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EP0084148A2 - Petrol middle distillate with modified flow properties - Google Patents

Petrol middle distillate with modified flow properties Download PDF

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Publication number
EP0084148A2
EP0084148A2 EP82111819A EP82111819A EP0084148A2 EP 0084148 A2 EP0084148 A2 EP 0084148A2 EP 82111819 A EP82111819 A EP 82111819A EP 82111819 A EP82111819 A EP 82111819A EP 0084148 A2 EP0084148 A2 EP 0084148A2
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Prior art keywords
ethylene
weight
vinyl propionate
copolymer
petrol
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EP82111819A
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German (de)
French (fr)
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EP0084148A3 (en
EP0084148B1 (en
Inventor
Hans Dr. Gropper
Franz Dr. Brandstetter
Erich Dr. Schwartz
Egon Buettner
Walter Dr. Ziegler
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BASF SE
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BASF SE
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    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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

Definitions

  • the invention relates to middle distillates, in particular light heating oil and diesel oil, containing a flow improver, which consists of a copolymer of ethylene with vinyl propionate.
  • middle distillates such as gas oils, diesel oils or heating oils, such as those obtained from petroleum by distillation
  • paraffin wax is excreted in the form of platelet-shaped crystals, some of which also contain oil.
  • the fluidity of the petroleum distillate fuels is significantly impaired. This leads e.g. in the case of diesel fuel, for clogging of filters and thus for interrupting or not evenly supplying the fuel to the combustion units, such as engines or jet engines.
  • Malfunctions in heating oils can also occur in winter if such precipitations occur due to low temperatures.
  • the pumping of middle distillates through pipelines over longer distances can also be affected in winter by the precipitation of paraffin crystals.
  • Such additives change the size and shape of the wax crystals so that the oil remains fluid even at low temperatures.
  • Such additives are under the name "Pour point improver” or flow improver “or” pour point improver "known.
  • ethylene-vinyl acetate copolymers which have a molecular weight of 1000 to 3000 and a vinyl acetate content of 1 to 40% by weight.
  • This object is achieved according to the invention with a distillate preparation consisting of a petroleum distillate in the boiling range from 120 to 400 ° C. and 0.005 to 0.5% by weight of an ethylene-vinyl propionate copolymer with a molecular weight of 1000 to 3000 and a comonomer content of 5 to 29%. %, preferably 12 to 28.5% by weight, vinyl propionate.
  • the ethylene-vinyl propionate copolymers are prepared in a manner known per se by any process for the radical polymerization of ethylene.
  • the copolymers to be used according to the invention are advantageously prepared by high-pressure polymerization without addition of solvents, at temperatures between 100 and 350 ° C. and pressures between 500 and 3000 bar using oxygen or conventional initiators such as di-t-butyl peroxide, t-butyl perpivalate or t-butyl perisononanate.
  • oxygen or conventional initiators such as di-t-butyl peroxide, t-butyl perpivalate or t-butyl perisononanate.
  • Conventional compounds such as aldehydes, ketones, mercaptans and alkenes and alkanes with 3 or more carbon atoms are used as regulators. Examples include propionaldehyde, acetone, propylene, butene, isobutane and pentane.
  • tubular reactors are tubular polymerization vessels whose length is 10,000 to 40,000 times the tube diameter.
  • autoclave reactors the interior of which is usually in the ratio of the height to the diameter of the circular cross section from 1: 1 to 20: 1, the reaction material is moved with the aid of stirrers.
  • a mixture of 12.6 kg / h of ethylene, 5.5 kg / h of vinyl propionate and 0.31 kg / h of propionaldehyde are passed continuously through a 1 l stirred autoclave kept at a pressure of 1500 bar.
  • the temperature in the autoclave is maintained at 250 ° C. by the continuous addition of 2.2 g / h of tert-butyl perisononanate in a paraffin hydrocarbon mixture (bp. 63-80 ° C.).
  • 4.9 kg of ethylene-vinyl propionate wax with a vinyl propionate content of 28.4% by weight and a melt viscosity (at 120 ° C.) of 250 mm 2 / s are obtained.
  • the average molecular weight (number average M n ) is 1730 (Mechrolab vapor phase osmometer Model 301 A, solvent toluene).
  • a mixture of 12.2 kg / h of ethylene, 5.6 kg / h of vinyl acetate and 0.55 kg / h of propionaldehyde are continuously passed through a 1 l stirred autoclave kept at a pressure of 1500 bar.
  • a temperature of 250 ° C. is maintained in the autoclave by the continuous addition of 5.5 g / h of tert-butyl perisononanate in a paraffin-hydrocarbon mixture (bp. 175-210).
  • 5.3 kg of ethylene-vinyl acetate wax were obtained with a vinyl acetate content of 28.3% by weight and a melt viscosity (at 120 ° C. ) of 250 mm 2 / s.
  • the average molecular weight (number average M n) is 1760 (Mechrolab vapor phase osmometer model 301 A, solvent toluene).
  • Table II shows the effectiveness of the copolymers described in Preparation Examples 1 to 6 with regard to their CFPP value.
  • Examples 4 and 5 are listed for comparison with products with a higher vinyl propionate content,
  • Example 6 is listed for comparison with ethylene-vinyl acetate copolymers.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

1. A petroleum distillate boiling at from 120 to 400 C which contains from 0.005 to 0.5% by weight of an ethylene/vinyl propionate copolymer having a molecular weight of from 1000 to 3000 and containing from 5 to 29% by weight, based on the copolymer, of vinyl propionate, said copolymer having been prepared by high-pressure polymerization, without the addition of solvent, at a temperature of from 100 to 350 C under a pressure of from 500 to 3000 bar.

Description

Die Erfindung betrifft Mitteldestillate, insbesondere leichtes Heizöl und Dieselöl, mit einem Gehalt eines Fließverbesserers, der aus einem Copolymerisat des Ethylens mit Vinylpropionat besteht.The invention relates to middle distillates, in particular light heating oil and diesel oil, containing a flow improver, which consists of a copolymer of ethylene with vinyl propionate.

Sogenannte Mitteldestillate, wie Gasöle, Dieselöle oder Heizöle, wie sie durch Destillation aus Erdölen gewonnen werden, haben je nach Herkunft des Rohöls unterschiedliche Gehalte an Paraffinen. Bei tiefen Temperaturen kommt es zur Ausscheidung von Paraffinwachs in Form plättchenförmiger Kristalle, die teilweise auch noch öl eingeschlossen enthalten. Hierdurch wird die Fließfähigkeit der Erdöldestillat-Brenn- bzw. Treibstoffe erheblich beeinträchtigt. Dies führt z.B. im Fall von Dieselkraftstoff zur Verstopfung von Filtern und damit zur Unterbrechung bzw. nicht gleichmäßigen Zufuhr des Kraftstoffs zu den Verbrennungsaggregaten wie Motoren oder Düsentriebwerken. Ebenso können Störungen bei Heizölen in Winter auftreten, wenn derartige Ausscheidungen, bedingt durch tiefe Teüperaturen, auftreten. Aber auch das Fördern von Mitteldestillaten durch Rohrleitungen über größere Entfernungen kann im Winter durch das Ausfallen von Paraffinkristallen beeinträchtigt werden.So-called middle distillates, such as gas oils, diesel oils or heating oils, such as those obtained from petroleum by distillation, have different paraffin contents depending on the origin of the crude oil. At low temperatures, paraffin wax is excreted in the form of platelet-shaped crystals, some of which also contain oil. As a result, the fluidity of the petroleum distillate fuels is significantly impaired. This leads e.g. in the case of diesel fuel, for clogging of filters and thus for interrupting or not evenly supplying the fuel to the combustion units, such as engines or jet engines. Malfunctions in heating oils can also occur in winter if such precipitations occur due to low temperatures. However, the pumping of middle distillates through pipelines over longer distances can also be affected in winter by the precipitation of paraffin crystals.

Es ist seit langem bekannt, verschiedene Zusätze als Modifikatoren für das Kristallwachstum den Erdöldestillat--Brenn- und Treibstoffen, insbesondere den Mitteldestillaten, zuzusetzen.It has long been known to add various additives as modifiers for crystal growth to petroleum distillate fuels, in particular middle distillates.

Derartige Zusätze verändern Größe und Form der Wachskristalle, so daß das öl auch bei tiefen Temperaturen fließfähig bleibt. Solche Zusätze sind unter der Bezeichnung "Stockpunktverbesserer" bzw. Fließverbesserer" oder "Fließpunktverbesserer" bekannt.Such additives change the size and shape of the wax crystals so that the oil remains fluid even at low temperatures. Such additives are under the name "Pour point improver" or flow improver "or" pour point improver "known.

Insbesondere sind gemäß der deutschen Patentschrift 1 147 799 Ethylen-Vinylacetat-Copolymere bekannt, die ein Molekulargewicht von 1000 bis 3000 und einen Vinylacetatgehalt von 1 bis 40 Gew.% aufweisen.In particular, according to German Patent 1,147,799, ethylene-vinyl acetate copolymers are known which have a molecular weight of 1000 to 3000 and a vinyl acetate content of 1 to 40% by weight.

Gemäß der deutschen Auslegeschrift 19 14 756 sollen besonders solche Copolymerisate der genannten Art wirksam sein, die durch Lösungsmittelpolymerisation unterhalb 130°C hergestellt worden sind.According to German Auslegeschrift 19 14 756 copolymers of the type mentioned are particularly effective, which have been prepared by solvent polymerization below 130 ° C.

Des weiteren ist aus der DE-OS 21 02 469 bekannt, Copolymerisate von Ethylen mit 30 bis 75 Gew.% Vinylestern oder Acrylsäure- und Methacrylsäureestern, die sich von Alkoholen mit 1 bis 12 Kohlenstoffatomen ableiten, als Zusatz zu Erdölfraktionen zu verwenden.Furthermore, it is known from DE-OS 21 02 469 to use copolymers of ethylene with 30 to 75% by weight of vinyl esters or acrylic and methacrylic acid esters, which are derived from alcohols with 1 to 12 carbon atoms, as an additive to petroleum fractions.

Alle bisher bekannten Zusätze führen in einer Reihe von Erdölfraktionen nur zu einer unbefriedigenden Verbesserung der Fließfähigkeit.All of the additives known to date only lead to an unsatisfactory improvement in flowability in a number of petroleum fractions.

Es bestand daher die Aufgabe einen Zusatz zu Erdölfraktionen zu finden, der zu einer Verbesserung der Fließfähigkeit in Erdölfraktionen führt, bei der bisher bekannte Zusätze einen nur ungenügenden Effekt erbrachten.It was therefore the task of finding an additive to petroleum fractions, which leads to an improvement in the flowability in petroleum fractions, in which previously known additives had an insufficient effect.

Diese Aufgabe wird erfindungsgemäß gelöst mit einer Destillatclzubereitung, bestehend aus einem Erdöldestillat im Siedebereich von 120 bis 400°C und 0,005 bis 0,5 Gew.% eines Ethylen-Vinylpropionatcopolymerisats mit einem Molekulargewicht von 1000 bis 3000 und einem Comonomerengehalt von 5 bis 29 Gew.%, vorzugsweise 12 bis 28,5 Gew.%, Vinylpropionat.This object is achieved according to the invention with a distillate preparation consisting of a petroleum distillate in the boiling range from 120 to 400 ° C. and 0.005 to 0.5% by weight of an ethylene-vinyl propionate copolymer with a molecular weight of 1000 to 3000 and a comonomer content of 5 to 29%. %, preferably 12 to 28.5% by weight, vinyl propionate.

Die Herstellung der Ethylen-Vinylpropionat-Copolymeren ' erfolgt in an sich bekannter Weise nach jedem Verfahren zur radikalischen Polymerisation von Ethylen.The ethylene-vinyl propionate copolymers are prepared in a manner known per se by any process for the radical polymerization of ethylene.

Die Herstellungsmethode der Copolymerisate durch Lösungsmittelpolymerisation ist in den genannten deutschen Patentschriften eingehend beschrieben, so daß bezüglich der Polymerisationsmethode nur auf diese Vorliteratur Bezug genommen wird.The method of preparation of the copolymers by solvent polymerization is described in detail in the aforementioned German patents, so that reference is made only to this preliminary literature with regard to the polymerization method.

Vorteilhaft stellt man jedoch die erfindungsgemäß zu verwendenden Copolymerisate durch Hochdruckpolymerisation ohne Lösungsmittelzusätze her, bei Temperaturen zwischen 100 und 350oC und Drücken zwischen 500 bis 3000 bar unter Verwendung von Sauerstoff oder üblichen Initiatoren, wie Di-t.-butylperoxid, t-Butylperpivalat oder t-Butylperisononanat. Als Regler verwendet man übliche Verbindungen wie Aldehyde, Ketone, Mercaptane und Alkene und Alkane mit 3 oder mehr C-Atomen. Beispiele hierfür sind Propionaldehyd, Aceton, Propylen, Buten, Isobutan und Pentan.However, the copolymers to be used according to the invention are advantageously prepared by high-pressure polymerization without addition of solvents, at temperatures between 100 and 350 ° C. and pressures between 500 and 3000 bar using oxygen or conventional initiators such as di-t-butyl peroxide, t-butyl perpivalate or t-butyl perisononanate. Conventional compounds such as aldehydes, ketones, mercaptans and alkenes and alkanes with 3 or more carbon atoms are used as regulators. Examples include propionaldehyde, acetone, propylene, butene, isobutane and pentane.

Derartige Polymerisationsverfahren sind beispielsweise in Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, 19. Band, S. 169-178 beschrieben. Die Anordnungen für die Polymerisationszone lassen sich zweckmäßig in Rohrreaktoren und/oder Autoklavenreaktoren einteilen. Unter Rohrreaktoren versteht man rohrförmige Polymerisationsgefäße, deren Längenausdehnung das 10 000- bis 40 000-fache des Rohrdurchmessers beträgt. In Autoklavenreaktoren, deren Innenraum meist im Verhältnis von Höhe zu Durchmesser des kreisförmigen Querschnitts von 1 : 1 bis ,20 : 1 hat, wird das Reaktionsgut mit Hilfe von Rührern bewegt.Polymerization processes of this type are described, for example, in Ullmann's Encyklopedia of Industrial Chemistry, 4th Edition, 19th Volume, pp. 169-178. The arrangements for the polymerization zone can advantageously be divided into tubular reactors and / or autoclave reactors. Tubular reactors are tubular polymerization vessels whose length is 10,000 to 40,000 times the tube diameter. In autoclave reactors, the interior of which is usually in the ratio of the height to the diameter of the circular cross section from 1: 1 to 20: 1, the reaction material is moved with the aid of stirrers.

Die folgenden Angaben beziehen sich sämtlich auf die Herstellung in einem kontinuierlich betriebenen Rührautoklaven mit einem Innenvolumen von 1 1.The following details all relate to the production in a continuously operated stirred autoclave with an internal volume of 1 1.

In den folgenden Beispielen ist die Herstellung der Ethylen-Vinylpropionat-Copolymerisate und die Wirkung als Mitteldestillatzusatz im einzelnen beschrieben.The preparation of the ethylene-vinyl propionate copolymers and the action as a middle distillate additive are described in detail in the following examples.

Herstellung der Ethylen-Vinylpropionat-CopolymerisateProduction of the ethylene-vinyl propionate copolymers

Beispiel 1example 1

Eine Mischung von 12,6 kg/h Ethylen, 5,5 kg/h Vinylpropionat und 0,31 kg/h Propionaldehyd werden kontinuierlich durch einen auf einem Druck von 1500 bar gehaltenen 1 1-Rührautoklaven geleitet. Durch die kontinuierliche Zugabe von 2,2 g/h tert.-Butylperisononanat in einem Paraffinkohlenwasserstoffgemisch (Kp. 63-80°C) wird eine Temperatur im Autoklaven von 250°C aufrechterhalten. Nach Entspannung des Reaktionsgemisches fallen 4,9 kg Ethylen--Vinylpropionat-Wachs mit einem Vinylpropionat-Gehalt von 28,4 Gew.% und einer Schmelzviskosität (bei 120°C) von 250 mm2/s an. Das mittlere Molekulargewicht (Zahlenmittel M n) beträgt 1730 (Mechrolab-Dampfphasenosmometer Model 301 A, Lösungsmittel Toluol).A mixture of 12.6 kg / h of ethylene, 5.5 kg / h of vinyl propionate and 0.31 kg / h of propionaldehyde are passed continuously through a 1 l stirred autoclave kept at a pressure of 1500 bar. The temperature in the autoclave is maintained at 250 ° C. by the continuous addition of 2.2 g / h of tert-butyl perisononanate in a paraffin hydrocarbon mixture (bp. 63-80 ° C.). After relaxation of the reaction mixture, 4.9 kg of ethylene-vinyl propionate wax with a vinyl propionate content of 28.4% by weight and a melt viscosity (at 120 ° C.) of 250 mm 2 / s are obtained. The average molecular weight (number average M n ) is 1730 (Mechrolab vapor phase osmometer Model 301 A, solvent toluene).

Figure imgb0001
Herstellung von Ethylen-Vinylacetat-Copolymerisat
Figure imgb0001
 Production of ethylene-vinyl acetate copolymer

Vergleichsbeispiel 6Comparative Example 6

Eine Mischung von 12,2 kg/h Ethylen, 5,6 kg/h Vinylacetat und 0,55 kg/h Propionaldehyd werden kontinuierlich durch einen auf einem Druck von 1500 bar gehaltenen 1 1-Rührautoklaven geleitet. Durch die kontinuierliche Zugabe von 5,5 g/h tert.-Butylperisononanat in einem Paraffinkohlenwasserstoffgemisch (Kp. 175-210) wird eine Temperatur im Autoklaven von 250°C aufrechterhalten. Nach Entspannung des Reaktionsgemisches fallen 5,3 kg Ethylen-Vinylacetat--Wachs mit einem Vinylacetatgehalt von 28,3 Gew.% und einer Schmelzviskosität (bei 120o C) von 250 mm2/s an. Das mittlere Molekulargewicht (Zahlenmittel Mn) beträgt 1760 (Mechrolab-Dampfphasenosmometer Modell 301 A, Lösungsmittel Toluol).A mixture of 12.2 kg / h of ethylene, 5.6 kg / h of vinyl acetate and 0.55 kg / h of propionaldehyde are continuously passed through a 1 l stirred autoclave kept at a pressure of 1500 bar. A temperature of 250 ° C. is maintained in the autoclave by the continuous addition of 5.5 g / h of tert-butyl perisononanate in a paraffin-hydrocarbon mixture (bp. 175-210). After the reaction mixture had been let down, 5.3 kg of ethylene-vinyl acetate wax were obtained with a vinyl acetate content of 28.3% by weight and a melt viscosity (at 120 ° C. ) of 250 mm 2 / s. The average molecular weight (number average M n) is 1760 (Mechrolab vapor phase osmometer model 301 A, solvent toluene).

Anwendungapplication

Die folgende Tabelle II gibt die Wirksamkeit der in den Herstellungsbeispielen 1 bis 6 beschriebenen Copolymeren bezüglich ihres CFPP-Wertes wieder. Beispiele 4 und 5 sind zum Vergleich mit Produkten höherer Vinylpropionatanteile, Beispiel 6 ist zum Vergleich mit Ethylen-Vinylacetatcopolymeren aufgeführt.

Figure imgb0002
The following Table II shows the effectiveness of the copolymers described in Preparation Examples 1 to 6 with regard to their CFPP value. Examples 4 and 5 are listed for comparison with products with a higher vinyl propionate content, Example 6 is listed for comparison with ethylene-vinyl acetate copolymers.
Figure imgb0002

Claims (2)

1. Erdöldestillat im Siedebereich von 120 bis 400°C, gekennzeichnet durch einen Gehalt von 0,005 bis 0,5 Gewichtsprozent eines Ethylen-Vinylpropionatcopolymerisats mit einem Molekulargewicht von 1000 bis 3000 und einem Vinylpropionatgehalt von 5 bis 29 Gew.%, bezogen auf das Copolymere.1. petroleum distillate in the boiling range from 120 to 400 ° C, characterized by a content of 0.005 to 0.5 percent by weight of an ethylene-vinyl propionate copolymer with a molecular weight of 1000 to 3000 and a vinyl propionate content of 5 to 29% by weight, based on the copolymer. 2. Erdöldestillat gemäß Anspruch 1 gekennzeichnet durch einen Gehalt eines Ethylen-Copolymeren mit einem Vinylpropionatgehalt von 12 bis 28,5 Gewichtsprozent bezogen auf das Copolymere.2. Petroleum distillate according to claim 1, characterized by a content of an ethylene copolymer with a vinyl propionate content of 12 to 28.5 percent by weight, based on the copolymer.
EP82111819A 1982-01-20 1982-12-20 Petrol middle distillate with modified flow properties Expired EP0084148B1 (en)

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Application Number Priority Date Filing Date Title
DE3201541 1982-01-20
DE19823201541 DE3201541A1 (en) 1982-01-20 1982-01-20 PETROLEUM DISTILLATES WITH IMPROVED FLOW PROPERTIES

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0217602A1 (en) * 1985-09-24 1987-04-08 Mitsubishi Petrochemical Co., Ltd. Fuel oil additive and fuel oil having improved flowability
JPS6295392A (en) * 1985-10-19 1987-05-01 Showa Shell Sekiyu Kk fuel oil composition
EP0309897A3 (en) * 1987-09-29 1991-05-15 Hoechst Aktiengesellschaft Copolymers of ethylene and methoxy acetic acid vinyl ester and their use as additives for mineral oil distillates
WO1994000537A1 (en) * 1992-06-30 1994-01-06 Exxon Chemical Patents Inc. Oil additives and compositions
US6071993A (en) * 1996-05-31 2000-06-06 Basf Aktiengesellschaft Paraffin dispersants for crude oil middle distillates
WO2014095408A1 (en) 2012-12-18 2014-06-26 Basf Se Polymer formulations in solvents with a high flash point, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products
WO2014095412A1 (en) 2012-12-18 2014-06-26 Basf Se Polymer compositions of ethylene-vinyl ester copolymers and alkyl(meth)acrylates, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products
US9574146B2 (en) 2012-12-18 2017-02-21 Basf Se Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products
WO2017089212A1 (en) 2015-11-27 2017-06-01 Basf Se Copolymers comprising α-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3048479A (en) * 1959-08-03 1962-08-07 Exxon Research Engineering Co Ethylene-vinyl ester pour depressant for middle distillates

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0217602A1 (en) * 1985-09-24 1987-04-08 Mitsubishi Petrochemical Co., Ltd. Fuel oil additive and fuel oil having improved flowability
US4802892A (en) * 1985-09-24 1989-02-07 Mitsubishi Petrochemical Co., Ltd. Fuel oil additive and fuel oil having improved flowability
JPS6295392A (en) * 1985-10-19 1987-05-01 Showa Shell Sekiyu Kk fuel oil composition
EP0309897A3 (en) * 1987-09-29 1991-05-15 Hoechst Aktiengesellschaft Copolymers of ethylene and methoxy acetic acid vinyl ester and their use as additives for mineral oil distillates
WO1994000537A1 (en) * 1992-06-30 1994-01-06 Exxon Chemical Patents Inc. Oil additives and compositions
US6071993A (en) * 1996-05-31 2000-06-06 Basf Aktiengesellschaft Paraffin dispersants for crude oil middle distillates
WO2014095408A1 (en) 2012-12-18 2014-06-26 Basf Se Polymer formulations in solvents with a high flash point, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products
WO2014095412A1 (en) 2012-12-18 2014-06-26 Basf Se Polymer compositions of ethylene-vinyl ester copolymers and alkyl(meth)acrylates, method for the production thereof and use thereof as pour-point depressants for crude oils, mineral oils or mineral oil products
US9574146B2 (en) 2012-12-18 2017-02-21 Basf Se Polymeric compositions composed of ethylene-vinyl ester copolymers alkyl (meth)acrylates, processes for production thereof and use thereof as pour point depressants for crude oils, mineral oils or mineral oil products
US10072115B2 (en) 2012-12-18 2018-09-11 Basf Se Polymeric compositions as pour point depressants for crude oils
US10287384B2 (en) 2012-12-18 2019-05-14 Basf Se Polymeric compositions as pour point depressants for crude oils
WO2017089212A1 (en) 2015-11-27 2017-06-01 Basf Se Copolymers comprising α-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products
US10781385B2 (en) 2015-11-27 2020-09-22 Basf Se Copolymers comprising a-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products
US11236282B2 (en) 2015-11-27 2022-02-01 Basf Se Copolymers comprising a-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products

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DE3201541A1 (en) 1983-07-28
DE3265469D1 (en) 1985-09-19
EP0084148A3 (en) 1983-08-03
EP0084148B1 (en) 1985-08-14

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