EP0111883B1 - Use of ethylene copolymers as mineral oil additives - Google Patents

Use of ethylene copolymers as mineral oil additives Download PDF

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Publication number
EP0111883B1
EP0111883B1 EP83112556A EP83112556A EP0111883B1 EP 0111883 B1 EP0111883 B1 EP 0111883B1 EP 83112556 A EP83112556 A EP 83112556A EP 83112556 A EP83112556 A EP 83112556A EP 0111883 B1 EP0111883 B1 EP 0111883B1
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Prior art keywords
weight
vinyl
waxy
units
ethylene
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German (de)
French (fr)
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EP0111883A1 (en
EP0111883B2 (en
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John Dr. Dipl.-Chem. Hobes
Karl Heinz Dr. Dipl.-Chem. Heier
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Hoechst AG
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Hoechst AG
Ruhrchemie AG
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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, 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
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • 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
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • 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

Definitions

  • the present invention relates to the use of copolymers of ethylene as pour point depressants and flow improvers for crude oils and middle distillates of crude oil distillation.
  • copolymers of ethylene with esters of vinyl alcohol, especially vinyl acetate are economically most important pour point depressants and flow improvers for crude oils and middle distillates.
  • Such copolymers and their use are e.g. B. in DE-A-1 914 756 and DE-A-2 515 805.
  • From GB-A-1 235 836 it is known to use copolymers of ethylene and vinyl methyl ketone as flow improvers.
  • copolymers mentioned are generally prepared in autoclaves at temperatures from 80 to 150 ° C. and pressures from 50 to 150 bar with peroxides as initiators and in the presence of organic solvents as the reaction medium.
  • the present invention relates to the use of waxy copolymers with a molecular weight of 500 to 20,000, which consist of at least 60% by weight of ethylene units, at least 1% by weight of alkenecarboxylic acid ester and / or vinyl ester units, and 1 to 30% by weight.
  • -% vinyl ketone units as well as minor amounts of customary other monomers copolymerizable with ethylene exist as flow improvers for crude oils and middle distillates of crude oil distillation.
  • waxy copolymers of ethylene which in addition to alkenecarboxylic acid ester units and / or vinyl ester units also contain vinyl ketone units, significantly improve the flowability of both middle distillates from crude oil distillation and crude oils themselves, compared to conventional products.
  • the improvement in flowability does not correspond to an additive effect of the content of ester and vinyl ketone units in the ethylene copolymers. Rather, it is shown that the action of the ester and vinyl ketone units increases synergistically.
  • the copolymers preferably contain 75 to 94% by weight of ethylene units, 5 to 15% by weight of alkenecarboxylic acid ester units and 1 to 10% by weight of vinyl ketone units.
  • the ethylene copolymers used according to the invention are prepared by polymerizing the monomer mixture at temperatures of 100-350 ° C. and pressures of 1000-8000 bar in the presence of initiators which form free radicals. The polymerization does not require the presence of a solvent as the reaction medium. Solvent-free products are therefore obtained immediately.
  • esters of alkenecarboxylic acids having 3 to 12 carbon atoms with primary, secondary or tertiary alcohols containing 1 to 8 carbon atoms can be used as alkenecarboxylic acid esters. Examples are methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyacrylate. Examples of vinyl esters are vinyl acetate, vinyl propionate; vinyl acetate is particularly suitable. Compounds such as vinyl methyl ketone, vinyl ethyl ketone, vinyl propyl ketone and preferably vinyl methyl ketone are suitable as vinyl ketones.
  • Conventional monomers copolymerizable with ethylene are, for. B. C 3 - to Ca alkenes, vinyl and alkenyl ethers, vinyl and alkenyl alcohols, N-vinyl and N-alkenyl compounds, such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylcaprolactam, acrylic and methacrylamides, acrylic and Methacrylonitriles, vinyl and alkene ketones, vinyl and alkenyl sulfones and sulfonates, dicarbonates, acid anhydrides and styrene.
  • alkenes vinyl and alkenyl ethers, vinyl and alkenyl alcohols
  • N-vinyl and N-alkenyl compounds such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylcaprolactam, acrylic and methacrylamides, acrylic and Methacrylonitriles, vinyl and alkene keto
  • the polymerization takes place in the presence of catalytic amounts of free radical initiators, e.g. B. oxygen, in amounts of 2 to 250 molppm, based on the ethylene to be polymerized.
  • free radical initiators e.g. B. oxygen
  • peroxides such as tert-butyl perbenzoate, dilauroyl peroxide, di-tert-butyl peroxide or azobutyronitrile in amounts of 2 to 200 molppm, based on the ethylene, can also be used as initiators.
  • moderators such as aliphatic alcohols and / or carbonyl compounds, saturated, unsaturated or chlorinated hydrocarbons or hydrogen.
  • copolymers used according to the invention have molecular weights of 500 to 20,000, determined according to K. Rast, Ber. 550, 1922.
  • copolymers described above improve the flow properties of mineral oils such as middle distillates from crude oil distillation and also from crude oil itself. Their effect is based on the fact that they influence the crystal growth of the paraffin which precipitates in the cold in such a way that the paraffin crystals remain small and do not agglomerate and therefore Filters can pass.
  • These copolymers are normally added to the mineral oil in the form of about 40 to 50% solutions in an aromatic hydrocarbon.
  • the amount of copolymer based on the mineral oil should be 0.001 to 2, preferably 0.005 to 0.5% by weight.
  • the copolymers can be used alone or together with other pour point depressants or dewaxing agents, corrosion inhibitors, antioxidants or sludge inhibitors.
  • the copolymers are also suitable as adhesives, as coating materials and for mixing with waxes whose properties they improve.
  • a paraffin-rich middle distillate with a boiling point of 175 ° C, 5% point 195 ° C, 95% point 365 ° C, boiling point 383 ° C and a CFPP value of + 5 ° C is mixed with 200 ppm of an additive, which is 48% of a copolymer wax contains ethylene and 20% vinyl acetate with a viscosity (at 140 ° C) of 450 mPas.
  • the middle distillate treated in this way has a CFPP value of 0 ° C.
  • the middle distillate of Comparative Example A is mixed with a copolymer wax made of ethylene and 22% t-butyl acrylate, which has a viscosity (at 140 ° C) of 550 mPas, under otherwise constant conditions, the middle distillate treated in this way has a CFPP value of +1 ° C.
  • Comparative Example A If the middle distillate of Comparative Example A is mixed under otherwise constant conditions with a copolymer wax of ethylene and 10% methyl vinyl ketone, which has a viscosity (at 140 ° C.) of 500 mPas, a CFPP value of + 1 ° C. is measured.
  • a middle distillate with a boiling point of 178 ° C, 5% point of 201 ° C, 95% point of 359 ° C, boiling point of 376 ° C and CFPP of -4 ° C is mixed with 200 ppm of an additive that contains 48% of a copolymer wax from ethylene and 24 % Contains vinyl acetate with a viscosity (at 140 "C) of 1600 mPas.
  • the middle distillate treated in this way has a CFPP value of ⁇ 7 ° C.
  • the middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 19% vinyl acetate and 1% methyl vinyl ketone with a viscosity (at 140 ° C.) of 440 mPas.
  • the middle distillate treated in this way has a CFPP value of -3 ° C.
  • the middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 15% t-butyl acrylate and 3% methyl vinyl ketone with a viscosity (at 140 ° C.) of 600 mPas.
  • the middle distillate treated in this way has one CFPP value of -4 ° C.
  • the middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 15% vinyl acetate and 5% methyl vinyl ketone with a viscosity (at 140 ° C.) of 1480 mPas.
  • the middle distillate treated in this way has a CFPP value of -4 ° C.
  • the middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% strength of a terpolymer wax made of ethylene, 5% vinyl acetate and 10% vinyl methyl ketone with a viscosity (at 140 ° C.) of 560 mPas.
  • the middle distillate treated in this way has a CFPP value of -6 ° C.
  • the middle distillate of Comparative Example D is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 10% vinyl acetate and 10% methyl vinyl ketone with a viscosity (at 140 ° C.) of 1450 mPas.
  • the middle distillate thus treated has a CFPP of -14 ° C.

Abstract

Waxy highly branched copolymers having a molecular weight of 500 to 20,000 comprised of at least 60% by weight of ethylene, 1 to 39% by weight of an alkene carboxylic acid ester and/or a vinyl ester and 1-30% by weight of a vinyl ketone produced by polymerization at 100 to 350 DEG C. and a pressure of about 1,000 to 8,000 bar in the presence of a radical forming initiator and in the absence of a solvent useful as oil additives to improve flow characteristics of crude oils and middle distillates derived from crude oil.

Description

Die vorliegende Erfindung betrifft die Verwendung von Copolymeren des Ethylens als Stockpunkterniedriger und Fließverbesserer für Rohöle und Mitteldestillate der Rohöldestillation.The present invention relates to the use of copolymers of ethylene as pour point depressants and flow improvers for crude oils and middle distillates of crude oil distillation.

Die wirtschaftlich wichtigsten Stockpunkterniedriger und Fließverbesserer für Rohöle und Mittedestillate sind Copolymerisate des Ethylens mit Estern des Vinylalkohols, insbesondere des Vinylacetats. Derartige Mischpolymerisate und ihre Verwendung sind z. B. in den DE-A-1 914 756 und DE-A-2 515 805 beschrieben. Aus der GB-A-1 235 836 ist es bekannt, Copolymerisate aus Ethylen und Vinylmethylketon als Fließverbessererzu verwenden.The economically most important pour point depressants and flow improvers for crude oils and middle distillates are copolymers of ethylene with esters of vinyl alcohol, especially vinyl acetate. Such copolymers and their use are e.g. B. in DE-A-1 914 756 and DE-A-2 515 805. From GB-A-1 235 836 it is known to use copolymers of ethylene and vinyl methyl ketone as flow improvers.

Die Herstellung der genannten Copolymeren erfolgt im allgemeinen in Autoklaven bei Temperaturen von 80 bis 150"C und Drücken von 50 bis 150 bar mit Peroxiden als Initiatoren und in Gegenwart organischer Lösungsmittel als Reaktionsmedium.The copolymers mentioned are generally prepared in autoclaves at temperatures from 80 to 150 ° C. and pressures from 50 to 150 bar with peroxides as initiators and in the presence of organic solvents as the reaction medium.

Gegenstand der vorliegenden Erfindung ist die Verwendung wachsartiger Copolymerisate mit einem Molekulargewicht von 500 bis 20000, die aus mindestens 60 Gew.-% Ethylen-Einheiten, mindestens 1 Gew.-% Alkencarbonsäureester- und/oder Vinylester-Einheiten, und 1 bis 30 Gew.-% Vinylketon-Einheiten sowie untergeordnete Mengen üblicher weiterer, mit Ethylen copolymerisierbarer Monomerer bestehen, als Fließverbesserer für Rohöle und Mitteldestillate der Rohöldestillation. Überraschenderweise hat sich nämlich herausgestellt, daß wachsartige Copolymerisate des Ethylens, die neben Alkencarbonsäureestereinheiten und/oder Vinylester-einheiten auch noch Vinylketoneinheiten enthalten, die Fließfähigkeit sowohl von Mitteldestillaten der Rohöldestillation als auch von Rohölen selbst, gegenüber herkömmlichen Produkten erheblich verbessern. Die Verbesserung der Fließfähigkeit entspricht dabei nicht einer additiven Wirkung des Gehaltes der Ethylenmischpolymeren an Ester- und Vinylketoneinheiten. Es zeigt sich vielmehr, daß sich die Wirkung der Ester-und Vinylketoneinheiten synergistisch verstärkt.The present invention relates to the use of waxy copolymers with a molecular weight of 500 to 20,000, which consist of at least 60% by weight of ethylene units, at least 1% by weight of alkenecarboxylic acid ester and / or vinyl ester units, and 1 to 30% by weight. -% vinyl ketone units as well as minor amounts of customary other monomers copolymerizable with ethylene exist as flow improvers for crude oils and middle distillates of crude oil distillation. Surprisingly, it has been found that waxy copolymers of ethylene, which in addition to alkenecarboxylic acid ester units and / or vinyl ester units also contain vinyl ketone units, significantly improve the flowability of both middle distillates from crude oil distillation and crude oils themselves, compared to conventional products. The improvement in flowability does not correspond to an additive effect of the content of ester and vinyl ketone units in the ethylene copolymers. Rather, it is shown that the action of the ester and vinyl ketone units increases synergistically.

Vorzugsweise enthalten die Copolymerisate 75 bis 94Gew.-% Ethylen-Einheiten, 5 bis 15 Gew.-% Alkencarbonsäureester-Einheiten und 1 bis 10 Gew.-% Vinylketon-Einheiten.The copolymers preferably contain 75 to 94% by weight of ethylene units, 5 to 15% by weight of alkenecarboxylic acid ester units and 1 to 10% by weight of vinyl ketone units.

Die Herstellung der erfindungsgemäß verwendeten Ethylencopolymerisate erfolgt durch Polymerisation des Monomerengemisches bei Temperaturen von 100-350°C und Drücken von 1000-8000 bar in Gegenwart Radikale bildender Initiatoren. Die Polymerisation erfordert nicht die Anwesenheit eines Lösungsmittels als Reaktionsmedium. Man erhält daher unmittelbar lösungsmittelfreie Produkte.The ethylene copolymers used according to the invention are prepared by polymerizing the monomer mixture at temperatures of 100-350 ° C. and pressures of 1000-8000 bar in the presence of initiators which form free radicals. The polymerization does not require the presence of a solvent as the reaction medium. Solvent-free products are therefore obtained immediately.

Das als Ausgangsstoff verwendete Ethylen wird in der für Polymerisationsreaktionen üblichen Reinheit von mindestens 99,9% eingesetzt. Als Alkencarbonsäureester können Ester von Alkencarbonsäuren mit 3 bis 12 Kohlenstoffatomen mit primären, sekundären oder tertiären Alkoholen die 1 bis 8 Kohlenstoffatome enthalten, verwendet werden. Beispiele sind Methylacrylat, Ethylacrylat, Butylacrylat oder 2-Ethylhexyacrylat. Beispiele für Vinylester sind Vinylacetat, Vinylpropionat; besonders geeignet ist Vinylacetat. Als Vinylketone kommen Verbindungen wie Vinylmethylketon, Vinylethylketon, Vinylpropylketon und bevorzugt Vinylmethylketon in Betracht.The ethylene used as the starting material is used in the purity of at least 99.9% customary for polymerization reactions. Esters of alkenecarboxylic acids having 3 to 12 carbon atoms with primary, secondary or tertiary alcohols containing 1 to 8 carbon atoms can be used as alkenecarboxylic acid esters. Examples are methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyacrylate. Examples of vinyl esters are vinyl acetate, vinyl propionate; vinyl acetate is particularly suitable. Compounds such as vinyl methyl ketone, vinyl ethyl ketone, vinyl propyl ketone and preferably vinyl methyl ketone are suitable as vinyl ketones.

Übliche, mit Ethylen copolymerisierbare Monomere, die in den Copolymerisaten zusätzlich enthalten sein können, sind z. B. C3- bis Ca-Alkene, Vinyl- und Alkenyläther, Vinyl- und Alkenylalkohole, N-Vinyl- und N-Alkenylverbindungen, wie N-Vinylpyrrolidon, N-Vinylcarbazol, N-Vinylcaprolactam, Acryl- und Methacrylamide, Acryl- und Methacrylnitrile, Vinyl- und Alkenketone, Vinyl- und Alkenylsulfone und -sulfonate, Dicarbonate, Säureanhydride und Styrol.Conventional monomers copolymerizable with ethylene, which may also be present in the copolymers, are, for. B. C 3 - to Ca alkenes, vinyl and alkenyl ethers, vinyl and alkenyl alcohols, N-vinyl and N-alkenyl compounds, such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylcaprolactam, acrylic and methacrylamides, acrylic and Methacrylonitriles, vinyl and alkene ketones, vinyl and alkenyl sulfones and sulfonates, dicarbonates, acid anhydrides and styrene.

Die Polymerisation läuft in Gegenwart katalytischer Mengen Radikale bildender Initiatoren, z. B. Sauerstoff, in Mengen von 2 bis 250 Molppm, bezogen auf das zu polymerisierende Ethylen ab. Neben Sauerstoff können als Initiatoren auch Peroxide, wie tert.-Butylperbenzoat, Dilauroylperoxid, Di-tert.-Butylperoxid oder Azobuttersäuredinitril in Mengen von 2 bis 200 Molppm, bezogen auf das Ethylen, verwendet werden. Die Einstellung der Molekulargewichte erfolgt mit Moderatoren, wie aliphatischen Alkoholen und/oder Carbonylverbindungen, gesättigten, ungesättigten oder clorierten Kohlenwasserstoffen oder Wasserstoff. In Abhängigkeit vom gewünschten Molekulargewicht werden sie in Konzentrationen zwischen 2 und 25 Vol.-%, bezogen auf Ethylen, angewandt. Die erfindungsgemäß eingesetzten Copolymerisate haben Molekulargewichte von 500 bis 20 000, bestimmt nach K. Rast, Ber. 550,1922.The polymerization takes place in the presence of catalytic amounts of free radical initiators, e.g. B. oxygen, in amounts of 2 to 250 molppm, based on the ethylene to be polymerized. In addition to oxygen, peroxides such as tert-butyl perbenzoate, dilauroyl peroxide, di-tert-butyl peroxide or azobutyronitrile in amounts of 2 to 200 molppm, based on the ethylene, can also be used as initiators. The molecular weights are adjusted using moderators, such as aliphatic alcohols and / or carbonyl compounds, saturated, unsaturated or chlorinated hydrocarbons or hydrogen. Depending on the desired molecular weight, they are used in concentrations of between 2 and 25% by volume, based on ethylene. The copolymers used according to the invention have molecular weights of 500 to 20,000, determined according to K. Rast, Ber. 550, 1922.

Die vorstehend beschriebenen Copolymerisate verbessern die Fließeigenschaften von Mineralölen wie Mitteldestillaten der Rohöldestillation und auch von Rohöl selbst. Ihre Wirkung beruht darauf, daß sie das Kristallwachstum des in der Kälte ausfallenden Paraffins in der Weise beeinflussen, daß die Paraffinkristalle klein bleiben und nicht agglomerieren und daher die Filter passieren können. Man setzt diese Copolymerisate dem Mineralöl normalerweise in Form von etwa 40 bis 50%igen Lösungen in einem aromatischen Kohlenwasserstoff zu. Die Copolymerisatmenge bezogen auf das Mineralöl soll 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% betragen. Die Copolymerisate können allein oder auch zusammen mit anderen Stockpunkterniedrigern oder EntwachsungshilfsmitteIn, Korrosionsinhibitoren, Antioxidantien oder Schlamminhibitoren. Darüber hinaus eignen sich die Copolymerisate auch als Kleber, als Beschichtungsmaterialien und zur Abmischung mit Wachsen deren Eigenschaften sie verbessern.The copolymers described above improve the flow properties of mineral oils such as middle distillates from crude oil distillation and also from crude oil itself. Their effect is based on the fact that they influence the crystal growth of the paraffin which precipitates in the cold in such a way that the paraffin crystals remain small and do not agglomerate and therefore Filters can pass. These copolymers are normally added to the mineral oil in the form of about 40 to 50% solutions in an aromatic hydrocarbon. The amount of copolymer based on the mineral oil should be 0.001 to 2, preferably 0.005 to 0.5% by weight. The copolymers can be used alone or together with other pour point depressants or dewaxing agents, corrosion inhibitors, antioxidants or sludge inhibitors. In addition, the copolymers are also suitable as adhesives, as coating materials and for mixing with waxes whose properties they improve.

In den folgenden Beispielen wird die Verbesserung der Fließfähigkeit bei Mitteldestillaten oder Rohöldestillation durch die erfindungsgemäße Verwendung bestimmter Copolymerisate des Ethylens an Hand des »Kalt-Filter-Verstopfungspunkt-Test« (CFPPT) gezeigt. Dieser Test ist in J. of the Inst. of Petr., Bd. 52, Juni 1966, S. 173 bis 185 sowie in DIN 51 428 beschrieben.The following examples show the improvement in fluidity in middle distillates or crude oil distillation by the use according to the invention of certain copolymers of ethylene using the "cold filter clogging point test" (CFPPT). This test is described in J. of the Inst. Of Petr., Vol. 52, June 1966, pp. 173 to 185 and in DIN 51 428.

Vergleichsbeispiel AComparative Example A

Ein paraffinreiches Mitteldestillat mit Siedebeginn 175°C, 5% Punkt 195°C, 95% Punkt 365° C, Siedeende 383° C und einem CFPP-Wert von +5°C wird mit 200 ppm eines Additivs versetzt, das 48% eines Copolymerwachses aus Ethylen und 20% Vinylacetat mit einer Viskosität (bei 140°C) von 450 mPas enthält. Das so behandelte Mitteldestillat hat einen CFPP-Wert von 0° C.A paraffin-rich middle distillate with a boiling point of 175 ° C, 5% point 195 ° C, 95% point 365 ° C, boiling point 383 ° C and a CFPP value of + 5 ° C is mixed with 200 ppm of an additive, which is 48% of a copolymer wax contains ethylene and 20% vinyl acetate with a viscosity (at 140 ° C) of 450 mPas. The middle distillate treated in this way has a CFPP value of 0 ° C.

Vergleichsbeispiel BComparative Example B

Wird das Mitteldestillat des Vergleichsbeispiels A unter sonst konstanten Bedingungen mit einem Copolymerwachs aus Ethylen und 22% t-Butylacrylat, das eine Viskosität (bei 140°C) von 550 mPas aufweist, versetzt, hat das so behandelte Mitteldestillat einen CFPP-Wert von +1°C.If the middle distillate of Comparative Example A is mixed with a copolymer wax made of ethylene and 22% t-butyl acrylate, which has a viscosity (at 140 ° C) of 550 mPas, under otherwise constant conditions, the middle distillate treated in this way has a CFPP value of +1 ° C.

Vergleichsbeispiel CComparative Example C

Wird das Mitteldestillat des Vergleichsbeispiels A unter sonst konstanten Bedingungen mit einem Copolymerwachs aus Ethylen und 10% Methylvinylketon, das eine Viskosität (bei 140° C) von 500 mPas aufweist, versetzt, so wird ein CFPP-Wert von +1°C gemessen.If the middle distillate of Comparative Example A is mixed under otherwise constant conditions with a copolymer wax of ethylene and 10% methyl vinyl ketone, which has a viscosity (at 140 ° C.) of 500 mPas, a CFPP value of + 1 ° C. is measured.

Vergleichsbeispiel DComparative Example D

Ein Mitteldestillat mit Siedebeginn 178° C, 5% Punkt 201 ° C, 95% Punkt 359° C, Siedeende 376° C und CFPP von -4°C wird mit 200 ppm eines Additivs versetzt, das 48% eines Copolymerwachses aus Ethylen und 24% Vinylacetat mit einer Viskosität (bei 140"C) von 1600 mPas enthält. Das so behandelte Mitteldestillat hat einen CFPP-Wert von―7°C.A middle distillate with a boiling point of 178 ° C, 5% point of 201 ° C, 95% point of 359 ° C, boiling point of 376 ° C and CFPP of -4 ° C is mixed with 200 ppm of an additive that contains 48% of a copolymer wax from ethylene and 24 % Contains vinyl acetate with a viscosity (at 140 "C) of 1600 mPas. The middle distillate treated in this way has a CFPP value of ― 7 ° C.

Beispiel 1example 1

Das Mitteldestillat des Vergleichsbeispiels A wird mit 200 ppm eines Additivs versetzt, das 48% eines Terpolymerwachses aus Ethylen, 19% Vinylacetat und 1% Methylvinylketon mit einer Viskosität (bei 140° C) von 440 mPas, enthält. Das so behandelte Mitteldestillat hat einen CFPP-Wert von -3° C.The middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 19% vinyl acetate and 1% methyl vinyl ketone with a viscosity (at 140 ° C.) of 440 mPas. The middle distillate treated in this way has a CFPP value of -3 ° C.

Beispiel 2Example 2

Das Mitteldestillat des Vergleichsbeispiels A wird mit 200 ppm eines Additivs versetzt, das 48% eines Terpolymerwachses aus Ethylen, 15% t-Butylacrylat und 3% Methylvinylketon mit einer Viskosität (bei 140"C) von 600 mPas enthält. Das so behandelte Mitteldestillat hat einen CFPP-Wert von -4°C.The middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 15% t-butyl acrylate and 3% methyl vinyl ketone with a viscosity (at 140 ° C.) of 600 mPas. The middle distillate treated in this way has one CFPP value of -4 ° C.

Beispiel 3Example 3

Das Mitteldestillat des Vergleichsbeispiels A wird mit 200 ppm eines Additivs versetzt, das 48% eines Terpolymerwachses aus Ethylen, 15% Vinylacetat und 5% Methylvinylketon mit einer Viskosität (bei 140°C) von 1480 mPas enthält. Das so behandelte Mitteldestillat hat einen CFPP-Wert von -4° C.The middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 15% vinyl acetate and 5% methyl vinyl ketone with a viscosity (at 140 ° C.) of 1480 mPas. The middle distillate treated in this way has a CFPP value of -4 ° C.

Beispiel 4Example 4

Das Mitteldestillat des Vergleichsbeispiels A wird mit 200 ppm eines Additivs versetzt, das 48%ig eines Terpolymerwachses aus Ethylen, 5% Vinylacetat und 10% Vinylmethylketon mit einer Viskosität (bei 140° C) von 560 mPas enthält. Das so behandelte Mitteldestillat hat einen CFPP-Wert von -6°C.The middle distillate of Comparative Example A is mixed with 200 ppm of an additive which contains 48% strength of a terpolymer wax made of ethylene, 5% vinyl acetate and 10% vinyl methyl ketone with a viscosity (at 140 ° C.) of 560 mPas. The middle distillate treated in this way has a CFPP value of -6 ° C.

Beispiel 5Example 5

Das Mitteldestillat des Vergleichsbeispiels D wird mit 200 ppm eines Additivs versetzt, das 48% eines Terpolymerwachses aus Ethylen, 10% Vinylacetat und 10% Methylvinylketon mit einer Viskosität (bei 140° C) von 1450 mPas, enthält. Das so behandelte Mitteldestillat hat einen CFPP-Wertvon -14°C.The middle distillate of Comparative Example D is mixed with 200 ppm of an additive which contains 48% of a terpolymer wax made of ethylene, 10% vinyl acetate and 10% methyl vinyl ketone with a viscosity (at 140 ° C.) of 1450 mPas. The middle distillate thus treated has a CFPP of -14 ° C.

Claims (7)

1. The use of waxy copolymerisates with a molecular weight of 500 to 20 000 consisting of at least 60 per cent by weight ethylene units, at least 1 to 40 per cent by weight alkene carboxylic acid ester and/or vinyl ester units and 1 to 30 per cent by weight vinyl ketone units as well as minor amounts of other common monomers which can be copolymerised with ethylene as flow improvers for crude oils and middle distillates from crude oil distillation.
2. The use of waxy copolymerisates according to claim 1, characterized in that they contain 75 to 94 per cent by weight ethylene units.
3. The use of waxy copolymerisates according to claims 1 and 2, characterized in that they contain 5 to 15 per cent by weight alkene carboxylic acid ester units.
4. The use of waxy copolymerisates according to claims 1 to 3, characterized in that they contain 1 to 10 per cent by weight vinyl ketone units.
5. The use of waxy copolymerisates according to claims 1 to 4, characterized in that as alkene carboxylic acid ester units they contain alkene carboxylic acids with 3 to 12 carbon atoms and primary, secondary or tertiary alcohols with 1 to 8 carbon atoms.
6. The use of waxy copolymerisates according to claims 1 to 5, characterized in that as a vinyl ester unit they contain vinyl acetate.
7. The use of waxy copolymerisates according to claims 1 to 6, characterized in that as vinyl ketone units they contain methyl vinyl ketone.
EP83112556A 1982-12-23 1983-12-14 Use of ethylene copolymers as mineral oil additives Expired EP0111883B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83112556T ATE15064T1 (en) 1982-12-23 1983-12-14 USE OF ETHYLENE COPOLYMERISATES AS MINERAL OIL ADDITIVES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3247753 1982-12-23
DE19823247753 DE3247753A1 (en) 1982-12-23 1982-12-23 USE OF ETHYLENE COPOLYMERISATES AS A MINERAL OIL ADDITIVE

Publications (3)

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EP0111883A1 EP0111883A1 (en) 1984-06-27
EP0111883B1 true EP0111883B1 (en) 1985-08-21
EP0111883B2 EP0111883B2 (en) 1988-10-26

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AT (1) ATE15064T1 (en)
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DE4020640A1 (en) * 1990-06-29 1992-01-02 Hoechst Ag TERPOLYMERISATES OF ETHYLENE, THEIR PRODUCTION AND THEIR USE AS ADDITIVES FOR MINERAL OIL DISTILLATES
US6495495B1 (en) 1999-08-20 2002-12-17 The Lubrizol Corporation Filterability improver
DE10309571A1 (en) * 2003-03-05 2004-09-16 Basf Ag Fuel compositions with improved cold flow properties
US20120302479A1 (en) 2009-12-07 2012-11-29 The Lubrizol Corporation Method of Lubricating a Manual Transmission
CN113366028A (en) * 2019-01-28 2021-09-07 日本聚乙烯株式会社 Polar group-containing olefin copolymer

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US3591502A (en) * 1968-07-15 1971-07-06 Exxon Research Engineering Co Copolymers containing ethylene and unsaturated ketones are wax crystal modifiers for mineral oil
GB1300227A (en) * 1969-05-09 1972-12-20 Exxon Research Engineering Co Flow improvers
US3853814A (en) * 1970-04-27 1974-12-10 J Guillet Photodegradable polymers of methyl methacrylate and unsaturated ketones
NL159413B (en) * 1973-01-16 1979-02-15 Ruhrchemie Ag PROCESS FOR PREPARING DEGRADABLE TERCOPOLYMERS FROM ETHENE, CARBON MONOXIDE AND VINYL ACETATE.
DE2822436A1 (en) * 1978-05-23 1979-12-06 Consortium Elektrochem Ind VINYLESTER AND VINYL HALOGENIDE COPOLYMERS CONTAINING HYDROXYL GROUPS
US4230843A (en) * 1979-02-02 1980-10-28 The Lubrizol Corporation Polymeric compositions, method for their preparation, and lubricants containing them

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US4772673A (en) 1988-09-20
NO163454C (en) 1990-05-30
EP0111883A1 (en) 1984-06-27
EP0111883B2 (en) 1988-10-26
NO163454B (en) 1990-02-19
NO834647L (en) 1984-06-25
DE3247753A1 (en) 1984-06-28
ATE15064T1 (en) 1985-09-15

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