EP0190553A1 - Process to improve the viscosity of mineral oils and of the distillates of mineral oils - Google Patents
Process to improve the viscosity of mineral oils and of the distillates of mineral oils Download PDFInfo
- Publication number
- EP0190553A1 EP0190553A1 EP86100143A EP86100143A EP0190553A1 EP 0190553 A1 EP0190553 A1 EP 0190553A1 EP 86100143 A EP86100143 A EP 86100143A EP 86100143 A EP86100143 A EP 86100143A EP 0190553 A1 EP0190553 A1 EP 0190553A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- vinyl acetate
- ethylene
- propene
- mineral oils
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
Definitions
- the present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of ethylene-vinyl acetate copolymers and ethylene-propene-vinyl acetate terpolymers.
- Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. For example, the ability of crude oil production and transport facilities to function until their complete failure are impaired. In diesel engines and combustion plants, the filters can become clogged, which ultimately results in an interruption in the fuel or heating medium supply.
- additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.
- Copoly has the greatest importance as pour point depressants and flow improvers for crude oils and middle distillates merisate of ethylene with carboxylic acid esters of vinyl alcohol.
- ethylene-vinyl acetate copolymers have proven particularly useful.
- Such copolymers and their use are described for example in DE-PS 1 914 756. They are generally prepared by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C. and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.
- Ethylene-vinyl acetate copolymers are generally commercially available as solutions in hydrocarbons. For economic reasons, these solutions should contain the active ingredient in the highest possible concentration and be easy to handle.
- the object was therefore to develop flow improvers for mineral oils which, at the same concentration in the mineral oil, are at least as effective as ethylene-vinyl acetate copolymers, but have a significantly better solubility in hydrocarbons or hydrocarbon mixtures than these.
- the invention consists in a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that a mixture of an ethylene-vinyl acetate copolymer and an ethylene-propene-vinyl acetate terpolymer is added to the mineral oils or mineral oil distillates.
- the ethylene-vinyl acetate copolymers used according to the invention contain 20 to 40% by weight of vinyl acetate. Copolymers with 25 to 35% by weight of vinyl acetate (based in each case on the copolymer) have proven particularly useful. Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, measured at 140 ° C. in each case and they have 2 to 10, in particular 3 to 7, CH 3 groups per 100 CH 2 groups.
- the production of the ethylene-vinyl acetate copolymers is known. It is carried out by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in an organic solvent as the reaction medium. However, the polymerization at pressures above 50 MPa and temperatures between 120 and 300 ° C in absentia is preferred - made uniform organic solvents.
- the ethylene-propene-vinyl acetate terpolymers of the new process contain 20 to 40% by weight, in particular 25 to 35% by weight, of vinyl acetate (in each case based on the terpolymer).
- Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C.
- Each 100 CH 2 groups have 8 to 25, in particular 12 to 20 CH 3 groups, which do not result from the acetate residue of the vinyl acetate.
- the preparation of the terpolymers is also described.
- Mixtures of ethylene, propene and vinyl acetate are used, which are polymerized in the presence of free radical initiators at pressures above 50 mPa and at temperatures from 150 to 350 ° C. in the absence of organic solvents.
- the molecular weight of the terpolymers is preferably adjusted by the propene, which also acts as a molecular weight regulator.
- other molecular weight regulators such as hydrocarbons, aldehydes, ketones can also be used.
- Monomer mixtures containing 30 to 60% by weight of ethylene, 20 to 50% by weight of propene and 15 to 35% by weight of vinyl acetate are used for the polymerization.
- the mineral oils and mineral oil distillates produced by the process according to the invention to improve their flowability are added to polymer mixtures which contain ethylene-vinyl acetate copolymer and ethylene-propene-vinyl acetate terpolymer in a weight ratio of 0.5 to 1 to 20 to 1. Mixtures containing the copolymer and Contain terpolymer in a weight ratio of 2 to 1 to 10 to 1. It is advisable to use copolymers and terpolymers in the polymer mixture whose vinyl acetate content (in% by weight) is approximately the same and in particular does not deviate from one another by more than 3% by weight.
- the viscosity of the polymers contained in the mixture should also be as equal as possible, and the deviations should in particular not be greater than 200 mPa.s, measured at 140 ° C.
- the mixtures of the polymers are added to the mineral oils or the mineral oil fractions in the form of 40 to 60% by weight solutions in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture.
- an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture For example, Kerosene.
- the amount of polymer, based on mineral oil or mineral oil fraction, should be 0.001 to 2, preferably 0.005 to 0.5,% by weight.
- the polymer mixtures can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, corrosion inhibitors, antioxidants or sludge inhibitors.
- Examples AF relate to the preparation of the ethylene-propene-vinyl acetate terpolymers
- examples G-I relate to the production of the ethylene-vinyl acetate copolymers.
- Examples 10-18 describe the flow behavior of middle distillates after the addition of copolymer-terpolymer mixtures according to the inventive method.
- Ethylene, propene and vinyl acetate are continuously polymerized in an autoclave.
- the monomer mixture is fed into the autoclave at the reaction pressure after the for the maintenance of the polymerization required amount of peroxide has been added as a solution in a gasoline fraction.
- the dwell time is about 80 seconds.
- the vinyl acetate content in the polymers is determined using the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask at 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The acetic acid formed is reacted with a NaJ / KJ0 3 solution and the released iodine is titrated with Na 2 S 2 0 3 solution.
- the degree of branching of the polymers is determined by H-NMR spectroscopy.
- the degree of branching is understood to mean the number of CH 3 groups per 100 CH 2 groups with the exception of the CH 3 groups, which originate from the acetate residue.
- the monomer mixture consisting of ethylene and vinyl acetate is polymerized in a tubular reactor at 150 MPa pressure in the absence of substantial amounts of a solvent.
- Organic peroxides are used as initiators.
- the vinyl acetate content and the degree of branching are determined by the methods given for the ethylene-propene-vinyl acetate terpolymers.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten durch Zusatz von Mischungen aus Ethylen-Vinylacetat-Copolymerisaten und Ethylen-Propen-Vinylacetat-Terpolymerisaten.The present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of ethylene-vinyl acetate copolymers and ethylene-propene-vinyl acetate terpolymers.
Mineralöle wie Rohöl, Dieselkraftstoff oder Heizöl enthalten Paraffin gelöst, das bei niedrigen Temperaturen auskriatallisiert. Diese Feststoffablagerungen führen häufig zu Störungen bei der Gewinnung und beim Einsatz von Mineralölen. So kann z.B. die Arbeitsfähigkeit von Förder- und Transporteinrichtungen für Rohöl bis zu deren völligem Ausfall beeinträchtigt werden. Bei Dieselmotoren und Feuerungsanlagen können Verstopfungen der Filter auftreten, die schließlich in einer Unterbrechung der Kraftstoff- bzw. Heizmittelzufuhr reaultieren.Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. For example, the ability of crude oil production and transport facilities to function until their complete failure are impaired. In diesel engines and combustion plants, the filters can become clogged, which ultimately results in an interruption in the fuel or heating medium supply.
Um diese unerwünschte Feststoffbildung zu vermeiden, setzt man Mineralölen Additive zu, die der Entstehung von Paraffinkristallen entgegenwirken. Dadurch wird ein Anstieg der Viskosität der Öle verhindert und ihr Stockpunkt gesenkt.In order to avoid this undesirable solid formation, additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.
Die größte Bedeutung als Stockpunktserniedriger und Fließverbesserer für Rohöle und Mitteldestillate haben Copolymerisate des Ethylens mit Carbonsäureestern des Vinylalkohols erlangt. Besonders bewährt haben sich unter ihnen Ethylen-Vinylacetat-Copolymerisate. Solche Mischpolymerisate und ihre Verwendung sind z.B. in der DE-PS 1 914 756 beschrieben. Ihre Herstellung erfolgt im allgemeinen durch Copolymerisation der Monomeren in Autoklaven bei Temperaturen von 80 bis 150°C und Drücken von 5 bis 15 MPa in Gegenwart von Peroxiden als Initiatoren und organischen Lösungsmittels als Reaktionsmedium.Copoly has the greatest importance as pour point depressants and flow improvers for crude oils and middle distillates merisate of ethylene with carboxylic acid esters of vinyl alcohol. Among them, ethylene-vinyl acetate copolymers have proven particularly useful. Such copolymers and their use are described for example in DE-PS 1 914 756. They are generally prepared by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C. and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.
Ethylen-Vinylacetat-Copolymerisate kommen im allgemeinen als Lösungen in Kohlenwasserstoffen in den Handel. Diese Lösungen sollen aus wirtschaftlichen Gründen den Wirkstoff in möglichst hoher Konzentration enthalten und leicht handhabbar sein.Ethylene-vinyl acetate copolymers are generally commercially available as solutions in hydrocarbons. For economic reasons, these solutions should contain the active ingredient in the highest possible concentration and be easy to handle.
Es ist ein Nachteil der als Fließverbesserer hervorragend geeigneten Ethylen-Vinylacetat-Copolymerisate, daß ihre Lösungen in den verschiedensten Lösungsmitteln, z.B. in Kerosin, relativ hohe Stock- bzw. Fließtemperaturen besitzen, wodurch ihre Anwendbarkeit erschwert Wird.It is a disadvantage of the ethylene-vinyl acetate copolymers which are outstandingly suitable as flow improvers that their solutions are present in a wide variety of solvents, e.g. in kerosene, have relatively high stock or flow temperatures, which makes their applicability more difficult.
Es bestand daher die Aufgabe, Fließverbesserer für Mineralöle zu entwickeln, die bei gleicher Konzentration im Mineralöl mindestens ebenso wirksam sind wie Ethylen-Vinylacetat-Copolymerisate, gegenüber diesen jedoch eine wesentlich bessere Löslichkeit in Kohlenwasserstoffen bzw. Kohlenwasserstoffgemischen aufweisen.The object was therefore to develop flow improvers for mineral oils which, at the same concentration in the mineral oil, are at least as effective as ethylene-vinyl acetate copolymers, but have a significantly better solubility in hydrocarbons or hydrocarbon mixtures than these.
Die Erfindung besteht in einem Verfahren zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten. Es ist dadurch gekennzeichnet, daß man den Mineralölen bzw. Mineralöldestillaten eine Mischung aus einem Ethylen-Vinylacetat-Copolymerisat und einem Ethylen-Propen-Vinylacetat-Terpolymerisat zusetzt.The invention consists in a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that a mixture of an ethylene-vinyl acetate copolymer and an ethylene-propene-vinyl acetate terpolymer is added to the mineral oils or mineral oil distillates.
Es ist überraschend, daß die gestellte Aufgabe durch die erfindungsgemäße Arbeitsweise gelöst wird. Denn es war nicht vorauszusehen, daß Ethylen-Propen-Vinylacetat-Terpolymerisatc die Löslichkeit von Ethylen-Vinylacetat-Copolymerisaten in Kohlenwasserstoffen oder Kohlenwasserstoffgemischen beeinflußt. Ebenso wenig war zu erwarten, daß Gemische aus Ethylen-Propen-Vinylacetat-Terpolymerisaten mit Ethylen-Vinylacetat-Copolymerisatcn mindestens gleich geeignete Fließverbesserer sind wie die Copolymerisate allein, denn Ethylen-Propen-Vinylacetat-Terpolymerisate für sich wirken nicht oder nur in geringem Maße als Fließverbesserer für Mineralöle und Mineralöldestillate.It is surprising that the task is solved by the procedure according to the invention. Because it could not have been foreseen that ethylene-propene-vinyl acetate terpolymers would influence the solubility of ethylene-vinyl acetate copolymers in hydrocarbons or hydrocarbon mixtures. Likewise, it was not to be expected that mixtures of ethylene-propene-vinyl acetate terpolymers with ethylene-vinyl acetate copolymers would be at least as suitable flow improvers as the copolymers alone, because ethylene-propene-vinyl acetate terpolymers do not work per se or only to a small extent as Flow improver for mineral oils and mineral oil distillates.
Die erfindungsgemäß eingesetzten Ethylen-Vinylacetat-Copolymerisate enthalten 20 bis 40 Gew.% Vinylacetat. Besonders bewährt haben sich Copolymerisate mit 25 bis 35 Gew.% Vinylacetat (jeweils bezogen auf das Copolymerisat). Ihre Viskosität beträgt 100 bis 5000 mPa.s, insbesondere 200 bis 1500 mPa.s, jeweils gemessen bei 140°C und sie weisen je 100 CH2-Gruppen 2 bis 10, insbesondere 3 bis 7 CH3-Gruppen auf.The ethylene-vinyl acetate copolymers used according to the invention contain 20 to 40% by weight of vinyl acetate. Copolymers with 25 to 35% by weight of vinyl acetate (based in each case on the copolymer) have proven particularly useful. Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, measured at 140 ° C. in each case and they have 2 to 10, in particular 3 to 7, CH 3 groups per 100 CH 2 groups.
Die Herstellung der Ethylen-Vinylacetat-Copolymerisate ist bekannt. Sie erfolgt durch Polymerisation des Monomerengemisches bei Drücken von 5 bis 15 MPa und Temperaturen von 70 bis 150°C in einem organischen Lösungsmittel als Reaktionsmedium. Bevorzugt wird jedoch die Polymerisation bei Drücken oberhalb 50 MPa und Temperaturen zwischen 120 und 300°C in Abwesen- heit organischer Lösungsmittel durchgeführt.The production of the ethylene-vinyl acetate copolymers is known. It is carried out by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in an organic solvent as the reaction medium. However, the polymerization at pressures above 50 MPa and temperatures between 120 and 300 ° C in absentia is preferred - made uniform organic solvents.
Die Ethylen-Propen-Vinylacetat-Terpolymerisate des neuen Verfahrens enthalten 20 bis 40 Gew.%, insbesondere 25 bis 35 Gew.% Vinylacetat (jeweils bezogen auf das Terpolymerisat).The ethylene-propene-vinyl acetate terpolymers of the new process contain 20 to 40% by weight, in particular 25 to 35% by weight, of vinyl acetate (in each case based on the terpolymer).
Ihre Viskosität beträgt 100 bis 5000 mPa.s, insbesondere 200 bis 1500 mPa.s, jeweils gemessen bei 140°C. Je 100 CH2-Gruppen weisen sie 8 bis 25, insbesondere 12 bis 20 CH3-Gruppen auf, die nicht aus dem Acetatrest des Vinylacetats herrühren.Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C. Each 100 CH 2 groups have 8 to 25, in particular 12 to 20 CH 3 groups, which do not result from the acetate residue of the vinyl acetate.
Auch die Herstellung der Terpolymerisate ist vorbeschrieben. Man geht von Gemischen aus Ethylen, Propen und Vinylacetat aus, die in Gegenwart Radikale bildender Initiatoren bei Drücken oberhalb 50 mPa und bei Temperaturen von 150 bis 350°C in Abwesenheit von organischen Lösungsmitteln polymerisiert werden. Das Molekulargewicht der Terpolymerisate wird vorzugsweise durch das auch als Molekulargewichtsregler wirkende Propen eingestellt. Andere Molekulargewichtsregler wie Kohlenwasserstoffe, Aldehyde, Ketone können jedoch zusätzlich verwendet werden. Zur Polymerisation werden Monomerengemische eingesetzt, die 30 bis 60 Gew.% Ethylen, 20 bis 50 Gew.% Propen und 15 bis 35 Gew.% Vinylacetat enthalten.The preparation of the terpolymers is also described. Mixtures of ethylene, propene and vinyl acetate are used, which are polymerized in the presence of free radical initiators at pressures above 50 mPa and at temperatures from 150 to 350 ° C. in the absence of organic solvents. The molecular weight of the terpolymers is preferably adjusted by the propene, which also acts as a molecular weight regulator. However, other molecular weight regulators such as hydrocarbons, aldehydes, ketones can also be used. Monomer mixtures containing 30 to 60% by weight of ethylene, 20 to 50% by weight of propene and 15 to 35% by weight of vinyl acetate are used for the polymerization.
Die nach dem erfindungsgemäßen Verfahren hergestellten Mineralöle und Mineralöldestillate zur Verbesserung ihrer Fließfähigkeit zugesetzten Polymermischungen enthalten Ethylen-Vinylacetat-Copolymerisat und Ethylen-Propen-Vinylacetat-Terpolymerisat in einem Gewichtsverhältnis von 0,5 zu 1 bis 20 zu 1. Bevorzugt werden Mischungen, die Copolymerisat und Terpolymerisat im Gewichtsverhältnis von 2 zu 1 bis 10 zu 1 enthalten. Es empfiehlt sich, in der Polymerenmischung Copolymerisate und Terpolymerisate zu verwenden, deren Vinylacetatgehalt (in Gew.%) annähernd gleich ist und insbesondere nicht mehr als 3 Gew.% absolut voneinander abweicht. Auch die Viskosität der in der Mischung enthaltenen Polymeren soll möglichst gleich sein, die Abweichungen sollen insbesondere nicht größer als 200 mPa.s, gemessen bei 140°C, betragen.The mineral oils and mineral oil distillates produced by the process according to the invention to improve their flowability are added to polymer mixtures which contain ethylene-vinyl acetate copolymer and ethylene-propene-vinyl acetate terpolymer in a weight ratio of 0.5 to 1 to 20 to 1. Mixtures containing the copolymer and Contain terpolymer in a weight ratio of 2 to 1 to 10 to 1. It is advisable to use copolymers and terpolymers in the polymer mixture whose vinyl acetate content (in% by weight) is approximately the same and in particular does not deviate from one another by more than 3% by weight. The viscosity of the polymers contained in the mixture should also be as equal as possible, and the deviations should in particular not be greater than 200 mPa.s, measured at 140 ° C.
Im allgemeinen setzt man die Mischungen der Polymeren den Mineralölen bzw. den Mineralölfraktionen in Form von 40 bis 60 Gew.%igen Lösungen in einem aliphatischen oder aromatischen Kohlenwasserstoff oder in einem Kohlenwasserstoffgemisch zu. Besonders geeignet ist z.B. Kerosin. Die Polymerisatmenge, bezogen auf Mineralöl bzw. Mineralölfraktion, soll 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.% betragen. Die Polymergemische können allein oder auch zusammen mit anderen Additiven verwendet werden, beispielsweise mit anderen Stockpunkterniedrigern oder Entwachsungshilfsmitteln, Korrosionsinhibitoren, Antioxidantien oder Schlamminhibitoren.In general, the mixtures of the polymers are added to the mineral oils or the mineral oil fractions in the form of 40 to 60% by weight solutions in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture. For example, Kerosene. The amount of polymer, based on mineral oil or mineral oil fraction, should be 0.001 to 2, preferably 0.005 to 0.5,% by weight. The polymer mixtures can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, corrosion inhibitors, antioxidants or sludge inhibitors.
Das erfindungsgemäße Verfahren wird durch die nachfolgenden Beispiele näher erläutert.The process according to the invention is explained in more detail by the following examples.
Die Beispiele A - F betreffen die Herstellung der Ethylen-Propen-Vinylacetat-Terpolymerisate, die Beispiele G - I die Herstellung der Ethylen-Vinylacetat-Copolymerisate.Examples AF relate to the preparation of the ethylene-propene-vinyl acetate terpolymers, examples G-I relate to the production of the ethylene-vinyl acetate copolymers.
In den Beispielen 1 - 6 ist die Wirksamkeit der Terpolymerisate, in den Beispielen 7 - 9 die Wirksamkeit der Copolymeri- 3ate als Fließverbesserer zusammengestellt.In Examples 1-6, the effectiveness of the terpolymers in Examples 7-9, the effectiveness of the copolymerization 3 ate collected as flow improvers.
Die Beispiele 10 - 18 beschreiben das Fließverhalten von Mitteldestillaten nach Zusatz von Copolymerisat-Terpolymerisat-Mischungen entsprechend dem erfindungsgemäßen Verfahren.Examples 10-18 describe the flow behavior of middle distillates after the addition of copolymer-terpolymer mixtures according to the inventive method.
Ethylen, Propen und Vinylacetat werden kontinuierlich in einem Autoklaven polymerisiert. Das Monomerengemisch wird beim Reaktionsdruck in den Autoklaven eingespeist, nachdem die für die Aufrechterhaltung der Polymerisation erforderliche Menge Peroxid als Lösung in einer Benzinfraktion zugesetzt worden ist. Die Verweilzeit beträgt etwa 80 sec.Ethylene, propene and vinyl acetate are continuously polymerized in an autoclave. The monomer mixture is fed into the autoclave at the reaction pressure after the for the maintenance of the polymerization required amount of peroxide has been added as a solution in a gasoline fraction. The dwell time is about 80 seconds.
Die jeweiligen Polymerisationsbedingungen und die für die erhaltenen Polymere charakteristischen Eigenschaftswerte sind in Tabelle 1 zusammengestellt.The respective polymerization conditions and the property values characteristic of the polymers obtained are summarized in Table 1.
Der Vinylacetatgehalt in den Polymeren wird nach der Pyrolysemethode bestimmt. Hierzu werden 200 mg des Polymeren mit 300 mg reinem Polyethylen in einem Pyrolysekolben 5 Minuten auf 450°C erhitzt und die Spaltgase in einem 250 ml-Rundkolben aufgefangen. Die gebildete Essigsäure wird mit einer NaJ/KJ03-Lösung umgesetzt und mit Na2S203-Lösung das freiwerdende Jod titriert.The vinyl acetate content in the polymers is determined using the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask at 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The acetic acid formed is reacted with a NaJ / KJ0 3 solution and the released iodine is titrated with Na 2 S 2 0 3 solution.
Die Bestimmung des Verzweigungsgrades der Polymeren erfolgt durch H-NMR-Spektroskopie. Unter Verzweigungsgrad versteht man die Anzahl CH3-Gruppen je 100 CH2-Gruppen mit Ausnahme der CH3-Gruppen, die aus dem Acetatrest stammen.
Die Polymerisation des aus Ethylen und Vinylacetat bestehenden Monomerengemisches erfolgt in einem Rohrreaktor bei 150 MPa Druck in Abwesenheit wesentlicher Mengen eines Lösungsmittels. Als Initiatoren finden organische Peroxide Anwendung.The monomer mixture consisting of ethylene and vinyl acetate is polymerized in a tubular reactor at 150 MPa pressure in the absence of substantial amounts of a solvent. Organic peroxides are used as initiators.
Die jeweiligen Polymerisationsbedingungen und für die erhaltenen Polymere charakteristischen Eigenschaftswerte sind in Tabelle 2 zusammengestellt.The respective polymerization conditions and property values characteristic of the polymers obtained are summarized in Table 2.
Die Bestimmung des Vinylacetatgehaltes und des Verzweigungsgrades erfolgt nach den für die Ethylen-Propen-Vinylacetat-Terpolymerisaten angegebenen Verfahren.
In den folgenden Beispielen 1 - 18 wird die Wirksamkeit von Ethylen-Propen-Vinylacetat-Terpolymerisaten, Ethylen-Vinylacetat-Copolymerisaten und Gemischen aus Copolymerisat und Terpolymerisat als Fließverbesserer an Hand des "Kalt-Filter-Verstopfungspunkt-Test" (CFPP-Test) beschrieben. Die Durchführung des Tests erfolgt nach DIN 51428, sie ist auch in J. of the Inst. of Petr., Bd. 52, Juni 1966, S. 173 bis 185 publiziert.In the following Examples 1-18, the effectiveness of ethylene-propene-vinyl acetate terpolymers, ethylene-vinyl acetate copolymers and mixtures of copolymer and terpolymer as a flow improver is described using the "cold filter clogging point test" (CFPP test) . The test is carried out in accordance with DIN 51428, and is also published in J. of the Inst. Of Petr., Vol. 52, June 1966, pp. 173 to 185.
Zur Prüfung werden drei Mitteldestillate Ml, M2 und M3 eingesetzt, die durch die in Tabelle 3 zusammengestellten Eigenschaftswerte gekennzeichnet sind.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3501384 | 1985-01-17 | ||
DE19853501384 DE3501384A1 (en) | 1985-01-17 | 1985-01-17 | METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0190553A1 true EP0190553A1 (en) | 1986-08-13 |
EP0190553B1 EP0190553B1 (en) | 1988-05-18 |
Family
ID=6260051
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86100143A Expired EP0190553B1 (en) | 1985-01-17 | 1986-01-08 | Process to improve the viscosity of mineral oils and of the distillates of mineral oils |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0190553B1 (en) |
DE (2) | DE3501384A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0251002A1 (en) * | 1986-06-26 | 1988-01-07 | Hoechst Aktiengesellschaft | Process to improve the flowability of mineral oils and mineral oil distillates |
EP0254284A1 (en) * | 1986-07-25 | 1988-01-27 | Hoechst Aktiengesellschaft | Process to improve the flowability of mineral oils and mineral oil distillates |
WO1994000515A1 (en) * | 1992-06-30 | 1994-01-06 | Exxon Chemical Patents Inc. | Oil additives and compositions |
WO2006106300A1 (en) * | 2005-04-04 | 2006-10-12 | Proflux Systems Llp | Wax-containing materials |
EP1881053A2 (en) * | 2006-07-18 | 2008-01-23 | Clariant International Ltd. | Additives for improving the cold properties of fuel oils |
EP1881055A2 (en) * | 2006-07-18 | 2008-01-23 | Clariant International Ltd. | Additives to improve the cold properties of fuel oils |
US8961622B2 (en) | 2006-07-18 | 2015-02-24 | Clariant Finance (Bvi) Limited | Additives for improving the cold properties of fuel oils |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19821736A1 (en) * | 1998-05-14 | 1999-11-18 | Wacker Chemie Gmbh | Process for the production of vinyl ester-ethylene copolymers with reduced surface tack |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1914756A1 (en) | 1968-04-01 | 1969-11-06 | Exxon Research Engineering Co | Process for the production of copolymers and their use in distillation units |
US3961916A (en) * | 1972-02-08 | 1976-06-08 | Exxon Research And Engineering Company | Middle distillate compositions with improved filterability and process therefor |
EP0003489A1 (en) * | 1977-12-20 | 1979-08-22 | Imperial Chemical Industries Plc | Crude oil having improved cold flow properties |
US4178951A (en) * | 1978-10-10 | 1979-12-18 | Texaco Inc. | Low pour point crude oil compositions |
US4354011A (en) * | 1978-10-02 | 1982-10-12 | Exxon Research & Engineering Co. | Copolymers of ethylene and ethylenically unsaturated monomers, process for their preparation and distillate oil containing said copolymers |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3661541A (en) * | 1969-04-22 | 1972-05-09 | Exxon Research Engineering Co | Fuel oil compositions containing a mixture of polymers to improve the pour point and flow properties |
DD161128A1 (en) * | 1980-03-03 | 1985-02-20 | Leuna Werke Veb | METHOD FOR PRODUCING A FLOW IMPROVER |
JPH0710900B2 (en) * | 1982-06-18 | 1995-02-08 | エクソン リサーチ アンド エンヂニアリング コムパニー | Fluidity improver for middle distillate fuel oil |
-
1985
- 1985-01-17 DE DE19853501384 patent/DE3501384A1/en not_active Withdrawn
-
1986
- 1986-01-08 EP EP86100143A patent/EP0190553B1/en not_active Expired
- 1986-01-08 DE DE8686100143T patent/DE3660207D1/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1914756A1 (en) | 1968-04-01 | 1969-11-06 | Exxon Research Engineering Co | Process for the production of copolymers and their use in distillation units |
US3961916A (en) * | 1972-02-08 | 1976-06-08 | Exxon Research And Engineering Company | Middle distillate compositions with improved filterability and process therefor |
EP0003489A1 (en) * | 1977-12-20 | 1979-08-22 | Imperial Chemical Industries Plc | Crude oil having improved cold flow properties |
US4354011A (en) * | 1978-10-02 | 1982-10-12 | Exxon Research & Engineering Co. | Copolymers of ethylene and ethylenically unsaturated monomers, process for their preparation and distillate oil containing said copolymers |
US4178951A (en) * | 1978-10-10 | 1979-12-18 | Texaco Inc. | Low pour point crude oil compositions |
Non-Patent Citations (1)
Title |
---|
J. OF THE INST. OF PETR., June 1966 (1966-06-01), pages 173 - 185 |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0251002A1 (en) * | 1986-06-26 | 1988-01-07 | Hoechst Aktiengesellschaft | Process to improve the flowability of mineral oils and mineral oil distillates |
EP0254284A1 (en) * | 1986-07-25 | 1988-01-27 | Hoechst Aktiengesellschaft | Process to improve the flowability of mineral oils and mineral oil distillates |
WO1994000515A1 (en) * | 1992-06-30 | 1994-01-06 | Exxon Chemical Patents Inc. | Oil additives and compositions |
EA016299B1 (en) * | 2005-04-04 | 2012-04-30 | Ойлфлоу Солюшнз Холдингз Лимитед | Method of treating wax-containing materials |
WO2006106300A1 (en) * | 2005-04-04 | 2006-10-12 | Proflux Systems Llp | Wax-containing materials |
GB2439036A (en) * | 2005-04-04 | 2007-12-12 | Proflux Systems Llp | Wax-containing materials |
US8357745B2 (en) | 2005-04-04 | 2013-01-22 | Oilflow Solutions Holdings Limited | Wax-containing materials |
EP1881055A2 (en) * | 2006-07-18 | 2008-01-23 | Clariant International Ltd. | Additives to improve the cold properties of fuel oils |
EP1881053A3 (en) * | 2006-07-18 | 2011-02-02 | Clariant Finance (BVI) Limited | Additives for improving the cold properties of fuel oils |
EP1881055A3 (en) * | 2006-07-18 | 2011-02-02 | Clariant Finance (BVI) Limited | Additives to improve the cold properties of fuel oils |
DE102006033150B4 (en) * | 2006-07-18 | 2008-10-16 | Clariant International Limited | Additives for improving the cold properties of fuel oils |
EP1881053A2 (en) * | 2006-07-18 | 2008-01-23 | Clariant International Ltd. | Additives for improving the cold properties of fuel oils |
US8961622B2 (en) | 2006-07-18 | 2015-02-24 | Clariant Finance (Bvi) Limited | Additives for improving the cold properties of fuel oils |
US8968428B2 (en) | 2006-07-18 | 2015-03-03 | Clariant Produkte (Deutschland) Gmbh | Additives for improving the cold properties of fuel oils |
US8979951B2 (en) | 2006-07-18 | 2015-03-17 | Clariant Finance (Bvi) Limited | Additives for improving the cold properties of fuel oils |
Also Published As
Publication number | Publication date |
---|---|
DE3660207D1 (en) | 1988-06-23 |
DE3501384A1 (en) | 1986-07-17 |
EP0190553B1 (en) | 1988-05-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0493769B1 (en) | Terpolymers of ethylene, their preparation and their use as additives for mineral oil distillates | |
EP0807642B1 (en) | Ethylene terpolymers, their preparation and their use as additives for mineral oil distillates | |
EP0463518B1 (en) | Terpolymers of ethylene, their preparation and their use for mineral oil distillates | |
EP0203554B1 (en) | Use of ethylene terpolymers as additives for mineral distillates oils and mineral oil | |
EP0922716B1 (en) | Process for the manufacture of terpolymers of ethylene and their use as additives to mineral oil and mineral oil distillates | |
EP0254284B1 (en) | Process to improve the flowability of mineral oils and mineral oil distillates | |
DE19757830C2 (en) | Fuel oils with improved lubrication | |
DE3640613A1 (en) | METHOD FOR THE PRODUCTION OF ETHYLENE MIXED POLYMERISATES AND THE USE THEREOF AS AN ADDITION TO MINERAL OIL AND MINERAL OIL FRACTIONS | |
DE19620119C1 (en) | Terpolymers of ethylene, their production and their use as additives for mineral oil distillates | |
EP0184083B1 (en) | Terpolymers of ethylene, process for their manufacture and their use | |
DE3320720A1 (en) | COPOLYMERS WITH NITROGEN FUNCTIONS, THE IN PARTICULAR. ARE USEABLE AS ADDITIVES TO LOWER THE TURBET POINT OF MEDIUM DISTILLATES OF HYDROCARBONS, AND COMPOSITIONS OF HYDROCARBON MEDIUM DISTILLATES THAT CONTAIN THESE COPOLYMERS | |
DE1147799B (en) | Petroleum distillate propellant or fuel | |
EP0258572B1 (en) | Process to improve the flowability of mineral oils and mineral oil distillates | |
EP1433836A1 (en) | Fuel oils with improved cold properties. | |
EP0405270B1 (en) | Process to improve mineral oil and mineral oil distillate flowability | |
EP0890589B1 (en) | Solutions or dispersions based on copolymers of olefins and unsaturated carboxylic esters and their use as additives for mineral oils | |
EP0190553B1 (en) | Process to improve the viscosity of mineral oils and of the distillates of mineral oils | |
EP0603573A2 (en) | Graft copolymer, the preparation thereof and its use as pour point depressant and flow improver in crude oils, residual oils and middle distillates | |
EP0061696A2 (en) | Process for improving the flow of mineral oils | |
EP0937108B1 (en) | Co- and terpolymers based on alpha,beta-unsaturated compounds and alpha,beta-unsaturated dicarboxylic acid anhydrides | |
EP0890633A1 (en) | Middle distillates and ethylene and unsaturated carboxylic esters copolymers containing fuel oils | |
EP0251002B1 (en) | Process to improve the flowability of mineral oils and mineral oil distillates | |
DE3247753A1 (en) | USE OF ETHYLENE COPOLYMERISATES AS A MINERAL OIL ADDITIVE | |
DE1770011C3 (en) | ||
DE3732721A1 (en) | COPOLYMERISATES FROM ETHYLENE AND METHOXY ACETIC ACID VINYL ESTER AND THEIR USE AS ADDITIVES FOR MINERAL OIL DISTILLATES |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE FR GB IT LU NL SE |
|
17P | Request for examination filed |
Effective date: 19860830 |
|
17Q | First examination report despatched |
Effective date: 19870811 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO MASSARI S.R.L. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT LU NL SE |
|
REF | Corresponds to: |
Ref document number: 3660207 Country of ref document: DE Date of ref document: 19880623 |
|
ET | Fr: translation filed | ||
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
BECA | Be: change of holder's address |
Free format text: 880518 *HOECHST A.G.:POSTFACH 80 03 20, 6230 FRANKFURT |
|
BECH | Be: change of holder |
Free format text: 880518 *HOECHST A.G. |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19890131 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19890131 Year of fee payment: 5 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: EXXON CHEMICAL PATENTS INC. Effective date: 19890220 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: EXXON CHEMICAL PATENTS INC. |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: EXXON CHEMICAL PATENTS INC. Effective date: 19890220 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19891219 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 19891220 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19891222 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19900112 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19900131 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19900224 Year of fee payment: 5 |
|
RDAG | Patent revoked |
Free format text: ORIGINAL CODE: 0009271 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT REVOKED |
|
27W | Patent revoked |
Effective date: 19900122 |
|
GBPR | Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state | ||
NLR2 | Nl: decision of opposition | ||
EUG | Se: european patent has lapsed |
Ref document number: 86100143.6 Effective date: 19900606 |