EP0407906B1 - Mineral oils with improved flow behaviour - Google Patents

Mineral oils with improved flow behaviour Download PDF

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Publication number
EP0407906B1
EP0407906B1 EP90112914A EP90112914A EP0407906B1 EP 0407906 B1 EP0407906 B1 EP 0407906B1 EP 90112914 A EP90112914 A EP 90112914A EP 90112914 A EP90112914 A EP 90112914A EP 0407906 B1 EP0407906 B1 EP 0407906B1
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meth
polyalkyl
degrees
acrylate
oils
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French (fr)
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EP0407906A1 (en
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Michael Dr. Müller
Heinz Dr. Grünig
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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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
    • 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

Definitions

  • the invention relates to mineral oils and mineral oil products with improved flow behavior, which contain a mixture of different types of polyalkyl (meth) acrylates as flow improvers.
  • the cold behavior of petroleum and petroleum products is decisively influenced by the paraffins they contain.
  • the paraffins crystallize on cooling. As a result, the fluidity of the oils is reduced or completely prevented.
  • the paraffins generally dissolve in the oil matrix when heated.
  • Their mode of action was interpreted with the following model: Paraffin-like compounds are built into the growing paraffin crystal surfaces and thus prevent the crystals from growing further and the formation of extensive crystal groups. (See Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 20, p. 548, Verlag Chemie 1981).
  • Polymers based on (meth) acrylic acid esters of long-chain alkanols are rightly considered to be effective flow improvers for crude oils (cf. DE-A 17 70 695).
  • Polybehenyl acrylate can e.g. considered as a prototype of a flow improver for crude oils.
  • Polybehenyl acrylate crystallizes even at a temperature of + 20 degrees C (determined in 0.1% concentration in isooctane by "cloud point" measurement according to DIN 51 597 or ASTM D 97-66), and fulfills the requirements very well to be able to interact with the long-chain paraffins in the crude oil.
  • the use of polybehenyl acrylate and comparable long-chain polyacrylates does, of course, stand in the way of the high price of the starting materials.
  • EP-AO 344 644 describes mineral oils containing paraffin from the group of crude oils, vacuum gas oils and residual oils with improved flow properties, the mineral oils having in common that the start of the paraffin crystallization is at a temperature ⁇ 30 ° C. and that they have a content of 1 to 10,000 ppm of at least one polymer P selected from the class of polyalkyl (meth) acrylates or polydialkyl fumarates, the start of crystallization of which is below 15 degrees C.
  • the start of paraffin crystallization in the oils as a function of the temperature can be determined as a significant characteristic for determining the flow-improving effect.
  • the determination methods see A. Ecker in “Petroleum and Coal” Vol. 38 (6) 281 (1985); A. Ecker, Erdöl, Erdgas 101 , 154 (1982); RL Blaine, NGLI-Spokesman, June 1976) .
  • the paraffins contained in the oils crystallize on cooling while releasing heat.
  • the heat released can be recorded by means of differential thermal analysis (DTA) or preferably differential scanning calorimetry (DSC) as an exothermic peak and thus the start of paraffin crystallization can be correctly determined, while the determinations based on visual observation of the "wax appearance point” or the “cloud point” "generally fail with dark products and residues.
  • DTA differential thermal analysis
  • DSC differential scanning calorimetry
  • the two polymer components P1 and P2 are preferably in a weight ratio of 1:50 to 50: 1, in particular 1:10 to 10: 1 to one another.
  • the polyalkyl (meth) acrylates P1 of type A with an association temperature above 15 degrees C will generally be formed from monomers with an alkyl radical> C18 or contain significant proportions thereof.
  • Particularly suitable are the polyalkyl (meth) acrylates of C18-C26 alkanols, especially of C18-C24 alkanols, especially polybehenyl acrylate (polymer P1-a).
  • the molecular weights of the polymers P1 and P2 are generally in the range 5,000 to 1,000,000, preferably 10,000 to 500,000. In general, compliance with the molecular weight range is ensured by using regulators known per se, for example of the sulfur regulator type. (See H. Rauch-Puntigam, Th.
  • Mercaptans such as dodecyl mercaptan in amounts of 0.01 to 2% by weight, based on the monomers, are particularly mentioned.
  • the molecular weights are determined by means of gel permeation chromatography, using polymethyl methacrylate as the calibration substance (see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd. Ed. Vol. 18, pg. 209 749, J. Wiley 1982).
  • the starting monomers are known per se or they can be prepared in a manner known per se, for example by transesterification of lower (meth) acrylates such as, for example, methyl or ethyl ester with the higher alcohols.
  • the preparation of the polymers can follow the free radical polymerization processes of the prior art are carried out. (See H. Rauch-Punktigam, Th. Völker, Acryl- und Methacryl für n-Verlag, Berlin 1967).
  • An inert medium preferably of the mineral oil type itself, for example 100 N oil, is recommended as the polymerization medium.
  • Possible reaction vessels are those which are usually used and which are expediently equipped with a stirrer, heating device, thermometer, reflux condenser and metering line; preferably one works under an inert gas such as carbon dioxide.
  • the usual free radical initiators are preferably used peresters, peroxides or azo compounds, for example tert-butyl perbenzoate, tert-butyl perpivalate in the usual concentrations, for example 0.1-5% by weight, preferably 0.3 to 1% by weight. based on the total amount of monomers.
  • the process is started at elevated temperature, preferably from 60 degrees C, in particular at 70-90, whereupon initiator is added and the temperature reaches a peak which can be above 80 degrees C, for example 140 ⁇ 10 degrees C. If necessary, the additional polymerization can be initiated by adding the initiator again and, if necessary, by heating. In general, the polymerization is completed in about 5 hours.
  • the mineral oils are The mineral oils.
  • paraffin crystallization as a function of the temperature is an important parameter for the mineral oil provenances or the petroleum products in question, the determination of which is carried out routinely by a person skilled in the art. As already mentioned, the preferred determination method is the DSC.
  • the content of mineral oils in the polymers P is 1-10,000, preferably 50 to 2,000 ppm, in adaptation to the provenances, the flow properties of which need to be improved.
  • the polymers P can advantageously with a suitable compatible solvent, for example a hydrocarbon such as Xylene, toluene, kerosene, SHELLSOL® can be diluted.
  • a suitable compatible solvent for example a hydrocarbon such as Xylene, toluene, kerosene, SHELLSOL® can be diluted.
  • the solution thus obtained can then be used in the preparation of the mineral oil mixtures. In special cases, this solution can be added to the crude oil directly at the probe head or in the pipeline.
  • the polymers P preferably in the form of the solutions mentioned, are advantageously mixed with the mineral oils, such as crude oils, vacuum gas oils or residual oils, at an elevated temperature, for example at 40 to 80 degrees C. The effect of the flow-improving additives is retained over the period that is normally required.
  • a model concept can be developed for the unexpected interaction of the two polymer components P1 and P2, the validity of which should, however, have no influence on the present technical teaching:
  • the component with the higher self-association temperature influences the crystallization of the long-chain crude oil paraffins.
  • the second component with a lower self-association temperature takes effect.
  • polybehenyl acrylate as component A), the following approach can be used, for example: In crude oils in which polybehenyl acrylate lowers the pour point by no more than 0 degrees C, mixed components B) with intrinsic crystallization temperatures between 0 and 15 degrees C are advantageous. In crude oils, in which the pour point can be lowered to below -5 degrees C with polybehenyl acrylate, mixed components B) with self-association temperatures ⁇ - 5 degrees C are optimal.
  • behenyl acrylate e.g. (ALFOL 20 +) acrylate (acrylic esters of C20, C22, C24 alcohol) can also be used.
  • the polymers P1-a-P2-e were added as a 10% solution in xylene to the crude oils at 80 degrees C. All dosages relate to polymer.
  • the pour points were determined in accordance with DIN 51 597 using an automatic measuring device from Herzog, Lauda.
  • the pour points in Example 8 were determined in accordance with DIN 51 597 (ASTM 097-66).

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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)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to mineral oils and mineral oil products of improved flow behaviour, from the group of crude oils, vacuum gas oils or residual oils, having a content of long-chain polyalkyl (meth)acrylates, the long-chain polyalkyl (meth)acrylates representing a mixture of A) a polyalkyl (meth)acrylate P1 having crystallisation starting temperatures above 15 degrees C (measured as the cloud point of a 0.1 % solution in isooctane) and B) a polyalkyl (meth)acrylate P2 having crystallisation starting temperatures at or below 15 degrees C, with the proviso that there is a temperature difference of at least 5 degrees C between the start of the crystallisation of the polyalkyl (meth)acrylates P1 and the start of the crystallisation of the polyalkyl (meth)acrylates P2.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft Mineralöle und Mineralölprodukte mit verbessertem Fließverhalten, die eine Mischung aus definiert verschiedenartigen Polyalkyl(meth)acrylaten als Fließverbesserer enthalten.The invention relates to mineral oils and mineral oil products with improved flow behavior, which contain a mixture of different types of polyalkyl (meth) acrylates as flow improvers.

Stand der TechnikState of the art

Das Kälteverhalten von Erdölen und Erdölprodukten wird entscheidend durch die darin enthaltenen Paraffine beeinflußt. Die Paraffine kristallisieren beim Abkühlen aus. Dadurch wird die Fließfähigkeit der Öle herabgesetzt bzw. ganz verhindert. Die Paraffine gehen im allgemeinen beim Erwärmen wieder in der Ölmatrix in Lösung. Die Technik hat polymere Fließverbesserer, beispielsweise sogenannte "Pour Point-Erniedriger", entwickelt, die den "Pour Point" (= Temperatur, bei der das Öl gerade noch fließt, vgl. DIN 51 597) bereits in Konzentrationen zwischen 0,05 und 1 Gew.-% wirksam herabsetzen. Deren Wirkweise wurde mit etwa folgender Modellvorstellung gedeutet: Paraffin-ähnliche Verbindungen werden in die wachsenden Paraffinkristallflächen eingebaut und verhindern so das Weiterwachsen der Kristalle und die Bildung ausgedehnter Kristallverbände. (Vgl. Ullmanns Encyclopädie der techn. Chemie, 4. Auflage, Bd. 20, S. 548, Verlag Chemie 1981).The cold behavior of petroleum and petroleum products is decisively influenced by the paraffins they contain. The paraffins crystallize on cooling. As a result, the fluidity of the oils is reduced or completely prevented. The paraffins generally dissolve in the oil matrix when heated. Technology has developed polymeric flow improvers, for example so-called "pour point depressants", which already have the "pour point" (= temperature at which the oil is still flowing, cf. DIN 51 597) in concentrations between 0.05 and 1 Effectively reduce% by weight. Their mode of action was interpreted with the following model: Paraffin-like compounds are built into the growing paraffin crystal surfaces and thus prevent the crystals from growing further and the formation of extensive crystal groups. (See Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 20, p. 548, Verlag Chemie 1981).

Polymere auf Basis von (Meth)acrylsäureestern langkettiger Alkanole (C > 12) gelten zu recht als wirksame Fließverbesserer für Rohöle (vgl. DE-A 17 70 695). Polybehenylacrylat kann z.B. als Prototyp eines Fließverbesserers für Rohöle gelten. Polybehenylacrylat kristallisiert selbst bei einer Temperatur von + 20 Grad C (bestimmt in 0,1 %iger Konzentration in Isooctan durch "Cloud Point"-Messung nach DIN 51 597 bzw. ASTM D 97 -66), und erfüllt sehr gut die Voraussetzungen, um mit den langkettigen Paraffinen im Rohöl in Wechselwirkung treten zu können. Der Verwendung von Polybehenylacrylat und vergleichbaren langkettigen Polyacrylaten steht freilich der hohe Preis der Ausgangsstoffe im Wege.Polymers based on (meth) acrylic acid esters of long-chain alkanols (C> 12) are rightly considered to be effective flow improvers for crude oils (cf. DE-A 17 70 695). Polybehenyl acrylate can e.g. considered as a prototype of a flow improver for crude oils. Polybehenyl acrylate crystallizes even at a temperature of + 20 degrees C (determined in 0.1% concentration in isooctane by "cloud point" measurement according to DIN 51 597 or ASTM D 97-66), and fulfills the requirements very well to be able to interact with the long-chain paraffins in the crude oil. The use of polybehenyl acrylate and comparable long-chain polyacrylates does, of course, stand in the way of the high price of the starting materials.

In EP-A-O 344 644 werden paraffinhaltige Mineralöle aus der Gruppe der Rohöle, Vakuum-Gasöle und Rückstandsöle mit verbesserten Fließeigenschaften beschrieben, wobei den Mineralölen gemeinsam ist, daß der Beginn der Paraffinkristallisation bei einer Temperatur < 30 Grad C liegt und daß sie einen Gehalt von 1 bis 10 000 ppm mindestens eines Polymeren P ausgewählt aus der Klasse der Polyalkyl(meth)acrylate oder der Polydialkylfumarate besitzen, deren Kristallisationsbeginn unterhalb 15 Grad C liegt.EP-AO 344 644 describes mineral oils containing paraffin from the group of crude oils, vacuum gas oils and residual oils with improved flow properties, the mineral oils having in common that the start of the paraffin crystallization is at a temperature <30 ° C. and that they have a content of 1 to 10,000 ppm of at least one polymer P selected from the class of polyalkyl (meth) acrylates or polydialkyl fumarates, the start of crystallization of which is below 15 degrees C.

Aufgabe und LösungTask and solution

Auch bei Kenntnis der grundlegenden Lehre des Standes der Technik, wonach langkettige Alkylester, insbesondere C₁₈-C₂₄-Alkylester der (Meth)acrylsäure das Tieftemperatur- Fließverhalten von Rohölen verbessern können, war keine technische Regel zu erkennen, die zu einer Optimierung der fließverbessernden Wirkung von Polyalkyl(meth)acrylaten hätte beitragen können.
Dessen ungeachtet stellten die relativ hohen Kosten der beschriebenen Fließverbesserer des Standes der Technik eine Herausforderung dar, nach kostengünstigeren und wenn möglich gleichartigen oder besseren Lösungen zu suchen.Even with knowledge of the basic teaching of the prior art, according to which long-chain alkyl esters, in particular C₁₈-C₂₄ alkyl esters of (meth) acrylic acid, the low-temperature There was no technical rule to improve the flow behavior of crude oils that could have helped to optimize the flow-improving effect of polyalkyl (meth) acrylates.
Regardless, the relatively high cost of the flow improvers described in the prior art presented a challenge to look for cheaper and, if possible, similar or better solutions.

Als eine signifikante Kenndate zur Bestimmung der fließverbessernden Wirkung kann beispielsweise der Beginn der Paraffinkristallisation in den Ölen in Abhängigkeit von der Temperatur bestimmt werden. (Zu den Bestimmungsmethoden vgl. A. Ecker in "Erdöl und Kohle" Bd. 38 (6) 281 (1985); A. Ecker, Erdöl, Erdgas 101, 154 (1982); R.L. Blaine, NGLI-Spokesman, June 1976).For example, the start of paraffin crystallization in the oils as a function of the temperature can be determined as a significant characteristic for determining the flow-improving effect. (For the determination methods see A. Ecker in "Petroleum and Coal" Vol. 38 (6) 281 (1985); A. Ecker, Erdöl, Erdgas 101 , 154 (1982); RL Blaine, NGLI-Spokesman, June 1976) .

Die in den Ölen enthaltenen Paraffine kristallieren beim Abkühlen unter Wärmefreisetzung aus. Die freigesetzte Wärme kann mittels Differentialthermoanalyse (DTA) bzw. vorzugsweise Differential Scanning Calorimetry (DSC) als exothermer Peak erfasst und damit der Beginn der Paraffinkristallisation einwandfrei bestimmt werden, während die auf visueller Beobachtung basierenden Bestimmungen des "Wax Appearance Point" oder des "Cloud Point" bei dunklen Produkten und bei Rückständen gemeinhin versagen.The paraffins contained in the oils crystallize on cooling while releasing heat. The heat released can be recorded by means of differential thermal analysis (DTA) or preferably differential scanning calorimetry (DSC) as an exothermic peak and thus the start of paraffin crystallization can be correctly determined, while the determinations based on visual observation of the "wax appearance point" or the "cloud point" "generally fail with dark products and residues.

Es wurde nun gefunden, daß bestimmte Mischungen von Polyalkyl(meth)acrylaten die Forderungen der Technik in besonderem Maße erfüllen. Dies ist umso unerwarteter, als die eine dieser Polyalkyl(meth)acrylat-Komponenten als an sich unwirksam oder zumindest als ziemlich schlecht wirksam eingestuft werden muß. Es liegt also ein synergistischer Effekt vor. Die vorliegende Erfindung betrifft demnach Mineralöle und Mineralölprodukte mit verbessertem Fließverhalten, aus der Gruppe der Rohöle, Vakuum-Gasöle oder Rückstandsöle mit einem Gehalt an langkettigen Polyalkyl(meth)acrylaten, wobei die langkettigen Polyalkyl(meth)acrylate eine Mischung aus

  • A) einem Polyalkyl(meth)acrylat P1 mit Beginn der Kristallisation bei Temperaturen oberhalb 15 Grad C (gemessen als Cloud Point gemäß DIN 51 597 einer 0,1 %igen Lösung in Isooctan) und
  • B) einem Polyalkyl(meth)acrylat P2 mit Beginn der Kristallisation bzw. Segregation bei Temperaturen gleich oder unterhalb 15 Grad C, mit der Maßgabe, daß zwischen dem Beginn der Kristallisation bei den Polyalkyl(meth)acrylaten nach A) und dem Beginn der Kristallisation bzw. Segregation der Polyalkyl(meth)acrylate nach B) eine Temperaturdifferenz von mindestens 5 Grad C, vorzugsweise 10 Grad C besteht,
darstellen.It has now been found that certain mixtures of polyalkyl (meth) acrylates meet the requirements of technology to a particular degree. This is all the more unexpected since the one of these polyalkyl (meth) acrylate components than must be classified as ineffective or at least fairly poorly effective. So there is a synergistic effect. The present invention accordingly relates to mineral oils and mineral oil products with improved flow behavior, from the group of crude oils, vacuum gas oils or residual oils containing long-chain polyalkyl (meth) acrylates, the long-chain polyalkyl (meth) acrylates being a mixture of
  • A) a polyalkyl (meth) acrylate P1 with the start of crystallization at temperatures above 15 degrees C (measured as a cloud point according to DIN 51 597 of a 0.1% solution in isooctane) and
  • B) a polyalkyl (meth) acrylate P2 with the start of crystallization or segregation at temperatures equal to or below 15 degrees C, with the proviso that between the start of crystallization in the polyalkyl (meth) acrylates according to A) and the start of crystallization or segregation of the polyalkyl (meth) acrylates according to B) there is a temperature difference of at least 5 degrees C, preferably 10 degrees C,
represent.

Die beiden Polymerkomponenten P1 und P2 stehen vorzugsweise im Gewichtsverhältnis 1 : 50 bis 50 : 1, insbesondere 1 : 10 bis 10 : 1 zueinander.The two polymer components P1 and P2 are preferably in a weight ratio of 1:50 to 50: 1, in particular 1:10 to 10: 1 to one another.

Die Polyalkyl(meth)acrylate P1 und P2The polyalkyl (meth) acrylates P1 and P2

Bekanntlich tritt bei Polyacryl- und -methacrylsäureestern von langkettigen Alkoholen im Unterschied zu den Estern niederer Alkohole eine Tendenz zur Kristallisation (Seitenkettenkristallisation) ein, wobei die Lage des Schmelzpunkts von der Kohlenstoff-Zahl bzw. der Seitenkettenlänge der Zahl und Verteilung im Homo- bzw. Copolymerisat maßgeblich beeinflußt wird.As is known, in the case of polyacrylic and methacrylic acid esters of long-chain alcohols, in contrast to the esters lower alcohols have a tendency to crystallize (side chain crystallization), the position of the melting point being significantly influenced by the carbon number or the side chain length of the number and distribution in the homopolymer or copolymer.

Die Polyalkyl(meth)acrylate P1 vom Typ A mit einer Assoziationstemperatur oberhalb 15 Grad C, werden in der Regel aus Monomeren mit einem Alkylrest > C18 gebildet sein, bzw. maßgebliche Anteile derselben enthalten. Insbesondere eignen sich die Polyalkyl(meth)acrylate von C₁₈-C₂₆-Alkanolen, speziell von C₁₈-C₂₄-Alkanolen, insbesondere Polybehenylacrylat (Polymer P1-a).The polyalkyl (meth) acrylates P1 of type A with an association temperature above 15 degrees C will generally be formed from monomers with an alkyl radical> C18 or contain significant proportions thereof. Particularly suitable are the polyalkyl (meth) acrylates of C₁₈-C₂₆ alkanols, especially of C₁₈-C₂₄ alkanols, especially polybehenyl acrylate (polymer P1-a).

Die erfindungsgemäß geforderten Polyalkyl(meth)acrylate P2 vom Typ B) mit einer Assoziationstemperatur (Kristallisationsbeginn) < 15 Grad C stellen Polymerisate von Estern der Acryl- bzw. der Methacrylsäure, insbesondere mit längerkettigen Alkanolen (ab C₁, vorzugsweise ab C₈ und bis C₄₀) also auch solche mit C₁₆-C₂₄-Alkylresten dar, wobei aber die Auswahl so getroffen wird, daß besagtes Merkmal der Assoziationstemperatur (< 15 Grad C) erfüllt wird. Dabei kann von folgenden Auswahlkriterien Gebrauch gemacht werden:

  • Polymerisation oder Copolymerisation von Estern der Acrylsäure mit Alkylresten < 18 C-Atomen, insbesondere 12 - 18 C-Atomen.
  • Polymerisation oder Copolymerisation von Estern der Methacrylsäure anstatt der Acrylsäure, insbesondere mit C₁₂-C₄₀-Alkylresten.
  • Copolymerisation mit Monomeren, die nicht zur Seitenkettenkristallisation befähigt sind, insbesondere mit Alkylresten < C₁₀ oder verzweigten Alkylresten mit C₁ bis C₄₀.
The polyalkyl (meth) acrylates P2 of type B) required according to the invention with an association temperature (start of crystallization) <15 degrees C are polymers of esters of acrylic or methacrylic acid, in particular with longer-chain alkanols (from C₁, preferably from C₈ and to C₄₀) thus also those with C₁₆-C₂₄ alkyl radicals, but the selection is made so that said characteristic of the association temperature (<15 degrees C) is met. The following selection criteria can be used:
  • Polymerization or copolymerization of esters of acrylic acid with alkyl radicals <18 carbon atoms, in particular 12-18 carbon atoms.
  • Polymerization or copolymerization of esters of meth acrylic acid instead of acrylic acid, especially with C₁₂-C₄₀ alkyl radicals.
  • Copolymerization with monomers which are not capable of side chain crystallization, in particular with alkyl radicals <C₁₀ or branched alkyl radicals with C₁ to C₄₀.

Beispielsweise erfüllen folgende Polymertypen die besagte Bedingung:
Polytalgfettacrylat (C₁₆-C₁₈-Alkylacrylat) = P2-a,
Polybehenylmethacrylat (C₁₈-C₂₄-Alkylmethacrylat) = P2-b
Copolymerisat aus Behenylacrylat (C₁₈-C₂₄-Alkylacrylat) und Isodecylacrylat = P2-c.
Die Molgewichte der Polymerisate P1 bzw. P2 liegen im allgemeinen im Bereich 5 000 bis 1 000 000, vorzugsweise 10 000 bis 500 000. Im allgemeinen wird die Einhaltung des Molgewichtsbereichs durch die Verwendung an sich bekannter Regler, beispielsweise vom Typ der Schwefelregler, sichergestellt. (Vgl. H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen, Springer-Verlag, Berlin 1967). Besonders genannt seien Mercaptane wie Dodecylmercaptan in Mengen von 0,01 bis 2 Gew.-% bezogen auf die Monomeren. Die Bestimmung der Molgewichte geschieht mittels Gelpermeationschromatographie, mit Polymethylmethacrylat als Eichsubstanz (vgl. Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd. Ed. Vol. 18, pg. 209 749, J. Wiley 1982).For example, the following types of polymers meet the above condition:
Poly tallow fat acrylate (C₁₆-C₁₈ alkyl acrylate) = P2-a,
Polybehenyl methacrylate (C₁₈-C₂₄ alkyl methacrylate) = P2-b
Copolymer of behenyl acrylate (C₁₈-C₂₄ alkyl acrylate) and isodecyl acrylate = P2-c.
The molecular weights of the polymers P1 and P2 are generally in the range 5,000 to 1,000,000, preferably 10,000 to 500,000. In general, compliance with the molecular weight range is ensured by using regulators known per se, for example of the sulfur regulator type. (See H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen, Springer-Verlag, Berlin 1967). Mercaptans such as dodecyl mercaptan in amounts of 0.01 to 2% by weight, based on the monomers, are particularly mentioned. The molecular weights are determined by means of gel permeation chromatography, using polymethyl methacrylate as the calibration substance (see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd. Ed. Vol. 18, pg. 209 749, J. Wiley 1982).

Die Ausgangsmonomeren sind an sich bekannt bzw. sie können in an sich bekannter Weise, beispielsweise durch Umesterung niederer (Meth)acrylate wie z.B. des Methyl oder Ethylesters mit den höheren Alkoholen hergestellt werden. Die Herstellung der Polymeren kann im Anschluß an die radikalischen Polymerisationsverfahren des Standes der Technik durchgeführt werden. (Vgl. H. Rauch-Punktigam, Th. Völker, Acryl- und Methacrylverbindungen, Springer-Verlag, Berlin 1967). Als Polymerisationsmedium empfiehlt sich ein inertes Medium, vorzugsweise vom Typ der Mineralöle selbst, beispielsweise 100 N-Öl.
Als Reaktionsgefäße kommen die gewöhnlich verwendeten, die zweckmäßig mit Rührer, Heizvorrichtung, Thermometer, Rückflußkühler und Dosierleitung ausgestattet sind, in Frage; vorzugsweise arbeitet man unter einem inerten Gas wie z.B. Kohlendioxid. Ferner bedient man sich der üblichen Radikal-Initiatoren vorzugsweise Perester, Peroxide oder Azoverbindungen, beispielsweise tert.Butylperbenzoat, tert.Butylperpivalat in den üblichen Konzentrationen, beispielsweise 0,1 - 5 Gew.-%, vorzugsweise 0,3 bis 1 Gew.-% bezogen auf die Gesamtmenge der Monomeren. Im allgemeinen wird das Verfahren bei erhöhter Temperatur, vorzugsweise ab 60 Grad C, insbesondere bei 70 - 90 begonnen, worauf Initiator zugesetzt wird und die Temperatur eine Spitze erreicht, die oberhalb 80 Grad C, beispielsweise 140 ± 10 Grad C liegen kann. Gegebenenfalls kann durch erneute Initiatorzugabe und wenn nötig durch Erwärmen die Nachpolymerisation eingeleitet werden. Im allgemeinen ist die Polymerisation innerhalb von ca. 5 Stunden abgeschlossen.The starting monomers are known per se or they can be prepared in a manner known per se, for example by transesterification of lower (meth) acrylates such as, for example, methyl or ethyl ester with the higher alcohols. The preparation of the polymers can follow the free radical polymerization processes of the prior art are carried out. (See H. Rauch-Punktigam, Th. Völker, Acryl- und Methacrylverbindungen, Springer-Verlag, Berlin 1967). An inert medium, preferably of the mineral oil type itself, for example 100 N oil, is recommended as the polymerization medium.
Possible reaction vessels are those which are usually used and which are expediently equipped with a stirrer, heating device, thermometer, reflux condenser and metering line; preferably one works under an inert gas such as carbon dioxide. Furthermore, the usual free radical initiators are preferably used peresters, peroxides or azo compounds, for example tert-butyl perbenzoate, tert-butyl perpivalate in the usual concentrations, for example 0.1-5% by weight, preferably 0.3 to 1% by weight. based on the total amount of monomers. In general, the process is started at elevated temperature, preferably from 60 degrees C, in particular at 70-90, whereupon initiator is added and the temperature reaches a peak which can be above 80 degrees C, for example 140 ± 10 degrees C. If necessary, the additional polymerization can be initiated by adding the initiator again and, if necessary, by heating. In general, the polymerization is completed in about 5 hours.

Die MineralöleThe mineral oils

Bei den Mineralölen bzw. Mineralölprodukten, deren Eigenschaften, insbesondere deren temperaturabhängiges Fließverhalten durch die vorliegende Erfindung verbessert wird, handelt es sich vorwiegend um Mineralölprodukte aus den folgenden Gruppen:

  • Roherdöle
  • Vakuumgasöle mit einer Siedelage 320 bis 500 Grad C bei Normaldruck (True Boiling Point)
  • Rückstandsöle (Destillationsrückstände, die über 350 Grad C destillieren wurden).
(Vgl. Winnacker-Küchler, Chemische Technologie, Band 5, 4. Auflage, Carl Hanser Verlag, München 1981).In the case of mineral oils or mineral oil products, their properties, in particular their temperature-dependent properties Flow behavior is improved by the present invention, it is mainly mineral oil products from the following groups:
  • Raw oils
  • Vacuum gas oils with a boiling point of 320 to 500 degrees C at normal pressure (true boiling point)
  • Residual oils (distillation residues that have been distilled above 350 degrees C).
(See Winnacker-Küchler, Chemische Technologie, Volume 5, 4th edition, Carl Hanser Verlag, Munich 1981).

Das Einsetzen der Paraffinkristallisation (CP) in Abhängigkeit von der Temperatur ist für die Mineralölprovenienzen bzw. die infrage kommenden Erdölprodukte eine wichtige Kenngröße, deren Bestimmung der Fachmann routinemäßig durchführt. Das bevorzugte Bestimmungsverfahren ist - wie bereits erwähnt - die DSC.The use of paraffin crystallization (CP) as a function of the temperature is an important parameter for the mineral oil provenances or the petroleum products in question, the determination of which is carried out routinely by a person skilled in the art. As already mentioned, the preferred determination method is the DSC.

Im allgemeinen beträgt der Gehalt der Mineralöle an den Polymerisaten P 1 - 10 000, vorzugsweise 50 bis 2 000 ppm, in Anpassung an die Provenienzen, deren Fließeigenschaften es zu verbessern gilt.In general, the content of mineral oils in the polymers P is 1-10,000, preferably 50 to 2,000 ppm, in adaptation to the provenances, the flow properties of which need to be improved.

Ausführung der ErfindungImplementation of the invention

Die Polymerisate P können nach erfolgter Polymerisation vorteilhaft mit einem geeigneten verträglichen Lösungsmittel, beispielsweise einem Kohlenwasserstoff wie Xylol, Toluol, Kerosin, SHELLSOL® verdünnt werden. Die so erhaltene Lösung kann dann bei der Herstellung der Mineralölgemische angewendet werden. Im speziellen Fall kann diese Lösung dem Rohöl direkt am Sondenkopf oder in der Pipeline zudosiert werden.
Man mischt die Polymerisate P, vorzugsweise in Form der genannten Lösungen den Mineralölen wie Rohölen, Vakuumgasölen bzw. Rückstandsölen zweckmäßig bei erhöhter Temperatur, beispielsweise bei 40 bis 80 Grad C zu. Die Wirkung der fließverbessernden Additive bleibt über den normalerweise zu fordernden Zeitraum erhalten. Neben den erfindungsgemäßen Polymeren P1 und P2 bedarf es nicht notwendig eines weiteren Zusatzes von Fließverbesserern, jedoch können noch weitere Komponenten wie z.B. Demulsifier zugesetzt werden.After the polymerization, the polymers P can advantageously with a suitable compatible solvent, for example a hydrocarbon such as Xylene, toluene, kerosene, SHELLSOL® can be diluted. The solution thus obtained can then be used in the preparation of the mineral oil mixtures. In special cases, this solution can be added to the crude oil directly at the probe head or in the pipeline.
The polymers P, preferably in the form of the solutions mentioned, are advantageously mixed with the mineral oils, such as crude oils, vacuum gas oils or residual oils, at an elevated temperature, for example at 40 to 80 degrees C. The effect of the flow-improving additives is retained over the period that is normally required. In addition to the polymers P1 and P2 according to the invention, it is not necessary to add further flow improvers, but other components such as demulsifiers can also be added.

Vorteilhafte WirkungenBeneficial effects

Die ausgezeichnete fließverbessernde Wirkung der Mischungen aus A) plus B) war umso weniger vorauszusehen, als die Polymerisate P2 mit ihren Eigenassoziationstemperaturen unterhalb 15 Grad C an sich unwirksam oder zumindest schlecht wirksam sind. In der Kombination erhält man - bezogen auf die Menge des eingesetzten Polymerisats - eine bessere bis gleichgute Wirksamkeit, wie mit der Polymerkomponente P1 allein.The excellent flow-improving effect of the mixtures of A) plus B) was all the less predictable, since the polymers P2, with their inherent association temperatures below 15 ° C., are ineffective or at least poorly effective. The combination gives - based on the amount of polymer used - better to equally good effectiveness as with polymer component P1 alone.

In jedem Fall beobachtet man eindeutig synergistische Effekte. Selbst im Falle einer nicht überlegenen sondern nur gleichguten Wirkung lägen - wegen der besserern Zugänglichkeit bzw. dem niederen Preis der zweiten Komponente - bedeutende Vorteile vor.In any case, one clearly observes synergistic effects. Even in the case of a non-superior but only equally good effect - because of the better ones Accessibility or the lower price of the second component - significant advantages.

Für das unerwartete Zusammenwirken der beiden Polymerkomponenten P1 und P2 läßt sich eine Modellvorstellung entwickeln, deren Stichhaltigkeit jedoch ohne Einfluß auf die vorliegende technische Lehre sein soll: In einer ersten Phase beeinflußt die Komponente mit der höheren Eigenassoziationstemperatur die Kristallisation der langkettigen Rohöl-Paraffine. In einer zweiten "Tieftemperaturphase" wird die zweite Komponente mit niedrigerer Eigenassoziationstemperatur wirksam. Daraus lassen sich gewisse Auswahlkriterien für bevorzugte Kombinationen ableiten, die aber nur als grobe Faustregeln zu verstehen sind, da es Ausnahmen und Überschneidungen gibt:
Für Polybehenylacrylat als Komponente A) kann z.B. von folgendem Ansatz ausgegangen werden:
In Rohölen, in denen Polybehenylacrylat den Pour Point höchstens bis 0 Grad C absenkt, sind Mischkomponenten B) mit Eigenkristallisationstemperaturen zwischen 0 und 15 Grad C vorteilhaft. In Rohölen, in denen mit Polybehenylacrylat der Pour Point auf unter -5 Grad C abgesenkt werden kann, sind Mischkomponenten B) mit Eigenassoziationstemperaturen <- 5 Grad C optimal.A model concept can be developed for the unexpected interaction of the two polymer components P1 and P2, the validity of which should, however, have no influence on the present technical teaching: In a first phase, the component with the higher self-association temperature influences the crystallization of the long-chain crude oil paraffins. In a second "low temperature phase" the second component with a lower self-association temperature takes effect. From this, certain selection criteria for preferred combinations can be derived, but these are only to be understood as rough rules of thumb, as there are exceptions and overlaps:
For polybehenyl acrylate as component A), the following approach can be used, for example:
In crude oils in which polybehenyl acrylate lowers the pour point by no more than 0 degrees C, mixed components B) with intrinsic crystallization temperatures between 0 and 15 degrees C are advantageous. In crude oils, in which the pour point can be lowered to below -5 degrees C with polybehenyl acrylate, mixed components B) with self-association temperatures <- 5 degrees C are optimal.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung.The following examples serve to illustrate the invention.

BEISPIELEEXAMPLES Beispiel 1example 1 Herstellung von Polybehenylacrylat P1-aPreparation of polybehenyl acrylate P1-a

In einem 100 l-Rührkessel wurden 51 kg Behenylacrylat (C18-24-Acrylat), 9 kg 100 N-Öl und 0,051 kg Dodecylmercaptan vorgelegt, mit CO₂-Eis entgast und auf 70 Grad C erwärmt. Anschließend wurden 0,191 kg t-Butylperpivalat und 0,115 kg t-Btuylperbenzoat zugegeben, um die Polymerisation zu starten. 1 Stunde nach Erreichen der Temperaturspitze von 134 Grad C wurde mit 0,077 kg Dodecylmercaptan und 0,051 kg t-Butylperbenzoat versetzt und bei 130 Grad C 3 Stunden lang nachpolymerisiert.

Mw (GPC, PMMA-Eichung)
= 560 000 g/mol
nsp/c (CHCl₃, 20 Grad C
= 48 ml/g
CP (0,1 % Isooctan)
= 19,5 Grad C.
51 kg of behenyl acrylate (C18-24 acrylate), 9 kg of 100 N oil and 0.051 kg of dodecyl mercaptan were placed in a 100 l stirred kettle, degassed with CO₂ ice and heated to 70 ° C. Then 0.191 kg of t-butyl perpivalate and 0.115 kg of t-butyl perbenzoate were added to start the polymerization. 1 hour after the temperature peak of 134 degrees C was reached, 0.077 kg of dodecyl mercaptan and 0.051 kg of t-butyl perbenzoate were added and the polymerization was continued at 130 degrees C for 3 hours.
Mw (GPC, PMMA calibration)
= 560,000 g / mol
nsp / c (CHCl₃, 20 degrees C
= 48 ml / g
CP (0.1% isooctane)
= 19.5 degrees C.

Anstelle von Behenylacrylat kann z.B. auch (ALFOL 20+)-acrylat (Acrylester von C20, C22, C24-Alkohol) eingesetzt werden.Instead of behenyl acrylate, e.g. (ALFOL 20 +) acrylate (acrylic esters of C20, C22, C24 alcohol) can also be used.

Beispiel 2Example 2 Herstellung von Polybehenylmethacrylat P2-bProduction of polybehenyl methacrylate P2-b

In einem 100 l-Rührkessel wurden 30 kg Behenylmethacrylat (C18-24-Methacrylat), 30 kg 100 N-Öl und 0,60 kg Dodecylmercaptan vorgelegt. Nach Entgasen der Mischung mit CO₂-Eis wurde auf 70 Grad C erwärmt und 0,60 kg t- Butylperpivalat wurden zugegeben. 2 Stunden nach Erreichen der Temperaturspitze von 96,5 Grad C wurde auf 130 Grad C erwärmt und 0,03 kg Dodecylmercaptan und 0,06 kg t-Butylperbenzoat wurden zugegeben. Nach 5 Stunden war die Polymerisation abgeschlossen.

Mw (GPC, PMMA-Eichung)
= 24 300 g/mol
ηsp/c (CHCl₃, 20 Grad C)
= 11 ml/g
CP (0,1 % in Isooctan)
= - 2 Grad C
30 kg of behenyl methacrylate (C18-24 methacrylate), 30 kg of 100 N oil and 0.60 kg of dodecyl mercaptan were placed in a 100 l stirred kettle. After degassing the mixture with CO₂ ice, the mixture was heated to 70 degrees C and 0.60 kg t Butyl perpivalate was added. Two hours after the temperature peak of 96.5 degrees C was reached, the temperature was raised to 130 degrees C and 0.03 kg of dodecyl mercaptan and 0.06 kg of t-butyl perbenzoate were added. The polymerization was complete after 5 hours.
Mw (GPC, PMMA calibration)
= 24 300 g / mol
ηsp / c (CHCl₃, 20 degrees C)
= 11 ml / g
CP (0.1% in isooctane)
= - 2 degrees C.

Beispiel 3Example 3 Herstellung von Polytalgfettacrylat P2-aProduction of poly tallow fat acrylate P2-a

In einem 200 l-Kessel wurden 102 kg Talgfettacrylat (C16-18-Acrylat), 18 kg 100 N-Öl und 2,55 kg Dodecylmercaptan vorgelegt. Die Mischung wurde durch Zugabe von CO₂-Eis entgast und anschließend auf 70 Grad C erwärmt. Dann wurden 0,612 kg t-Butylperpivalat zugegeben. Die Temperatur stieg auf 142 Grad C an. 1 und 2 Stunden nach Erreichen der Temperaturspitze wurden bei 130 Grad C jeweils 0,204 kg Dodecylmercaptan und 0,102 kg t-Butylperbenzoat zugegeben. Nach 5 Stunden war die Polymerisation abgeschlossen.

Mw (GPC, PMMA-Eichung)
= 20 100 g/mol
ηsp/c (CHCl₃, 20 Grad C)
= 9,3 ml/g
CP (0,1 % in Isooctan)
= 9,5 Grad C.
102 kg of tallow fat acrylate (C16-18 acrylate), 18 kg of 100 N oil and 2.55 kg of dodecyl mercaptan were placed in a 200 l kettle. The mixture was degassed by adding CO₂ ice and then heated to 70 degrees C. Then 0.612 kg of t-butyl perpivalate was added. The temperature rose to 142 degrees Celsius. 1 and 2 hours after the temperature peak was reached, 0.204 kg of dodecyl mercaptan and 0.102 kg of t-butyl perbenzoate were added at 130 degrees C. The polymerization was complete after 5 hours.
Mw (GPC, PMMA calibration)
= 20 100 g / mol
ηsp / c (CHCl₃, 20 degrees C)
= 9.3 ml / g
CP (0.1% in isooctane)
= 9.5 degrees C.

Beispiel 4Example 4 Herstellung von Polytalgfettacrylat P2-a′Production of poly tallow fat acrylate P2-a ′

In einem 150 l-Kessel wurden 85 kg Talgfettacrylat (C16-18-Acrylat), 15 kg 100 N-Öl und 0,425 kg Dodecylmercaptan vorgelegt. Die Mischung wurde durch Zugabe von CO₂-Eis entgast und anschließend auf 70 Grad C erwärmt. Dann wurden 0,425 kg t-Butylperpivalat zugegeben. Die Temperatur stieg auf 148 Grad C an. 1 und 2 Stunden nach Erreichen der Temperaturspitze wurden bei 130 Grad C jeweils 0,17 kg Dodecylmercaptan und 0,085 kg t-Butylperbenzoat zugegeben. Nach 5 Stunden war die Polymerisation abgeschlossen.

Mw (GPC, PMMA-Eichung)
= 118 000 g/mol
ηsp/c (CHCl₃, 20 Grad C)
= 21 ml/g
CP (0,1 % in Isooctan)
= + 10 Grad C
85 kg of tallow fat acrylate (C16-18 acrylate), 15 kg of 100 N oil and 0.425 kg of dodecyl mercaptan were placed in a 150 l kettle. The mixture was degassed by adding CO₂ ice and then heated to 70 degrees C. Then 0.425 kg of t-butyl perpivalate was added. The temperature rose to 148 degrees Celsius. 1 and 2 hours after the temperature peak was reached, 0.17 kg of dodecyl mercaptan and 0.085 kg of t-butyl perbenzoate were added at 130 degrees C. The polymerization was complete after 5 hours.
Mw (GPC, PMMA calibration)
= 118,000 g / mol
ηsp / c (CHCl₃, 20 degrees C)
= 21 ml / g
CP (0.1% in isooctane)
= + 10 degrees C.

Beispiel 5Example 5 Herstellung eines Copolymeren aus Behenylmethacrylat und Methylmethacrylat P2-cPreparation of a copolymer of behenyl methacrylate and methyl methacrylate P2-c

In einem 200 l-Rührkessel wurden 67,1 kg Behenylmethacrylat (C18-24-Methacrylat), 7,9 kg Methylmethacrylat, 75 kg 100 N-Öl und 1,875 kg Dodecylmercaptan vorgelegt. Die Mischung wurde durch Zugabe von CO₂-Eis entgast und auf 70 Grad C erwärmt. Anschließend wurden 0,3 kg t-Butylperpivalat zugegeben, worauf die Temperatur auf 94 Grad C anstieg. 5 Stunden nach Reaktionsbeginn wurden bei 70 Grad C erneut 0,075 kg Dodecylmercaptan und 0,15 kg t-Butylperpivalat zugesetzt. Nach weiteren 6 Stunden bei 70 Grad C war die Polymerisation abgeschlossen.

Mw (GPC, PMMA-Eichung)
= 26 000 g/mol
ηsp/c (CHCl₃, 20 Grad C)
= 11 ml/g
CP (0,1 % in Isooctan)
= -7 Grad C
67.1 kg of behenyl methacrylate (C18-24 methacrylate), 7.9 kg of methyl methacrylate, 75 kg of 100 N oil and 1.875 kg of dodecyl mercaptan were placed in a 200 l stirred kettle. The mixture was degassed by adding CO₂ ice and heated to 70 degrees C. Then 0.3 kg of t-butyl perpivalate was added, whereupon the temperature rose to 94 degrees C. 5 hours after the start of the reaction, 0.075 kg of dodecyl mercaptan and 0.15 kg of t-butyl perpivalate were again added at 70 ° C. After a further 6 hours at 70 degrees C, the polymerization was complete.
Mw (GPC, PMMA calibration)
= 26,000 g / mol
ηsp / c (CHCl₃, 20 degrees C)
= 11 ml / g
CP (0.1% in isooctane)
= -7 degrees C.

Beispiel 6Example 6 Herstellung von Poly(C16-18-Alkylmethacrylat9 P2-dPreparation of poly (C16-18 alkyl methacrylate9 P2-d

In einem 150 l-Rührkessel wurden 4,889 kg C16-18-Alkylmethacrylat (z.B. auf Basis Alfol 1618 SR-Alkohol der Condea), 44,0 kg 100 N-Öl und 0,172 kg t-Butylperoctoat vorgelegt. Nach dem Entgasen mit CO₂-Eis wurde auf 85 Grad C erwärmt. Anschließend wurden innerhalb 3,5 Stunden 51,111 kg C16-18-Alkylmethacrylat und 0,153 kg t-Butylperoctoat mittels einer Dosierpumpe zugegeben. 2 Stunden nach Zulaufende wurden erneut 0,112 kg t-Butylperoctoat zugegeben. Nach weiteren 5 Stunden war die Polymerisation abgeschlossen.

Mw (GPC, PMMA-Eichung)
= 220 000 g/mol
ηsp/c (CHCl₃, 20 Grad C)
= 44 ml/g
CP (0,1 % in Isooctan)
= -14 Grad C
In a 150 l stirred kettle, 4,889 kg of C16-18 alkyl methacrylate (based, for example, on Alfol 1618 S R alcohol from Condea), 44.0 kg of 100 N oil and 0.172 kg of t-butyl peroctoate were introduced. After degassing with CO₂ ice, the temperature was raised to 85 degrees C. Then 51.111 kg of C16-18 alkyl methacrylate and 0.153 kg of t-butyl peroctoate were added by means of a metering pump within 3.5 hours. 2 hours after the end of the feed, 0.112 kg of t-butyl peroctoate were again added. The polymerization was complete after a further 5 hours.
Mw (GPC, PMMA calibration)
= 220,000 g / mol
ηsp / c (CHCl₃, 20 degrees C)
= 44 ml / g
CP (0.1% in isooctane)
= -14 degrees C.

Beispiel 7Example 7 Herstellung von Poly(C12-18-alkylmethacrylat) P2-ePreparation of poly (C12-18 alkyl methacrylate) P2-e

In einem 150 l-Rührkessel wurden 2,967 kg eines C12-18-Alkylmethacrylates (mittlere C-Zahl 14, 18 % verzweigt, z.B. auf Basis einer Mischung aus Dobanol 25 L R der Shell und Talgfettalkohol), 26,7 kg 100 N-Öl und 0,083 kg t-Butylperoctoat vorgelegt, mit CO₂-Eis entgast und auf 85 Grad C erwärmt. Innerhalb von 3,5 Stunden wurden dann 37,033 kg C12-18-Alkylmethacrylat und 0,0741 kg t-Butylperoctoat zudosiert. 2 Stunden nach Zulaufende wurden erneut 0,08 kg t-Butylperoctoat zugegeben. Nach weiteren 5 Stunden wurde mit 33,3 kg 100 N-Öl verdünnt.

Mw (GPC, PMMA-Eichung)
= 410 000 g/mol
ηsp/c (CHCl₃, 20 Grad C)
= 65 ml/g
CP (0,1 % in Isooctan)
= < -45 Grad C
In a 150 l stirred kettle, 2.967 kg of a C12-18 alkyl methacrylate (average C number 14, 18% branched, for example based on a mixture of Dobanol 25 L R from Shell and tallow fatty alcohol), 26.7 kg of 100 N oil and submitted 0.083 kg of t-butyl peroctoate, degassed with CO₂ ice and heated to 85 degrees C. 37.033 kg of C12-18 alkyl methacrylate and 0.0741 kg of t-butyl peroctoate were then metered in within 3.5 hours. Another 2 hours after the end of the feed, 0.08 kg of t-butyl peroctoate were added. After a further 5 hours, the mixture was diluted with 33.3 kg of 100 N oil.
Mw (GPC, PMMA calibration)
= 410,000 g / mol
ηsp / c (CHCl₃, 20 degrees C)
= 65 ml / g
CP (0.1% in isooctane)
= <-45 degrees C.

Beispiele 8 - 12:Examples 8-12:

Die Polymere P1-a - P2-e wurden als 10 %ige Lösung in Xylol den Rohölen bei 80 Grad C zugesetzt. Alle Dosierungen beziehen sich auf Polymerisat. Die Pour Points wurden in Anlehnung an DIN 51 597 mit einem automatischen Meßgerät der Fa. Herzog, Lauda, bestimmt. Die Pour Points in Beispiel 8 wurden nach DIN 51 597 (ASTM 097-66) bestimmt.The polymers P1-a-P2-e were added as a 10% solution in xylene to the crude oils at 80 degrees C. All dosages relate to polymer. The pour points were determined in accordance with DIN 51 597 using an automatic measuring device from Herzog, Lauda. The pour points in Example 8 were determined in accordance with DIN 51 597 (ASTM 097-66).

Die Beispiele belegen bessere Wirksamkeit der Mischungen gegenüber den Einzelkomponenten.

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
 The examples demonstrate better effectiveness of the mixtures compared to the individual components.
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006

Claims (3)

1. Mineral oils and mineral oil products with an improved flow behaviour from the group of crude oils, vacuum gas oils or residual oils, containing long-chain polyalkyl(meth)acrylates, characterised in that the long-chain polyalkyl(meth)acrylates are a mixture of
A) a polyalkyl(meth)acrylate P1 which starts to crystallize at temperatures above 15 degrees C (measured as cloud point according to DIN 51597 of a 0.1% solution in isooctane) and
B) a polyalkyl(meth)acrylate P2 which starts to crystallize at temperatures at or below 15 degrees C, with the proviso that between the commencement of the crystallization of the polyalkyl(meth)acrylate P1 and the commencement of the crystallization of the polyalkyl(meth)acrylate P2, there is a temperature difference of at least 5 degrees C.
2. Mineral oil mixture according to claim 1, characterised in that the weight ratio of the polyalkyl(meth)acrylate is in the range from 1 : 50 to 50 : 1, preferably 1 : 10 to 10 : 1.
3. Mineral oil mixture according to claims 1 and 2, characterised in that the polyalkyl(meth)acrylate P1 is synthesised from acrylic esters of C₁₈-C₂₄-alkanols.
EP90112914A 1989-07-14 1990-07-06 Mineral oils with improved flow behaviour Expired - Lifetime EP0407906B1 (en)

Priority Applications (1)

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DE3818438A1 (en) * 1988-05-31 1989-12-07 Roehm Gmbh MINERAL OIL WITH IMPROVED FLOW BEHAVIOR

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JPH0356593A (en) 1991-03-12
CA2021246C (en) 1994-03-15
EP0407906A1 (en) 1991-01-16
ATE75768T1 (en) 1992-05-15
DE3923249A1 (en) 1991-01-24
DE59000113D1 (en) 1992-06-11
CA2021246A1 (en) 1991-01-15
JP2760886B2 (en) 1998-06-04

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