EP0320766A2 - Viscosity index-modifying polymer blends for petroleum fractions - Google Patents

Viscosity index-modifying polymer blends for petroleum fractions Download PDF

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Publication number
EP0320766A2
EP0320766A2 EP88120410A EP88120410A EP0320766A2 EP 0320766 A2 EP0320766 A2 EP 0320766A2 EP 88120410 A EP88120410 A EP 88120410A EP 88120410 A EP88120410 A EP 88120410A EP 0320766 A2 EP0320766 A2 EP 0320766A2
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weight
copolymer
vinyl acetate
ethylene
olefin
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German (de)
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EP0320766B1 (en
EP0320766A3 (en
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Herbert Dr. Wirtz
Michael Dr. Feustel
Juliane Balzer
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Hoechst AG
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Hoechst 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • 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
    • C10L1/197—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
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups

Definitions

  • Mineral oil distillates such as diesel fuel or heating oil contain different amounts of long-chain n-paraffins depending on the provenance of the base crude oil and depending on the processing method in the refinery.
  • n-paraffins crystallize when the saturation temperature falls below the orthorhombic crystal lattice in the form of thin trapezoidal or diamond-shaped plates and thin needles. These crystal modifications continue to tend to grow together and agglomerate, resulting in the formation of a three-dimensional network.
  • the crystallization of the n-paraffins is accompanied by a decrease in fluidity and an increase in viscosity.
  • blockages of the filters can occur in diesel engines and combustion systems, which impair safe metering of the fuel and, in the worst case, completely block the fuel supply.
  • n-paraffins / flow improvers adducts enable smooth operation of diesel engines and fuel systems even at low temperatures.
  • additives or flow improvers mainly copolymers of ethylene and vinyl acetate (EVA copolymers) in various variations are used to improve the low-temperature stability of diesel fuels and heating oil.
  • This category includes Middle distillates with a high boiling point (S.E.> 380 ° C).
  • the cloud point (CP) of such oils is often significantly above CP: ⁇ 0 ° C.
  • the invention relates to polymer mixtures of a copolymer (A1) made of 10-60% by weight vinyl acetate and 40-90% by weight ethylene or a copolymer (A2) made of 15-50% by weight Vinyl acetate, 0.5-20% by weight of C6-C24- ⁇ -olefin and 30 -70% by weight of ethylene and a copolymer (B) of 10-90% by weight of C6-C24- ⁇ -olefin and 10-90 % N-C6-C22-alkylmaleimide, the mixing ratio of the copolymers (A1) or (A2) to (B) being 100: 1 to 1: 1.
  • the copolymers mentioned under A1 and A2 are obtained via a high pressure synthesis (reaction pressure: 100-200 MPa; reaction temperature: 120-280 ° C) in a bulk polymerization according to methods known per se.
  • the polymer (A1) are preferred those containing 15-40 wt .-% vinyl acetate and correspondingly 60-85 wt .-% ethylene.
  • the polymer (A2) preferably contains 20 to 30 wt .-% vinyl acetate and 2 to 5 wt .-% ⁇ -olefin. Polymers of this type are partially described in DE-PS 21 02 469 and are produced by the processes described there.
  • the copolymers (B) preferably contain 50% by weight of the ⁇ -olefin and 50% by weight of the N-alkylmaleimide.
  • the ⁇ -olefins preferably contain 8-18 C atoms, the alkyl group in the N-alkylmaleimides preferably contains 12-22 C atoms.
  • the copolymers mentioned under (B) are obtained by solution polymerization of N-alkylmaleimides and ⁇ -olefins at 120 ° C. using typical radical initiators such as tert-butyl perbenzoate or azobisisobutyronitrile.
  • the monomeric maleimide is obtained beforehand by stoichiometric conversion of maleic anhydride and the corresponding amine at 120-150 ° C. using an aromatic hydrocarbon such as toluene or xylene as an entrainer and p-toluenesulfonic acid as a catalyst. The progress of the reaction can be determined via the acid number.
  • the ⁇ -olefin and the free-radical catalyst are then added to this solution and polymerization is carried out by heating to approximately 100-140 ° C.
  • this polymerization can also be carried out in the melt without solvent, with the solvent which was required for the preparation of the N-alkylmaleimide was distilled off before the polymerization.
  • the average molecular weight of all three copolymers is about 1000 to 10000 g mol ⁇ 1.
  • the mixing ratio of the polymers (A1) or (A2) to (B) is 100: 1 to 1: 1, preferably 10: 1 to 6: 1 parts by weight.
  • the polymer mixtures according to the invention are produced by simply mixing the individual components.
  • the polymer mixtures described are notable for their very broad activity and also enable the cold properties of the problem oils mentioned at the beginning to be improved.
  • the polymer mixtures are added to the petroleum distillates in amounts of approximately 10 to 500 ppm.
  • Example II.1 200 g of the solution prepared according to Example I.2 are initially charged with 200 g of a mixture of C20-, C22- and C24- ⁇ -olefins and heated to 120 ° C. A mixture of 2 g of t-butylbenzoyl peroxide in 40 g of toluene is added dropwise over 20 minutes and the mixture is then kept at 140 ° C. for a further 2 hours.
  • Example II.1 specified rule 200 g of the solution prepared according to Example I.3 with 200 g of C18- ⁇ -olefin (octadecene) and heated to 120 ° C. A mixture of 2 g of AIBN in 40 g of toluene is added dropwise over 20 minutes and the mixture is then kept at 120 ° C. for 2 hours

Abstract

Polymer blends of a copolymer (A1) of 10-60% by weight of vinyl acetate and 40-90% by weight of ethylene or of a copolymer (A2) of 15-50% by weight of vinyl acetate, 0.5-20% by weight of C6-C24- alpha -olefine and 30-70% by weight of ethylene and a copolymer (B) of 10-90% by weight of C6-C24- alpha -olefine and 10-90% of N-C6-C12-alkyl- maleimide, the mixing ratio of the copolymers (A1) or (A2) to (B) being 100:1 to 1:1, are used as flow improvers in mineral oil distillates.

Description

Mineralöldestillate wie Dieselkraftstoff oder Heizöl enthalten je nach Provenienz des Basisrohöls und in Abhängigkeit von der Verarbeitungsweise in der Raffinerie unterschiedliche Mengen langkettiger n-Paraffine. Wie schon lange bekannt, wird das Fleißverhalten derartiger Erdölprodukte unter Kälteeinwirkung hauptsächlich durch diesen Gehalt an n-Paraffinen beeinflußt. Solche n-Paraffine kristallisieren bei Unterschreitung der Sättigungstemperatur im orthorhombischen Kristallgitter in Form von dünnen trapez- bzw. rautenförmigen Plättchen sowie dünnen Nadeln aus. Diese Kristallmodifikationen neigen weiterhin zum Ineinanderwachsen und Agglomerieren, wobei es zur Ausbildung eines dreidimensionalen Netzwerkes kommt. Der Kristallisation der n-Paraffine geht eine Abnahme der Fließfähigkeit und Zunahme der Viskosität parallel. Als Folge davon können bei Dieselmotoren und Feuerungsanlagen Verstopfungen der Filter auftreten, die eine sichere Dosierung des Brennstoffes beeinträchtigen und im schlimmsten Fall die Kraftstoffzufuhr gänzlich unterbinden.Mineral oil distillates such as diesel fuel or heating oil contain different amounts of long-chain n-paraffins depending on the provenance of the base crude oil and depending on the processing method in the refinery. As has long been known, the dilution behavior of such petroleum products under the influence of cold is mainly influenced by this content of n-paraffins. Such n-paraffins crystallize when the saturation temperature falls below the orthorhombic crystal lattice in the form of thin trapezoidal or diamond-shaped plates and thin needles. These crystal modifications continue to tend to grow together and agglomerate, resulting in the formation of a three-dimensional network. The crystallization of the n-paraffins is accompanied by a decrease in fluidity and an increase in viscosity. As a result, blockages of the filters can occur in diesel engines and combustion systems, which impair safe metering of the fuel and, in the worst case, completely block the fuel supply.

Durch die Verwendung sogenannter Fließverbesserer kann in den meisten Fällen dem geschilderten Problem der Filterverlegung durch n-Paraffine begegnet werden. Die gebildeten n-Paraffine/Fließverbesserer Addukte ermöglichen auch bei tiefen Temperaturen den reibungslosen Betrieb von Dieselmotoren und Brennstoffanlagen. Als derartige Additive oder Fließverbesserer werden hauptsächlich Copolymerisate aus Ethylen und Vinylacetat (EVA-Copolymere) in verschiedenen Variationen zur Verbesserung der Kältestabilität von Dieselkraftstoffen und Heizöl eingesetzt.The use of so-called flow improvers can in most cases counter the described problem of filter installation using n-paraffins. The formed n-paraffins / flow improvers adducts enable smooth operation of diesel engines and fuel systems even at low temperatures. As such additives or flow improvers, mainly copolymers of ethylene and vinyl acetate (EVA copolymers) in various variations are used to improve the low-temperature stability of diesel fuels and heating oil.

In zunehmendem Umfang tauchen nun aber auch solche Mitteldestillatschnitte auf, bei denen diese Standard-­Additive versagen. Zu dieser Kategorie zählen u.a. Mitteldestillate mit hohem Siedeende (S.E. > 380°C). Der Cloud Point (CP) solcher Öle liegt nicht selten deutlich oberhalb CP: ± 0°C.However, those middle distillate cuts are increasingly appearing where these standard additives fail. This category includes Middle distillates with a high boiling point (S.E.> 380 ° C). The cloud point (CP) of such oils is often significantly above CP: ± 0 ° C.

Dies Auswertung der Patentliteratur zeigt, daß durch Zusätze zu den bereits erwähnten Ethylen-Vinylacetat-Copolymeren versucht wird, die Wirksamkeit zu steigern, um auch solcher kritischen Öle Herr zu werden.This evaluation of the patent literature shows that attempts are made to add to the ethylene-vinyl acetate copolymers already mentioned to increase the effectiveness in order to master such critical oils.

So werden z.B. Mischungen aus EVA-Copolymeren mit unterschiedlicher Molmasse und unterschiedlichem Vinylacetatgehalt beschrieben (DT-OS 2 206 719). Bekannt sind ferner Zusätze polymerer Stoffe anderer Zusammensetzung wie Polyacrylate (US 4 058 371, DT-OS 2 613 316), Ethylen-α-Olefin-Copolymere (BE-Pat. 749 254) und Ester von Stearylalkoholen (FR. Pat. 2 115 718). Ebenfalls bekannt ist die Verwendung von Umsetzungsprodukten aus α-Olefinen, Acrylsäureestern und Maleinsäurederivaten mit Aminen.For example, Mixtures of EVA copolymers with different molecular weights and different vinyl acetate content described (DT-OS 2 206 719). Also known are additions of polymeric substances of different composition such as polyacrylates (US 4,058,371, DT-OS 2,613,316), ethylene-α-olefin copolymers (BE Pat. 749 254) and esters of stearyl alcohols (FR. Pat. 2 115) 718). The use of reaction products of α-olefins, acrylic acid esters and maleic acid derivatives with amines is also known.

Die inhibierende Wirkung dieser Produkte ist jedoch nicht ausreichend, so daß es insbesondere bei niedrigen Temperaturen zur Ausfällung von Paraffinen kommt. Natchteilig ist außerdem, daß die Anwendbarkeit bestimmter bekannter Additive nur auf bestimmte Mitteldestillate beschränkt ist.However, the inhibitory effect of these products is not sufficient, so that paraffins are precipitated, especially at low temperatures. Another disadvantage is that the applicability of certain known additives is limited only to certain middle distillates.

Es wurde nun gefunden, daß durch die im folgenden beschriebenen Polymermischungen eine deutliche Verbesserung des Kaltfließverhaltens bei Mitteldestillaten erreicht werden kann.It has now been found that a significant improvement in the cold flow behavior of middle distillates can be achieved by the polymer mixtures described below.

Gegenstand der Erfindung sind Polymermischungen aus einem Copolymer (A₁) aus 10-60 Gew.-% Vinylacetat und 40-90 Gew.-% Ethylen oder einem Copolymer (A₂) aus 15-50 Gew.-% Vinylacetat, 0.5-20 Gew.-% C₆-C₂₄-α-Olefin und 30 -70 Gew.-% Ethylen und einem Copolymer (B) aus 10-90 Gew.-% C₆-C₂₄-α- Olefin und 10-90 % N-C₆-C₂₂-Alkylmaleinsäureimid, wobei das Mischungsverhältnis der Copolymeren (A₁) oder (A₂) zu (B) 100:1 bis 1:1 beträgt.The invention relates to polymer mixtures of a copolymer (A₁) made of 10-60% by weight vinyl acetate and 40-90% by weight ethylene or a copolymer (A₂) made of 15-50% by weight Vinyl acetate, 0.5-20% by weight of C₆-C₂₄-α-olefin and 30 -70% by weight of ethylene and a copolymer (B) of 10-90% by weight of C₆-C₂₄-α-olefin and 10-90 % N-C₆-C₂₂-alkylmaleimide, the mixing ratio of the copolymers (A₁) or (A₂) to (B) being 100: 1 to 1: 1.

Die unter A₁ und A₂ genannten Copolymeren werden über eine Hochdrucksynthese (Reaktionsdruck: 100-200 MPa; Reaktionstemperatur: 120-280°C) in einer Massenpolymerisation nach an sich bekannten Verfahren erhalten. Als Polymer (A₁) sind solche bevorzugt, die 15-40 Gew.-% Vinylacetat und dementsprechend 60-85 Gew.-% Ethylen enthalten. Das Polymer (A₂) enthält bevorzugt 20 bis 30 Gew.-% Vinylacetat und 2 bis 5 Gew.-% α-Olefin. Polymere dieser Art sind teilweise in der DE-PS 21 02 469 beschrieben und werden nach den dort beschriebenen Verfahren hergestellt.The copolymers mentioned under A₁ and A₂ are obtained via a high pressure synthesis (reaction pressure: 100-200 MPa; reaction temperature: 120-280 ° C) in a bulk polymerization according to methods known per se. As the polymer (A₁) are preferred those containing 15-40 wt .-% vinyl acetate and correspondingly 60-85 wt .-% ethylene. The polymer (A₂) preferably contains 20 to 30 wt .-% vinyl acetate and 2 to 5 wt .-% α-olefin. Polymers of this type are partially described in DE-PS 21 02 469 and are produced by the processes described there.

Die Copolymeren (B) enthalten vorzugsweise 50 Gew.-% des α-Olefins und 50 Gew.-% des N-Alkylmaleinsäureimids. Die α-Olefine enthalten bevorzugt 8-18 C-Atome, die Alkylgruppe in den N-Alkylmaleinsäureimiden enthält bevorzugt 12-22 C-Atome. Die unter (B) genannten Copolymere erhält man durch Lösungspolymerisation von N-Alkylmaleinimiden und α-Olefinen bei 120°C mit typischen Radikalstartern wie tert-Butylperbenzoat oder Azobisisobutyronitril. Das monomere Maleinimid wird zuvor durch stöchiometrischen Umsatz von Maleinsäureanhydrid und dem entsprechenden Amin bei 120 - 150°C mit einem aromatischen Kohlenwasserstoff wie etwa Toluol oder Xylol als Schleppmittel und p-Toluolsulfonsäure als Katalysator erhalten. Der Fortschritt der Reaction kann über die Säurezahl bestimmt werden.The copolymers (B) preferably contain 50% by weight of the α-olefin and 50% by weight of the N-alkylmaleimide. The α-olefins preferably contain 8-18 C atoms, the alkyl group in the N-alkylmaleimides preferably contains 12-22 C atoms. The copolymers mentioned under (B) are obtained by solution polymerization of N-alkylmaleimides and α-olefins at 120 ° C. using typical radical initiators such as tert-butyl perbenzoate or azobisisobutyronitrile. The monomeric maleimide is obtained beforehand by stoichiometric conversion of maleic anhydride and the corresponding amine at 120-150 ° C. using an aromatic hydrocarbon such as toluene or xylene as an entrainer and p-toluenesulfonic acid as a catalyst. The progress of the reaction can be determined via the acid number.

Zu dieser Lösung gibt man dann das α-Olefin sowie den radikalischen Katalysator und polymerisiert durch Erhitzen auf ungefähr 100-140°C. Man kann diese Polymerisation aber auch ohne Lösungsmittel in der Schmelze durchführen, wobei man vor der Polymerisation das Lösemittel abdestilliert, das für die Herstellung des N-Alkylmaleinsäureimids benötigt wurde. Die mittlere Molmasse aller drei Copolymeren beträgt etwa 1000 bis 10000 g mol⁻¹. Das Mischungsverhältnis der Polymeren (A₁) bzw. (A₂) z u (B) beträgt 100:1 bis 1:1, vorzugsweise 10:1 bis 6 :1 Gewichtsteile.The α-olefin and the free-radical catalyst are then added to this solution and polymerization is carried out by heating to approximately 100-140 ° C. However, this polymerization can also be carried out in the melt without solvent, with the solvent which was required for the preparation of the N-alkylmaleimide was distilled off before the polymerization. The average molecular weight of all three copolymers is about 1000 to 10000 g mol⁻¹. The mixing ratio of the polymers (A₁) or (A₂) to (B) is 100: 1 to 1: 1, preferably 10: 1 to 6: 1 parts by weight.

Die erfindungsgemäßen Polymermischungen werden durch einfaches Vermischen der einzelnen Komponenten hergestellt.The polymer mixtures according to the invention are produced by simply mixing the individual components.

Die beschriebenen Polymermischungen zeichnen sich aus durch eine sehr breite Wirksamkeit und ermöglichen auch eine Verbesserung der Kälteeigenschaften bei den eingangs genannten Problemölen. Die Polymermischungen werden den Erdöldestillaten in Mengen von ca. 10 bis 500 ppm zugegeben.The polymer mixtures described are notable for their very broad activity and also enable the cold properties of the problem oils mentioned at the beginning to be improved. The polymer mixtures are added to the petroleum distillates in amounts of approximately 10 to 500 ppm.

I. Herstellung der N-AlkylmaleinimideI. Preparation of the N-alkylmaleimides Beispiel 1example 1

In einem 1-Liter-4-Halskolben mit Rührer, Innenthermometer und Wasserabscheider werden 98 g (1 mol) Maleinsäureanhydrid und 0,35 g p-Toluolsulfonsäure in 100 g Toluol bei 50°C gelöst. Dazu tropft man 101 g (1 mol) n-Hexylamin so langsam zu, daß die Temperatur zwischen 80°C und 90°C gehalten werden kann. Nach Abklingen der exothermen Reaktion wird die Innentemperatur auf 120°C erhöht. Im Verlauf von 6 h werden insgesamt 8 bis 12 g Wasser ausgekreist. Die Innentemperatur liegt dabei anfangs bei 120°C zum Schluß bei 140°C. Man erhält eine hellbraune Lösung mit der Säurezahl 20.98 g (1 mol) of maleic anhydride and 0.35 g of p-toluenesulfonic acid are dissolved in 100 g of toluene at 50 ° C. in a 1 liter 4-necked flask equipped with a stirrer, internal thermometer and water separator. 101 g (1 mol) of n-hexylamine are added dropwise so slowly that the temperature can be kept between 80 ° C. and 90 ° C. After the exothermic reaction has subsided, the internal temperature is raised to 120 ° C. A total of 8 to 12 g of water are removed in the course of 6 hours. The inside temperature is initially 120 ° C and finally 140 ° C. A light brown solution with an acid number of 20 is obtained.

Beispiel 2Example 2

Analog zu Beispiel 1 werden zu 98 g (1 Mol) Maleinsäure­anhydrid 325 g (1 Mol) aufgeschmolzenes Docosylamin gegeben. Man erhält nach diesem Verfahren eine braune Paste mit der Säurezahl 50.Analogously to Example 1, 325 g (1 mol) of melted docosylamine are added to 98 g (1 mol) of maleic anhydride. A brown paste with an acid number of 50 is obtained by this process.

Beispiel 3Example 3

Analog zum Beispiel 1 werden zu 98 g (1 Mol) Maleinsäure­anhydrid 270 g (1 Mol) aufgeschmolzenes Stearylamin gegeben. Man erhält nach diesem Verfahren eine braune Paste mit der Säurezahl 30.Analogously to Example 1, 270 g (1 mol) of melted stearylamine are added to 98 g (1 mol) of maleic anhydride. A brown paste with an acid number of 30 is obtained by this process.

II. Herstellung des N-Alkylmaleinimid/α-Olefin-CopolymersII. Preparation of the N-alkylmaleimide / α-olefin copolymer Beispiel 1example 1

In einem 1-Liter-4-Halskolben, ausgestattet mit wandgängigem Rührer, Rückflußkühler, Kontaktthermometer und Tropftrichter werden 200 g der nach I.1 hergestellten Lösung zusammen mit 200 g Hexen -(1) vorgelegt. Man erhitzt das Gemisch auf 100°C und tropft über 20 Min. eine Lösung von 2 g AIBN (Azobis­isobutyronitril) in 40 g Toluol zu. Nach beendeter Zugabe wird noch 2h bei 120°C gehalten.200 g of the solution prepared according to I.1 together with 200 g of hexene - (1) are placed in a 1 liter 4-necked flask equipped with a stirrer, reflux condenser, contact thermometer and dropping funnel. The mixture is heated to 100 ° C. and a solution of 2 g of AIBN (azobisisobutyronitrile) in 40 g of toluene is added dropwise over 20 minutes. After the addition has ended, the mixture is kept at 120 ° C. for a further 2 hours.

Beispiel 2Example 2

Nach der in Beispiel II.1 angegebenen Vorschrift werden 200 g der nach Beispiel I.2 hergestellten Lösung mit 200 g eines Gemisches aus C₂₀-, C₂₂- und C₂₄-α-Olefin vorgelegt und auf 120°C erhitzt. Man tropft über 20 Min. eine Mischung von 2 g t-Butylbenzoylperoxid in 40 g Toluol zu und hält danach noch 2 h bei 140°C.According to the procedure given in Example II.1, 200 g of the solution prepared according to Example I.2 are initially charged with 200 g of a mixture of C₂₀-, C₂₂- and C₂₄-α-olefins and heated to 120 ° C. A mixture of 2 g of t-butylbenzoyl peroxide in 40 g of toluene is added dropwise over 20 minutes and the mixture is then kept at 140 ° C. for a further 2 hours.

Beispiel 3Example 3

200 g des von Toluol befreiten Imids nach Beispiel I.2, werden zusammen mit 200 g Octadecen-(1) auf 120°C gebracht. Dazu gibt man in kleinen Portionen 2 g t-Butylbenzoylperoxid. Nach Abklingen der exothermen Reaktion erhält man ein rotbraunes Copolymer.
Der K-Wert (25°C/5 % in Toluol) liegt in allen Fällen zwischen 10 und 15.200 g of the toluene-free imide according to Example I.2 are brought to 120 ° C. together with 200 g of octadecene (1). 2 g of t-butylbenzoyl peroxide are added in small portions. After the exothermic reaction has subsided, a red-brown copolymer is obtained.
The K value (25 ° C / 5% in toluene) is between 10 and 15 in all cases.

Beispiel 4Example 4

Nach der in Beispiel II.1. angegebene Vorschrift werden 200 g der nach Beispiel I.3 hergestellten Lösung mit 200 g C₁₈-α-Olefin (Octadecen) vorgelegt und auf 120°C erhitzt. Man tropft über 20 Min. eine Mischung von 2 g AIBN in 40 g Toluol zu und hält danach noch 2 Stunden bei 120°CAccording to the in Example II.1. specified rule 200 g of the solution prepared according to Example I.3 with 200 g of C₁₈-α-olefin (octadecene) and heated to 120 ° C. A mixture of 2 g of AIBN in 40 g of toluene is added dropwise over 20 minutes and the mixture is then kept at 120 ° C. for 2 hours

AnwendungsbeispieleExamples of use

Als standardisierte Prüfmethode hat sich der CFPP-Test (Cold Filter Plugging Point) bewährt. Dabei bezeichnet der CFPP (bestimmt nach DIN 51428) den Grenzwert der Filtrierbarkeit.
Alle Messungen wurden am CFPP-Gerät MC 840-D6 der Fa. Herzog ausgeführt.
Es wurden folgende Polymere getestet:

  • A: Mischung aus 6 Gew.-Teilen eines Ethylen-Vinylacetat Copolymers, Gehalt an Vinylacetat 26,5 Gew.-%; Molmasse 1000-4000 g mol⁻¹ und 1 Gew.-Teil eines Copolymers aus 50 Gew.-% 1-Octadecen und 50 Gew.-% N-Stearylmalein­säureimid.
  • B: Mischung aus 10 Gew.-Teilen des Ethylen-Vinylacetat Copolymers wie unter A und 1 Teil des Octadecen/­Stearylmaleinsäureimids wie unter A.
  • C: Mischung aus 6 Gew.-Teilen eines Terpolymers aus 60 Gew.-% Ethylen, 26 Gew.-% Vinylacetat und 5 Gew.-% Di-isobutylen sowie 1 Gew.-Teil eines Copolymers aus 50 Gew.-% 1-Octadecen und 50 Gew.-% N-Stearylmalein­säureimid.
  • D: Ethylen-Vinylacetat Copolymer wie unter A. Gehalt an Vinylacetat 26,5 Gew.-%
  • E: Terpolymer wie unter C angegeben; 69 % Ethylen, 26 % Vinylacetat und 5 % Di-isobutylen.
  • F: Ethylen-Vinylacetat-Copolymer mit einem Vinylacetat-­Gehalt von 26.4 Gew.-% und einem Feststoffgehalt von 57.3 Gew.-%.
  • G: Ethylen-Vinylacetat-Copolymer mit 50 Gew.-% Feststoff-­Gehalt.
  • H: Ethylen-Vinylacetat-Copolymer mit einem Vinylacetat-­Gehalt von 26,4 Gew.-% und einem Feststoffgehalt von 65.7 Gew.-%.
  • I: Ethylen-Vinylpropionat-Copolymer
  • J: Ethylen-Vinylacetate-2-Olefin-Terpolymer, abgemischt mit Wachsoxidaten.
The CFPP test (Cold Filter Plugging Point) has proven itself as a standardized test method. The CFPP (determined according to DIN 51428) denotes the limit value of the filterability.
All measurements were carried out on the CFPP device MC 840-D6 from Herzog.
The following polymers were tested:
  • A: Mixture of 6 parts by weight of an ethylene-vinyl acetate copolymer, vinyl acetate content 26.5% by weight; Molar mass 1000-4000 g mol⁻¹ and 1 part by weight of a copolymer of 50 wt .-% 1-octadecene and 50 wt .-% N-stearylmaleimide.
  • B: Mixture of 10 parts by weight of the ethylene-vinyl acetate copolymer as under A and 1 part of the octadecene / stearyl maleimide as under A.
  • C: Mixture of 6 parts by weight of a terpolymer of 60% by weight of ethylene, 26% by weight of vinyl acetate and 5% by weight of di-isobutylene and 1 part by weight of a copolymer of 50% by weight of 1- Octadecene and 50% by weight N-stearyl maleimide.
  • D: ethylene-vinyl acetate copolymer as under A. content of vinyl acetate 26.5% by weight
  • E: terpolymer as indicated under C; 69% ethylene, 26% vinyl acetate and 5% di-isobutylene.
  • F: ethylene-vinyl acetate copolymer with a vinyl acetate content of 26.4% by weight and a solids content of 57.3% by weight.
  • G: ethylene-vinyl acetate copolymer with a solids content of 50% by weight.
  • H: ethylene-vinyl acetate copolymer with a vinyl acetate content of 26.4% by weight and a solids content of 65.7% by weight.
  • I: ethylene vinyl propionate copolymer
  • J: Ethylene vinyl acetate 2-olefin terpolymer mixed with wax oxidates.

Die in der folgenden Tabelle angegebenen Resultate zeigen deutlich, daß mitden erfindungsgemäßen Polymermischungen die besten Ergebnisse in Bezug auf die Fleißfähigkeit von Mineralöldestillaten in der Kälte erhalten werden. TABELLE CFPP-Ansprechverhalten Mitteldest. A B C D E F G H I J Dosierung (ppm) Heizöl -15 -19 -3 -5 0 -1 150 CFPP: -1°C S,B.: 165°C S.E.: 381°C Gasöl -18 -17 -15 -8 -7 -8 -9 -9 600 CP: +2°C CFPP: -2°C Gasöl -20 -20 -18 -6 -7 -10 -7 600 CP: +2°C CFPP: -4°C Heizöl -15 -13 -15 -11 -3 -13 -4 300 CP: +4°C CFPP: +2°C Dieselkraftstoff -14 -14 -11 -3 -2 -1 -4 300 CP: +4°C CFPP: 0°C S.B.: 168°C S.E.: 400°C Gasöl -7 -6 -3 +7 +7 +6 +6 1000 CP: +10°C CFPP: +8°C Heizöl -8 -11 +2 -6 +2 +2 100 CP: +5°C -10 +1 500 CFPP Gasöl -15 -15 -14 -6 -7 -14 -11 -7 300 CP: -1°C CFPP: -4°C CP = Cloud Point; CFPP = Cold Filter Plugging Point S.B.= Siedebeginn; SE= Siedeende The results given in the following table clearly show that the polymer mixtures according to the invention give the best results with regard to the dilatability of mineral oil distillates in the cold. TABLE CFPP response Middle dist. A B C. D E F G H I. J Dosage (ppm) Heating oil -15 -19 -3 -5 0 -1 150 CFPP: -1 ° C S, B .: 165 ° C SE: 381 ° C Gas oil -18 -17 -15 -8th -7 -8th -9 -9 600 CP: + 2 ° C CFPP: -2 ° C Gas oil -20 -20 -18 -6 -7 -10 -7 600 CP: + 2 ° C CFPP: -4 ° C Heating oil -15 -13 -15 -11 -3 -13 -4 300 CP: + 4 ° C CFPP: + 2 ° C Diesel fuel -14 -14 -11 -3 -2 -1 -4 300 CP: + 4 ° C CFPP: 0 ° C SB: 168 ° C SE: 400 ° C Gas oil -7 -6 -3 +7 +7 +6 +6 1000 CP: + 10 ° C CFPP: + 8 ° C Heating oil -8th -11 +2 -6 +2 +2 100 CP: + 5 ° C -10 +1 500 CFPP Gas oil -15 -15 -14 -6 -7 -14 -11 -7 300 CP: -1 ° C CFPP: -4 ° C CP = cloud point; CFPP = Cold Filter Plugging Point SB = start of boiling; SE = end of boiling

Claims (6)

1. Polymermischungen aus einem Copolymer (A₁) aus 10 - 60 Gew.-% Vinylacetat und 40 - 90 Gew.-% Ethylen oder einem Copolymer (A₂) aus 15 - 50 Gew.-% Vinylacetat, 0,5 - 20 Gew.-% C₆-C₂₄-α-Olefin und 30 - 70 Gew.-% Ethylen und einem Copolymer (B) aus 10 - 90 Gew.-% C₆-C₂₄-α-Olefin und 10 - 90 Gew.-% N-C₆-C₂₂-Alkylmalein­säureimid, wobei das Mischungsverhältnis der Copolymeren (A₁) oder (A₂) zu (B) 100:1 bis 1:1 beträgt.1. polymer mixtures of a copolymer (A₁) from 10 - 60 wt .-% vinyl acetate and 40 - 90 wt .-% ethylene or a copolymer (A₂) from 15 - 50 wt .-% vinyl acetate, 0.5 - 20 wt. -% C₆-C₂₄-α-olefin and 30 - 70 wt .-% ethylene and a copolymer (B) from 10 - 90 wt .-% C₆-C₂₄-α-olefin and 10 - 90 wt .-% N-C₆ -C₂₂-alkylmaleimide, the mixing ratio of the copolymers (A₁) or (A₂) to (B) being 100: 1 to 1: 1. 2. Polymermischungen nach Anspruch 1, dadurch gekennzeichnet, daß das Mischungsverhältnis der Copolymeren (A₁) oder (A₂) zu (B) 10:1 bis 6:1 beträgt.2. Polymer mixtures according to claim 1, characterized in that the mixing ratio of the copolymers (A₁) or (A₂) to (B) is 10: 1 to 6: 1. 3. Polymermischungen nach Anspruch 1, dadurch gekennzeichnet, daß das Copolymer (A₁) 15 bis 40 Gew.-% Vinylacetat und das Copolymer (A₂) 20 bis 30 Gew.-% Vinylacetat sowie 2 bis 5 Gew.-% α-Olefin enthält.3. Polymer mixtures according to claim 1, characterized in that the copolymer (A₁) contains 15 to 40% by weight of vinyl acetate and the copolymer (A₂) contains 20 to 30% by weight of vinyl acetate and 2 to 5% by weight of α-olefin . 4. Polymermischungen nach Anspruch 1, dadurch gekennzeichnet, daß das Copolymer (B) aus 50 Gew.-% α-Olefin und 50 Gew.-% N-Alkylmaleinsäureimid besteht.4. Polymer mixtures according to claim 1, characterized in that the copolymer (B) consists of 50% by weight of α-olefin and 50% by weight of N-alkylmaleimide. 5. Verfahren zur Herstellung des Copolymeren (B) nach Anspruch 1, dadurch gekennzeichnet, daß man zunächst in einem Lösemittel Maleinsäureanhydrid mit einer stöchiometrischen Menge eines C₆-C₂₂-Alkylamins umsetzt und das so erhaltene N-Alkylmaleinsäureimid direkt mit einem C₆-C₂₄-α-Olefin polymerisiert.5. A process for the preparation of the copolymer (B) according to claim 1, characterized in that first reacting maleic anhydride with a stoichiometric amount of a C₆-C₂₂-alkylamine in a solvent and the N-alkylmaleimide thus obtained directly with a C₆-C₂₄-α - Olefin polymerized. 6. Verwendung der Polymermischungen nach Anspruch 1 als Zusatz bei Mineralöldestillaten zur Verbesserung der Fließfähigkeit.6. Use of the polymer mixtures according to claim 1 as an additive in mineral oil distillates to improve the flowability.
EP88120410A 1987-12-16 1988-12-07 Viscosity index-modifying polymer blends for petroleum fractions Revoked EP0320766B1 (en)

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FI97234C (en) 1996-11-11
FI97234B (en) 1996-07-31
EP0320766B1 (en) 1994-01-12
JP2777810B2 (en) 1998-07-23
DE3742630A1 (en) 1989-06-29
JPH01201348A (en) 1989-08-14
CA1337888C (en) 1996-01-02
NO885579D0 (en) 1988-12-15
DE3887115D1 (en) 1994-02-24
NO174261C (en) 1994-04-06
NO885579L (en) 1989-06-19
NO174261B (en) 1993-12-27
FI885781A (en) 1989-06-17
FI885781A0 (en) 1988-12-14
EP0320766A3 (en) 1989-12-20
US4985048A (en) 1991-01-15

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