneinander abweichen.10.) Process according to Claims 1 to 9, characterized in that the viscosities of the copolymers contained in the mixture do not differ from one another by more than 200 mPa.s, measured at 140 ° C.
EP86100143A 1985-01-17 1986-01-08 Process to improve the viscosity of mineral oils and of the distillates of mineral oils Expired EP0190553B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3501384 1985-01-17
DE19853501384 DE3501384A1 (en) 1985-01-17 1985-01-17 METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES

Publications (2)

Publication Number Publication Date
EP0190553A1 true EP0190553A1 (en) 1986-08-13
EP0190553B1 EP0190553B1 (en) 1988-05-18

Family

ID=6260051

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86100143A Expired EP0190553B1 (en) 1985-01-17 1986-01-08 Process to improve the viscosity of mineral oils and of the distillates of mineral oils

Country Status (2)

Country Link
EP (1) EP0190553B1 (en)
DE (2) DE3501384A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0251002A1 (en) * 1986-06-26 1988-01-07 Hoechst Aktiengesellschaft Process to improve the flowability of mineral oils and mineral oil distillates
EP0254284A1 (en) * 1986-07-25 1988-01-27 Hoechst Aktiengesellschaft Process to improve the flowability of mineral oils and mineral oil distillates
WO1994000515A1 (en) * 1992-06-30 1994-01-06 Exxon Chemical Patents Inc. Oil additives and compositions
WO2006106300A1 (en) * 2005-04-04 2006-10-12 Proflux Systems Llp Wax-containing materials
EP1881055A2 (en) * 2006-07-18 2008-01-23 Clariant International Ltd. Additives to improve the cold properties of fuel oils
EP1881053A2 (en) * 2006-07-18 2008-01-23 Clariant International Ltd. Additives for improving the cold properties of fuel oils
US8961622B2 (en) 2006-07-18 2015-02-24 Clariant Finance (Bvi) Limited Additives for improving the cold properties of fuel oils

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19821736A1 (en) * 1998-05-14 1999-11-18 Wacker Chemie Gmbh Process for the production of vinyl ester-ethylene copolymers with reduced surface tack

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1914756A1 (en) 1968-04-01 1969-11-06 Exxon Research Engineering Co Process for the production of copolymers and their use in distillation units
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
EP0003489A1 (en) * 1977-12-20 1979-08-22 Imperial Chemical Industries Plc Crude oil having improved cold flow properties
US4178951A (en) * 1978-10-10 1979-12-18 Texaco Inc. Low pour point crude oil compositions
US4354011A (en) * 1978-10-02 1982-10-12 Exxon Research & Engineering Co. Copolymers of ethylene and ethylenically unsaturated monomers, process for their preparation and distillate oil containing said copolymers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3661541A (en) * 1969-04-22 1972-05-09 Exxon Research Engineering Co Fuel oil compositions containing a mixture of polymers to improve the pour point and flow properties
DD161128A1 (en) * 1980-03-03 1985-02-20 Leuna Werke Veb METHOD FOR PRODUCING A FLOW IMPROVER
JPH0710900B2 (en) * 1982-06-18 1995-02-08 エクソン リサーチ アンド エンヂニアリング コムパニー Fluidity improver for middle distillate fuel oil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1914756A1 (en) 1968-04-01 1969-11-06 Exxon Research Engineering Co Process for the production of copolymers and their use in distillation units
US3961916A (en) * 1972-02-08 1976-06-08 Exxon Research And Engineering Company Middle distillate compositions with improved filterability and process therefor
EP0003489A1 (en) * 1977-12-20 1979-08-22 Imperial Chemical Industries Plc Crude oil having improved cold flow properties
US4354011A (en) * 1978-10-02 1982-10-12 Exxon Research & Engineering Co. Copolymers of ethylene and ethylenically unsaturated monomers, process for their preparation and distillate oil containing said copolymers
US4178951A (en) * 1978-10-10 1979-12-18 Texaco Inc. Low pour point crude oil compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. OF THE INST. OF PETR., June 1966 (1966-06-01), pages 173 - 185

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0251002A1 (en) * 1986-06-26 1988-01-07 Hoechst Aktiengesellschaft Process to improve the flowability of mineral oils and mineral oil distillates
EP0254284A1 (en) * 1986-07-25 1988-01-27 Hoechst Aktiengesellschaft Process to improve the flowability of mineral oils and mineral oil distillates
WO1994000515A1 (en) * 1992-06-30 1994-01-06 Exxon Chemical Patents Inc. Oil additives and compositions
EA016299B1 (en) * 2005-04-04 2012-04-30 Ойлфлоу Солюшнз Холдингз Лимитед Method of treating wax-containing materials
WO2006106300A1 (en) * 2005-04-04 2006-10-12 Proflux Systems Llp Wax-containing materials
GB2439036A (en) * 2005-04-04 2007-12-12 Proflux Systems Llp Wax-containing materials
US8357745B2 (en) 2005-04-04 2013-01-22 Oilflow Solutions Holdings Limited Wax-containing materials
EP1881053A2 (en) * 2006-07-18 2008-01-23 Clariant International Ltd. Additives for improving the cold properties of fuel oils
EP1881053A3 (en) * 2006-07-18 2011-02-02 Clariant Finance (BVI) Limited Additives for improving the cold properties of fuel oils
EP1881055A3 (en) * 2006-07-18 2011-02-02 Clariant Finance (BVI) Limited Additives to improve the cold properties of fuel oils
DE102006033150B4 (en) * 2006-07-18 2008-10-16 Clariant International Limited Additives for improving the cold properties of fuel oils
EP1881055A2 (en) * 2006-07-18 2008-01-23 Clariant International Ltd. Additives to improve the cold properties of fuel oils
US8961622B2 (en) 2006-07-18 2015-02-24 Clariant Finance (Bvi) Limited Additives for improving the cold properties of fuel oils
US8968428B2 (en) 2006-07-18 2015-03-03 Clariant Produkte (Deutschland) Gmbh Additives for improving the cold properties of fuel oils
US8979951B2 (en) 2006-07-18 2015-03-17 Clariant Finance (Bvi) Limited Additives for improving the cold properties of fuel oils

Also Published As

Publication number Publication date
DE3660207D1 (en) 1988-06-23
EP0190553B1 (en) 1988-05-18
DE3501384A1 (en) 1986-07-17

Similar Documents

Publication Publication Date Title
EP0493769B1 (en) Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates
EP0807642B1 (en) Ethylene terpolymers, their preparation and their use as additives for mineral oil distillates
EP0463518B1 (en) Terpolymers of ethylene, their preparation and their use for mineral oil distillates
EP0203554B1 (en) Use of ethylene terpolymers as additives for mineral distillates oils and mineral oil
EP0254284B1 (en) Process to improve the flowability of mineral oils and mineral oil distillates
DE19757830C2 (en) Fuel oils with improved lubrication
DE3640613A1 (en) METHOD FOR THE PRODUCTION OF ETHYLENE MIXED POLYMERISATES AND THE USE THEREOF AS AN ADDITION TO MINERAL OIL AND MINERAL OIL FRACTIONS
EP0184083B1 (en) Terpolymers of ethylene, process for their manufacture and their use
EP0922716A1 (en) Process for the manufacture of terpolymers of ethylene and their use as additives to mineral oil and mineral oil distillates
DE3320720A1 (en) COPOLYMERS WITH NITROGEN FUNCTIONS, THE IN PARTICULAR. ARE USEABLE AS ADDITIVES TO LOWER THE TURBET POINT OF MEDIUM DISTILLATES OF HYDROCARBONS, AND COMPOSITIONS OF HYDROCARBON MEDIUM DISTILLATES THAT CONTAIN THESE COPOLYMERS
DE1147799B (en) Petroleum distillate propellant or fuel
DE2017920B2 (en) MINERAL OIL BLEND
EP0258572B1 (en) Process to improve the flowability of mineral oils and mineral oil distillates
EP1433836A1 (en) Fuel oils with improved cold properties.
EP0405270B1 (en) Process to improve mineral oil and mineral oil distillate flowability
EP0890589B1 (en) Solutions or dispersions based on copolymers of olefins and unsaturated carboxylic esters and their use as additives for mineral oils
EP0190553B1 (en) Process to improve the viscosity of mineral oils and of the distillates of mineral oils
DE1914559B2 (en) Process for the production of esterified copolymers and their use
EP0061696A2 (en) Process for improving the flow of mineral oils
EP0892012B2 (en) Flow improvers for mineral oils
DE19729055C2 (en) Fuel oils based on middle distillates and copolymers of ethylene and unsaturated carboxylic acid esters
EP0937108B1 (en) Co- and terpolymers based on alpha,beta-unsaturated compounds and alpha,beta-unsaturated dicarboxylic acid anhydrides
EP0251002B1 (en) Process to improve the flowability of mineral oils and mineral oil distillates
EP0309897B1 (en) Copolymers of ethylene and methoxy acetic acid vinyl ester and their use as additives for mineral oil distillates
DE3247753A1 (en) USE OF ETHYLENE COPOLYMERISATES AS A MINERAL OIL ADDITIVE

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 FR GB IT LU NL SE

17P Request for examination filed

Effective date: 19860830

17Q First examination report despatched

Effective date: 19870811

ITF It: translation for a ep patent filed

Owner name: STUDIO MASSARI S.R.L.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 3660207

Country of ref document: DE

Date of ref document: 19880623

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
BECA Be: change of holder's address

Free format text: 880518 *HOECHST A.G.:POSTFACH 80 03 20, 6230 FRANKFURT

BECH Be: change of holder

Free format text: 880518 *HOECHST A.G.

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

Ref country code: LU

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

Effective date: 19890131

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

Ref country code: NL

Payment date: 19890131

Year of fee payment: 5

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: EXXON CHEMICAL PATENTS INC.

Effective date: 19890220

NLR1 Nl: opposition has been filed with the epo

Opponent name: EXXON CHEMICAL PATENTS INC.

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: EXXON CHEMICAL PATENTS INC.

Effective date: 19890220

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

Ref country code: SE

Payment date: 19891219

Year of fee payment: 5

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

Ref country code: LU

Payment date: 19891220

Year of fee payment: 5

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

Ref country code: FR

Payment date: 19891222

Year of fee payment: 5

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

Ref country code: BE

Payment date: 19900112

Year of fee payment: 5

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

Ref country code: GB

Payment date: 19900131

Year of fee payment: 5

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

Ref country code: DE

Payment date: 19900224

Year of fee payment: 5

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19900122

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state
NLR2 Nl: decision of opposition
EUG Se: european patent has lapsed

Ref document number: 86100143.6

Effective date: 19900606