JP2009532543A - Automotive fuel composition containing renewable raw materials - Google Patents

Abstract

  The present invention relates to an automotive fuel composition comprising at least one mineral-derived diesel fuel and at least one biodiesel fuel, comprising at least 20% by weight of the mineral-derived diesel fuel and at least one polymer comprising ester groups. 0.05% by mass to 5% by mass of a repeating unit derived from an ester monomer having 16 to 40 carbon atoms in the alcohol group and a repeating unit derived from an ester monomer having 7 to 15 carbon atoms in the alcohol group The present invention relates to an automobile fuel composition characterized by containing a fuel composition. The invention further relates to the use of polymers containing ester groups as flow improvers and also to a method for driving a diesel engine.

Description

  The present invention relates to a fuel composition comprising renewable raw materials, the use of an ester-containing polymer in the fuel composition, and a method of driving a diesel engine with the fuel composition of the present invention.

  Currently, fuel is generally obtained from fossil sources. However, these resources are limited, so alternatives are sought. Therefore, there is a growing interest in renewable raw materials that can be used to produce fuel. A very interesting alternative is in particular biodiesel fuel.

  In many cases, the term biodiesel refers to a mixture of fatty acid esters, usually fatty acid methyl esters (FAME), having a chain length of 14 to 24 carbon atoms with 0 to 3 double bonds. Understand what it means. The more carbon atoms and the fewer double bonds, the higher the melting point of FAME. Typical raw materials are vegetable oils (ie glycerides) such as rapeseed oil, sunflower oil, soybean oil, coconut oil, coconut oil and, if isolated, waste vegetable oil. These are usually converted to the FAME by transesterification using methanol under a basic catalyst.

  In contrast to rapeseed oil methyl ester (RME), which is often used in Europe and typically contains approximately 5% C16: 0 + C18: 0-FAME, coconut oil methyl ester (PME) is approximately 50% C16 : 0 + C18.0-FAME. Similarly high amounts of 16: 0 + C18: 0-FAME are also present in similar derivatives of tallow, such as beef tallow. Such high wax content is almost unaffected by the polymer flow improver and is typically added in an additive amount of 2% or less. Compared to rapeseed oil, coconut oil can yield more than three times the yield per hectare. This produces enormous economic benefits. However, as a disadvantage, the PME pour point is high, about + 12 ° C.

  The use of pure biodiesel is important from an environmental point of view. However, these fuel oils differ from conventional diesel fuels in important characteristics. For example, biodiesel has been found to destroy many sealing materials. Failure of the sealing material inevitably leads to engine damage. Furthermore, in the case of direct injection diesel engines, fuel can be put into the lubricating oil, which can be deposited in the engine due to the low chemical stability of the vegetable oil esters. In addition, biodiesel fuel exhibits different combustion due to differences in viscosity compared to mineral diesel fuel, which leads to different spray behavior. In the case of modern diesel engines, the engine electronics are specifically adapted for fossil diesel fuel, and therefore problems can arise as a result of changes in combustion characteristics. In particular, the development of economical and high performance diesel engines that are optimal for the use of fossil combustion has thus hindered the use of pure biodiesel fuel.

  In addition to the use of 100% biodiesel (usually RME) in Europe, fossil diesel mixtures, ie, crude oil distillation middle distillates and biodiesel, are therefore also noted with improved low temperature properties and improved combustion properties Has been. Even as an admixture, consumers can gain tax gains on renewable raw materials. In addition to these economic benefits, an ecological equilibrium in favor of renewable raw material biodiesel shall of course also be mentioned. For example, in Europe, a 5% blend of fossil diesel and biodiesel (usually RME) and over 20% blend (usually PME) in Asia (Korea, India, Indonesia, Malaysia, Thailand, Philippines) and Australia. ) Is being considered. Furthermore, in the case of a 20% PME blend, very many waxy chains are present in the fuel mixture with approximately 10% C16: 0 + C18: 0-FAME compared to RME (approximately 5%). In addition, H.C. Vogel, A.M. Bertola: Palmelmethylester-eine new vaultilhafte Biokoponente fuer Dieselkraftstoffe

  PA (M) A, a polyalkyl (meth) acrylate, without M (M) A (eg, US Pat. No. 3,869,396, Shell Oil Company), and M (M) A (eg, US Pat. No. 5312884, Rohm & Haas Company), established as a pour point improver for mineral oils or as a pour point improver for vegetable oils (US Pat. No. 5,696,066, Rohm & Haas Company), and has been reported several times Yes. However, the use of these polymers in fuel compositions comprising at least one mineral-derived diesel fuel and at least one biodiesel has not been reported.

  Furthermore, the publication International Application No. 01/40334 (RohMax Additives GmbH) describes polyalkyl (meth) acrylates that can be used for biodiesel fuel. This publication relates to specific preparations that give these polymers exceptional properties. However, there is no example here regarding biodiesel fuel. Furthermore, the advantages of polymers having a high content of specific ester-containing repeat units are not detailed. Furthermore, the low temperature properties obtained in lubricating oils by adding additives may not necessarily apply to mineral diesel fuels because their boiling behavior, viscosity and here the composition of hydrocarbons are different. Mixtures comprising mineral diesel fuel and biodiesel are not described in International Application No. 01/40334. Furthermore, in the reference, hydroxy-functional PAMA is known as a flow improver for biodiesel (European Patent No. 1032620, RohMax Additives GmbH). In the summary part of the publication EP 1032620 a mixture of biodiesel and fossil fuels is described, but no examples using such a mixture are cited. In this regard, it can be deduced from this specification that an RME-based biodiesel fuel with particularly good low-temperature properties should be provided. It can be seen that the effect of the polymers detailed in general terms in EP 1032620 can be improved when using a mixture of high content mineral-derived diesel fuel.

Oil-soluble polymer flow improvers of fossil diesel and biodiesel mixtures are also known (International Application No. 94/10267, Exxon Chemical Patents Inc.). However, in the examples, only ethylene vinyl acetate copolymer (EVA) and copolymers containing C ₁₂ / C ₁₄ -alkyl fumarate and vinyl acetate units are described. There is no comprehensive and explicit description of specific ester-containing polymers in International Application No. 94/10267.

  In addition, EVA copolymers that are optimal for a series of diesel-biodiesel mixtures are also becoming known (European Patent No. 1541662-664). For example, EP 1541663 details a mixture comprising 75% by volume of mineral-derived diesel fuel and 25% by volume of biodiesel, which includes 150 ppm poly (dodecyl methacrylate) and 100-200 ppm ethylene vinyl acetate copolymer (EVA). including. Here, however, the use of EVA is formally described. However, EVA is a fairly expensive additive. Thereby, as an alternative, it is desirable to be able to omit the use of EVA. In EP 1541663 there is no mention of the advantages of certain ester-containing polymers.

  Accordingly, in view of the prior art, an object of the present invention is to provide a fuel composition that has a characteristic profile that naturally corresponds to that of mineral diesel fuel and contains the maximum amount of renewable raw materials. At the same time, the fuel in particular has very good low temperature properties. Furthermore, the combustion behavior, in particular the behavior of the fuel with respect to engine control characteristics, should correspond as much as possible to the behavior of mineral diesel fuel. Furthermore, the object of the present invention was to provide a fuel with high stability to oxidation. Furthermore, this fuel shall have the maximum cetane number. At the same time, a new fuel is to be generated easily and inexpensively. Furthermore, the object of the present invention was to provide a method for driving a diesel engine with high environmental adaptability.

  From the connections described herein as a prelude, this object and additional objects not expressly shown but inferred or considered are realized by a combustion composition having all the features of claim 1. In the sub-claims, appropriate modifications of the fuel composition of the present invention are protected. Regarding the method of driving diesel engines and the use of ester-containing polymers as flow improvers, claims 24 and 25 constitute a solution to the problem.

  20% by mass of mineral-derived diesel fuel and at least one type of repeating unit derived from an ester monomer having 16 to 40 carbon atoms in an alcohol group and a repeating unit derived from an ester monomer having 7 to 15 carbon atoms in an alcohol group Surprisingly, a fuel composition comprising 0.05 to 5% by weight of an ester-containing polymer can provide a fuel composition comprising at least one mineral-derived diesel fuel and at least one biodiesel fuel. This fuel composition has a characteristic profile very similar to that of mineral diesel fuel and contains a very high proportion of renewable raw materials.

At the same time, the fuel composition of the present invention can realize a series of additional advantages. These include the following:
The fuel composition of the present invention can be used in conventional diesel engines without conventionally destroying the sealing material used.

  Furthermore, modern diesel engines can be driven with the fuel of the present invention without altering engine control.

  Preferred fuel compositions of the present invention have a particularly high cetane number that can be improved by using a biodiesel fuel, particularly with a high proportion of long chain saturated fatty acids.

  Furthermore, the present invention is directed to the use of biodiesel fuel that is very oxidatively stable. This makes it possible to reduce engine deposit formation, which can lead to a decrease in overall engine performance.

  Furthermore, a very high proportion of coconut oil alkyl ester can be used for the fuel. For environmental and economic reasons, coconut oil is preferred over commonly used rapeseed oil. For example, the production yield of palm oil is significantly higher than that of rapeseed oil. Furthermore, very large amounts of environmentally problematic chemicals, in particular fertilizers and crop protection compositions, are used to obtain rapeseed. At the same time, rapeseed is not self-compatible in production, but must be cultivated in a rotation system, in which case rapeseed can be cultivated on the same arable land only every 3-5 years. For this reason, it is difficult to further increase rape production.

  However, coconut oil alkyl esters have significantly higher cloud points (approximately + 13 ° C. for methyl esters) compared to rapeseed oil alkyl esters, and rapeseed oil alkyl esters have significantly lower cloud points (methyl). In the case of esters, approximately -7 ° C). Thus, in certain embodiments, the present invention allows the use of a particularly high proportion of coconut oil alkyl esters in the production of fuel compositions without low temperature properties taking unacceptable values.

  The fuel composition of the present invention comprises a mineral derived diesel fuel, i.e. diesel, light oil or diesel oil. Mineral diesel fuels are widely known per se and are commercially available. This is understood to mean a mixture of various hydrocarbons that are suitable as fuel for diesel engines. Diesel can be obtained as a middle distillate, in particular by distillation of crude oil. The main constituents of diesel fuel preferably include alkanes, cycloalkanes, and aromatic hydrocarbons having about 10 to 22 carbon atoms per molecule.

  The boiling point of the mineral-derived diesel fuel is preferably 120 to 450 ° C, more preferably 170 and 390 ° C. It is preferred to use these middle distillates containing 0.05% by weight or less of sulfur, more preferably 350 ppm or less of sulfur, in particular 200 ppm or less of sulfur and, in the specific case, 50 ppm or less of sulfur, for example 10 ppm or less of sulfur. These are purified under hydrogenation conditions, and therefore these middle distillates containing only small amounts of polycyclic aromatic and polar compounds are preferred. These are preferably those intermediate distillates having a 95% distillation point of 370 ° C. or less, in particular 350 ° C. or less and in specific cases 330 ° C. or less. For example, synthetic fuels obtainable by the Fischer-Tropsch process are also suitable as mineral-derived diesel fuels.

The kinematic viscosity of the mineral derived diesel fuel used is by ASTM D445, measured at 40 ° C., preferably 0.5 to 8 mm ² / s, more preferably 1 to 5 mm ² / s, especially preferably 1. 5 to ³ mm ² / s.

  The fuel composition according to the invention comprises at least 20% by weight of mineral-derived diesel fuel, in particular at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight and most preferably at least 80% by weight.

  Furthermore, the fuel composition of the present invention comprises at least one biodiesel fuel component. Biodiesel fuels are substances, especially oils, which are derived from plant or animal material or both or derivatives thereof, which can be used primarily as a replacement for mineral diesel fuel.

  In preferred embodiments, the biodiesel fuel, often referred to as “biodiesel” or “biofuel”, is preferably a fatty acid having 6 to 30 carbon atoms, more preferably 12 to 24 carbon atoms and 1 to 4 carbon atoms. Fatty acid alkyl esters formed from monohydric alcohols having a number. Often, some of the fatty acids can contain 1, 2 or 3 double bonds. Monohydric alcohols include in particular methanol, ethanol, propanol and butanol, with methanol being preferred.

  Examples of oils that are derived from animal or plant material and can be used in the present invention include coconut oil, rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond There are oils, palm kernel oil, coconut oil, mustard oil, tallow, especially beef tallow oil, bone oil, fish oil and waste edible oil. Further examples include cereals, wheat, jute, sesame, rice husk, oil from jatropha, peanut oil and linseed oil. The fatty acid alkyl esters preferably used can be obtained from these oils by methods known in the prior art.

  In the present invention, high C16: 0 / C18: 0-glyceride-containing oils such as oils derived from coconut oil and tallow and further derivatives thereof, particularly coconut oil alkyl esters derived from monohydric alcohols are preferred. Palm oil (and also palm fat) is obtained from fresh fruit of the palm fruit. Sterilize and compress the fruit. Due to the high carotene content, the fruits and oils have an orange-red color that is removed during purification. The oil can contain up to 80% C18: 0-glycerides.

  Particularly suitable biodiesel fuels are lower alkyl esters of fatty acids. Useful examples herein are ethyl, propyl, butyl and especially fatty acids having 6-30, preferably 12-24, more preferably 14-22 carbon atoms, such as caprylic acid, capric acid, Lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petrothelic acid, ricinoleic acid, elaeostearic acid, Commercial mixture of methyl esters of linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid.

  In a particular embodiment of the invention, the biodiesel fuel used is preferably at least 30% by weight, more preferably at least 35% by weight and most preferably at least 40% saturated fatty acid esters having at least 16 carbon atoms of fatty acid groups. Including mass%. These include in particular esters of palmitic acid and stearic acid.

  In view of cost, these fatty acid esters are generally used as a mixture. The biodiesel fuel that can be used in the present invention preferably has an iodine number of at most 150, in particular at most 125, more preferably at most 70 and most preferably at most 60. In the content of unsaturated compounds fat or oil, the iodine value is a known measurement per se and can be determined according to DIN 53241-1. As a result of this, the fuel composition of the present invention forms a small amount of deposits, especially in diesel engines. Furthermore, these fuel compositions have a particularly high cetane number.

  In general, the fuel composition according to the invention may comprise at least 0.5% by weight of biodiesel fuel, in particular at least 3% by weight, preferably at least 5% by weight and more preferably at least 15% by weight.

  Furthermore, the fuel composition of the present invention contains 0.05 to 5% by mass, preferably 0.08 to 3% by mass and more preferably 0.1 to 1.0% by mass of at least one ester-containing polymer.

  In the context of the present invention, an ester-containing polymer is understood to mean a polymer obtainable by polymerizing a monomer composition comprising an ethylenically unsaturated compound having at least one ester group, which is referred to below as ester Called monomer. Thereby, these polymers contain ester groups as side chain moieties. These polymers include in particular polyalkyl (meth) acrylates (PAMA), polyalkyl fumarate and / or polyalkyl maleate.

  Ester monomers are known per se. These include in particular (meth) acrylates, maleic acid and fumaric acid, which can have various alcohol groups. The term (meth) acrylate encompasses methacrylate and acrylate and also a mixture of the two. These monomers are widely known. In this regard, the alkyl group may be linear, cyclic or branched. Furthermore, the alkyl group can have a known substituent.

  The ester-containing polymer contains a repeating unit derived from an ester monomer having 16 to 40 carbon atoms in the alcohol group and a repeating unit derived from an ester monomer having 7 to 15 carbon atoms in the alcohol group.

  The phrase “repeat unit” is widely known in the technical field. The ester-containing polymers of the present invention are preferably obtained via free radical polymerization of monomers, ATRP, RAFT and NMP methods, which are described in detail below in the context of the present invention. , No restrictions shall be imposed. In polymerization, double bonds are opened to form covalent bonds. Thereby, repeating units are formed from the monomers used. The ester-containing polymer is 5 to 99.9% by weight, particularly 20 to 98% by weight, preferably 30 to 95% by weight and most preferably 70 to 50% by weight of repeating units derived from ester monomers having 7 to 15 carbon atoms in the alcohol group. -92 mass% can be contained.

  In a particular embodiment, the ester-containing polymer is 0.1 to 80%, preferably 0.5 to 60%, more preferably 2 repeating units derived from an ester monomer having 16 to 40 carbon atoms in the alcohol group. It can contain -50% by weight and most preferably 5-20% by weight.

  Further, the ester-containing polymer can contain 0.1 to 30% by mass, preferably 0.5 to 20% by mass, of a repeating unit derived from an ester monomer having 1 to 6 carbon atoms in the alcohol group.

  The ester-containing polymer preferably comprises at least 40%, more preferably at least 60%, particularly preferably at least 80% and most preferably at least 95% by weight of repeating units derived from ester monomers.

［式中、Ｒは、水素またはメチルであり、Ｒ¹は、炭素原子１〜６個を有する直鎖または分岐鎖アルキル基であり、Ｒ²およびＲ³は、それぞれ独立して、水素または式−ＣＯＯＲ’（式中、Ｒ’は水素または炭素原子１〜６個を有するアルキル基である）の基である］
の１種または複数種のエチレン性不飽和エステル化合物０〜４０質量％、好ましくは０．１〜３０質量％、特に０．５〜２０質量％を含有することができる。 The mixture from which the ester-containing polymer of the present invention can be obtained has the formula (I)

Wherein R is hydrogen or methyl, R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are each independently hydrogen or formula —COOR ′ (wherein R ′ is hydrogen or an alkyl group having 1 to 6 carbon atoms)]
One or a plurality of ethylenically unsaturated ester compounds may be contained in an amount of 0 to 40% by mass, preferably 0.1 to 30% by mass, particularly 0.5 to 20% by mass.

As an example of constituent substance (I),
(Meth) acrylate, fumaric acid and maleic acid derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate,
Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate,
There are (meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.

［式中、Ｒは、水素またはメチルであり、Ｒ⁴は、炭素原子７〜１５個を有する直鎖または分岐鎖アルキル基であり、Ｒ⁵およびＲ⁶は、それぞれ独立して水素または式−ＣＯＯＲ’’（式中、Ｒ’’は、水素または炭素原子７〜１５個を有するアルキル基である）の基である］
の１種または複数種のエチレン性不飽和エステル化合物１０〜９８質量％、特に２０〜９５質量％を含有することが好ましい。 The polymerizing composition has the formula (II)

[Wherein R is hydrogen or methyl, R ⁴ is a linear or branched alkyl group having 7 to 15 carbon atoms, and R ⁵ and R ⁶ are each independently hydrogen or formula − COOR ″ (wherein R ″ is hydrogen or an alkyl group having 7 to 15 carbon atoms)]
It is preferable to contain 10-98 mass%, especially 20-95 mass% of 1 type or multiple types of ethylenically unsaturated ester compounds.

As an example of the constituent (II),
(Meth) acrylates derived from saturated alcohols, fumaric acid and maleic acid, such as 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3- Iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methyl-undecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) Acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate,
(Meth) acrylates derived from unsaturated alcohols, such as oleyl (meth) acrylate,
There are cycloalkyl (meth) acrylates, such as 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, and the fumaric and maleic acids.

［式中、Ｒは、水素またはメチルであり、Ｒ⁷は、炭素原子１６〜４０個、好ましくは１６〜３０個を有する直鎖または分岐鎖アルキル基であり、Ｒ⁸およびＲ⁹は、それぞれ独立して水素または式−ＣＯＯＲ’’’（式中、Ｒ’’’は、水素または炭素原子１６〜４０個、好ましくは１６〜３０個を有するアルキル基である）の基である］
の１種または複数種のエチレン性不飽和エステル化合物０．１〜８０質量％、好ましくは０．５〜６０質量％、より好ましくは２〜５０質量％および最も好ましくは５〜２０質量％を含有する。 Further preferred monomer compositions are those of formula (III)

Wherein R is hydrogen or methyl, R ⁷ is a linear or branched alkyl group having 16 to 40, preferably 16 to 30 carbon atoms, and R ⁸ and R ⁹ are each Independently hydrogen or a group of the formula —COOR ′ ″, where R ′ ″ is hydrogen or an alkyl group having 16 to 40, preferably 16 to 30 carbon atoms.
One or more ethylenically unsaturated ester compounds of 0.1 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight To do.

Examples of the constituent (III) include (meth) acrylates derived from saturated alcohols, such as hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, and 5-isopropylheptadecyl (meth). Acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-isopropyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyl Eicosyl (meth) acrylate, stearyl eicosyl (meth) acrylate, docosyl (meth) acrylate and / or eicosyltetratriacontyl (meth) acrylate,
Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate,
And the fumaric acid and maleic acid.

  Ester compounds having long chain alcohol groups, in particular constituents (II) and (III), can be obtained by reacting, for example, (meth) acrylates, fumaric acid, maleic acid and / or such acids with long chain fatty alcohols. In general, this results in ester mixtures, for example (meth) acrylates with various long chain alcohol groups. These fatty alcohols are Oxo Alcohol (R) 7911 and Oxo Alcohol (R) 7900, Oxo Alcohol (R) 1100; Alfol (R) 610, Alfol (R) 810, Lial (R) 125 And Nafol (R) type (Sasol); Alphal (R) 79 (ICI); Epal (R) 610 and Epal (R) 810 (Afton); Linevol (R) 79, Linevol (R) 911 and Neodol® 25E (Shell AG); Dehydad®, Hydrenol® and Lorol® type (Cognis); Acropol® 35 And Exxal (R) 10 (Exxon Chemicals); Kalcol2465 (Kao Chemicals) is.

  Of the ethylenically unsaturated ester compounds, (meth) acrylates are particularly preferred over maleic acid and fumaric acid, ie, in particularly preferred embodiments, R2, R3, R5 of formulas (I), (II) and (III) , R6, R8 and R9 are each hydrogen.

  The mass ratio of the ester monomer of formula (II) to the ester monomer of formula (III) may be in a wide range. The ratio of the ester compound of formula (II) containing 7 to 15 carbon atoms in the alcohol group to the ester compound of formula (III) containing 16 to 40 carbon atoms in the alcohol group is preferably 50: 1. ˜1: 30, more preferably 10: 1 to 1: 3, particularly preferably 5: 1 to 1: 1.

  The constituent (IV) comprises in particular an ethylenically unsaturated monomer which can be copolymerized with an ethylenically unsaturated ester compound of the formula (I), (II) and / or (III).

［式中、Ｒ¹*およびＲ²*は、それぞれ独立して水素、ハロゲン、ＣＮ、ハロゲン原子１〜（２ｎ＋１）個により置換されることができる炭素原子１〜２０個、好ましくは１〜６個およびより好ましくは１〜４個を有する直鎖または分岐鎖アルキル基からなる群から選択され、この場合、ｎはアルキル基（例えば、ＣＦ₃）の炭素原子数であり、ハロゲン原子、好ましくは塩素１〜（２ｎ−１）個により置換されることができる炭素原子２〜１０個、好ましくは２〜６個およびより好ましくは２〜４個を有するα、β−不飽和直鎖または分岐鎖アルケニルまたはアルキニル基、この場合、ｎはアルキル基の炭素原子数であり、例えば、ＣＨ₂＝ＣＣｌ−、ハロゲン原子、好ましくは塩素１〜（２ｎ−１）個により置換されることができる炭素原子３〜８個を有するシクロアルキル基、この場合、ｎはシクロアルキル基の炭素原子数であり、Ｃ（＝Ｙ*）Ｒ⁵*、Ｃ（＝Ｙ*）ＮＲ⁶*Ｒ⁷*、Ｙ*Ｃ（＝Ｙ*）Ｒ⁵*、ＳＯＲ⁵*、ＳＯ₂Ｒ⁵*、ＯＳＯ₂Ｒ⁵*、ＮＲ⁸*ＳＯ₂Ｒ⁵*、ＰＲ⁵*₂、Ｐ（＝Ｙ*）Ｒ⁵*₂、Ｙ*ＰＲ⁵*₂、Ｙ*Ｐ（＝Ｙ*）Ｒ⁵*₂、ＮＲ⁸*₂、これは、追加のＲ⁸*、アリールまたはヘテロシクリル基で四級化することができ、この場合、Ｙ*は、ＮＲ⁸*、ＳまたはＯ、好ましくはＯであってよく、Ｒ⁵*は、炭素原子１〜２０個を有するアルキル基、炭素原子１〜２０個を有するアルキルチオ、ＯＲ¹⁵（Ｒ¹⁵は、水素またはアルカリ金属である）、炭素原子１〜２０個のアルコキシ、アリールオキシまたはヘテロシクリルオキシであり、Ｒ⁶*およびＲ⁷*は、それぞれ独立して水素または炭素原子１〜２０個を有するアルキル基であり、またはＲ⁶*およびＲ⁷*はともに、炭素原子２〜７個、好ましくは２〜５個を有するアルキレン基を形成することができ、この場合、これらは、３〜８員の、好ましくは３〜６員環を形成し、Ｒ⁸*は、水素、炭素原子１〜２０個を有する直鎖または分岐鎖アルキルまたはアリール基であり、Ｒ³*およびＲ⁴*は、独立して水素、ハロゲン（好ましくはフッ素または塩素）、炭素原子１〜６個を有するアルキル基およびＣＯＯＲ⁹*からなる群から選択され、この場合、Ｒ⁹*は、水素、アルカリ金属または炭素原子１〜４０個を有するアルキル基であり、またはＲ³*およびＲ⁴*はともに、式（ＣＨ₂）nの基を形成することができ、これは、ハロゲン原子またはＣ1−Ｃ4アルキル基１〜２ｎ’個により置換することができ、または式Ｃ（＝Ｏ）−Ｙ*−Ｃ（＝Ｏ）を形成し、式中ｎ’は２〜６、好ましくは３または４であり、Ｙ*は上記に定義される通りであり、Ｒ¹*、Ｒ²*、Ｒ³*およびＲ⁴*基の少なくとも２個は水素またはハロゲンである］
に対応するものである。 However, particularly suitable comonomers for polymerization in the present invention are those of formula (IV):

[Wherein R ¹ * and R ² * are each independently hydrogen, halogen, CN, 1 to 20 carbon atoms which can be substituted by 1 to (2n + 1) halogen atoms, preferably 1 to 6 Selected from the group consisting of linear and branched alkyl groups having 1 and more preferably 1 to 4 wherein n is the number of carbon atoms of the alkyl group (eg CF ₃ ) and preferably a halogen atom, preferably Α, β-unsaturated straight or branched chain having 2 to 10 carbon atoms, preferably 2 to 6 and more preferably 2 to 4 carbon atoms which can be substituted by 1 to (2n-1) chlorine alkenyl or alkynyl group, in this case, n is the number of carbon atoms in the alkyl group, e.g., CH ₂ = CCL, a halogen atom, a carbon source which preferably can be substituted by chlorine 1~ (2n-1) pieces A cycloalkyl group having 3-8, in this case, n is the number of carbon atoms of the cycloalkyl group, C (= Y *) R 5 *, C (= Y *) NR 6 * R 7 *, Y * C (= Y *) R ⁵ *, SOR ⁵ *, SO ₂ R ⁵ *, OSO ₂ R ⁵ *, NR ⁸ * SO ₂ R ⁵ *, PR ⁵ * ₂ , P (= Y *) R ⁵ * ₂ , Y * PR ⁵ * ₂ , Y * P (= Y *) R ⁵ * ₂ , NR ⁸ * ₂ , which can be quaternized with an additional R ⁸ *, aryl or heterocyclyl group, in this case , Y * may be NR ⁸ *, S or O, preferably O, and R ⁵ * is an alkyl group having 1 to 20 carbon atoms, an alkylthio having 1 to 20 carbon atoms, OR ¹⁵ ( R ¹⁵ is hydrogen or an alkali metal), alkoxy having 1 to 20 carbon atoms, aryloxy or heterocyclyloxy, and R ⁶ * and R ⁷ * are each independently Hydrogen or an alkyl group having 1 to 20 carbon atoms, or R ⁶ * and R ⁷ * together can form an alkylene group having 2 to 7, preferably 2 to 5 carbon atoms. In which case they form a 3- to 8-membered, preferably 3- to 6-membered ring, and R ⁸ * is hydrogen, a linear or branched alkyl or aryl group having 1 to 20 carbon atoms , R ³ * and R ⁴ * are independently selected from the group consisting of hydrogen, halogen (preferably fluorine or chlorine), alkyl groups having 1 to 6 carbon atoms and COOR ⁹ *, where R ⁹ * Is hydrogen, an alkali metal or an alkyl group having 1 to 40 carbon atoms, or R ³ * and R ⁴ * together can form a group of formula (CH ₂ ) n, which is Halogen atom or C1-C4 alkyl group 1 Can be substituted by 2n 'or form the formula C (= O) -Y * -C (= O), where n' is 2-6, preferably 3 or 4, and Y * is As defined above, at least two of the R ¹ *, R ² *, R ³ * and R ⁴ * groups are hydrogen or halogen]
It corresponds to.

Preferred constituents (IV) are hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1 , 6-hexanediol (meth) acrylate, 1,10-decanediol (meth) acrylate; aminoalkyl (meth) acrylate such as N- (3-dimethylaminopropyl) methacrylamide, 3-diethylamino-pentyl methacrylate, 3 Dibutylaminohexadecyl (meth) acrylate; nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as N- (methacryloyloxyethyl) diisobutylketimine, N- ( Tacrylyloxyethyl) dihexadecylketimine, methacryloylamide acetonitrile, 2-methacryloyloxyethylmethyl-cyanamide, cyanomethyl methacrylate; aryl (meth) acrylates such as benzyl methacrylate or phenyl methacrylate, where the aryl group is Each may be unsubstituted or quaternary substituted; carbonyl-containing methacrylates such as 2-carboxyethyl methacrylate, carboxymethyl methacrylate, oxazolidinylethyl methacrylate, N- (methacryloyloxy) -formamide, acetonyl methacrylate, N -Methacryl-oil morpholine, N-methacryloyl-2-pyrrolidinone, N- (2-methacryloyloxyethyl) -2- Loridinone, N- (3-methacryl-oiloxypropyl) -2-pyrrolidinone, N- (2-methacryl-oiloxypentadecyl) -2-pyrrolidinone, N- (3-methacryl-oiloxyheptadecyl) -2- Pyrrolidinone; glycol dimethacrylate, such as 1,4-butanediol methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate; methacrylate of ether alcohol, such as tetrahydrofurfuryl methacrylate, vinyloxyethoxy Ethyl methacrylate, methoxyethoxyethyl methacrylate, 1-butoxypropyl methacrylate, 1-methyl- (2-vinyloxy) ethyl methacrylate, cyclohexyloxy Cymethyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl Methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate; methacrylates of halogenated alcohols such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, 2-bromoethyl methacrylate 2-iodoethyl methacrylate, chloromethyl methacrylate; oxiranyl Methacrylate, for example, 2,3-epoxy butyl methacrylate, 3,4-epoxy butyl methacrylate, 10,11-epoxy undecyl methacrylate, 10,11-epoxy hexadecyl methacrylate, 2,3-epoxycyclohexyl methacrylate; glycidyl methacrylate;
Phosphorus, boron and / or silicon-containing methacrylates such as 2- (dimethylphosphato) propyl methacrylate, 2- (ethylenephosphito) propyl methacrylate, dimethylphosphinomethyl methacrylate, dimethylphosphonoethyl methacrylate, diethylmethacrylic acid phosphonate, Dipropyl methacrylic acid phosphate, 2- (dibutylphosphono) -ethyl methacrylate, 2,3-butylene methacryloyl ethyl borate, methyl diethoxy methacryloyl ethoxysilane, diethyl phosphatotoethyl methacrylate;
Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;
Heterocyclic (meth) acrylates, such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloxyethyl) -2-pyrrolidinone;
Vinyl esters such as vinyl acetate;
Styrene, substituted styrenes having an alkyl substituent in the side chain, such as α-methyl-styrene and α-ethylstyrene, substituted styrenes having an alkyl substituent in the ring, such as vinyltoluene and p-methylstyrene, halogenated styrene, For example, monochlorostyrene, dichlorostyrene, tribromostyrene and tetrabromoostyrene;
Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinyl-pyrimidine Vinylpiperidine, 9-vinylcarbazole, 3-vinyl-carbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinyl-pyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazole and hydrogenated vinylthiazole, vinyloxazole and hydrogenated vinyloxazole;
Vinyl and isoprenyl ethers;
Maleic acid and maleic acid derivatives different from those described under (I), (II) and (III), such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide;
Including fumaric acid and fumaric acid derivatives different from those described under (I), (II) and (III).

  The proportion of comonomer (IV) can be varied depending on the method of use and the profile of the polymer. In general, this proportion may be from 0 to 60% by weight, preferably from 0.01 to 20% by weight and more preferably from 0.1 to 10% by weight. Due to combustion characteristics and for environmental reasons, the proportion of monomers containing aromatic, heteroaromatic, nitrogen-containing, phosphorus-containing and sulfur-containing groups should be minimal. The proportion of these monomers can therefore be limited to 1% by weight, in particular 0.5% by weight and preferably 0.01% by weight.

  Comonomers (IV) and ester monomers of the formulas (I), (II) and (III) can be used individually or as a mixture, respectively.

  Surprisingly, ester-containing polymers are more active in mixtures of mineral and biodiesel fuels, and in some cases contain only a small amount of units derived from hydroxyl-containing monomers. This is especially true for biodiesel fuels with a high proportion of saturated fatty acids having at least 16 carbon atoms in the acid groups. Thereby, the ester-containing polymer preferably used in the fuel mixture according to the invention has a maximum of 5% by weight of units derived from hydroxyl-containing monomers, preferably at most 3% by weight, more preferably at most 1% by weight and most preferably at 0. It is preferable to contain 1 mass%. These include hydroxyalkyl (meth) acrylates and vinyl alcohol. These monomers are described in detail above.

［式中、
Ｒは、水素またはメチルであり、Ｒ¹⁰は、ＯＨ基により置換され、炭素原子２〜２０個を有するアルキル基、または式（Ｖ）

［式中、Ｒ¹³およびＲ¹⁴は、それぞれ独立して、水素またはメチルであり、Ｒ¹⁵は、水素または炭素原子１〜２０個を有するアルキル基であり、ｎは１〜３０の整数である］のアルコキシル化基であり、Ｒ¹¹およびＲ¹²は、それぞれ独立して水素または式−ＣＯＯＲ’’’’（式中、Ｒ’’’’は、水素またはＯＨ基により置換され、炭素原子２〜２０個を有するアルキル基である）の基、または式（Ｖ）

［式中、Ｒ¹³およびＲ¹⁴は、それぞれ独立して水素またはメチルであり、Ｒ¹⁵は、水素または炭素原子１〜２０個を有するアルキル基であり、ｎは１〜３０の整数である］のアルコキシル化基である］
の酸素含有アルコール基を有するモノマー由来の繰り返し単位を少量のみ含む。 Similarly, ester-containing polymers are more active in mixtures of mineral and biodiesel fuels, and in some cases, formula (IV ′)

[Where:
R is hydrogen or methyl, R ¹⁰ is an alkyl group substituted with an OH group and having 2 to 20 carbon atoms, or a compound of formula (V)

Wherein R ¹³ and R ¹⁴ are each independently hydrogen or methyl, R ¹⁵ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 30. And R ¹¹ and R ¹² are each independently hydrogen or the formula —COOR ″ ″ (where R ″ ″ is substituted by hydrogen or an OH group, A group of ˜20 alkyl groups) or formula (V)

[Wherein R ¹³ and R ¹⁴ are each independently hydrogen or methyl, R ¹⁵ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 30] Is an alkoxylated group of
Only a small amount of a repeating unit derived from a monomer having an oxygen-containing alcohol group is included.

The ester-containing polymer used preferably has a thickening efficiency TE100 of 4.0 to 50 mm ² / s, preferably 7.5 to 29 mm ² / s. Thickening Efficiency (TE100), using the 5 wt% polymer, determined at 100 ° C. in 150N reference oil ^{(KV100 = 5.42mm 2 /s,KV40=31.68mm 2 /} s and VI = 103) The For KV100 and KV40 designations, ASTM D445 represents the kinematic viscosity of oil at 100 ° C and 40 ° C, respectively, and the abbreviation VI is the viscosity index determined by ASTM D2270.

In general, the ester-containing polymer used in the present invention has a molecular weight of 1000 to 1000000 g / mol, preferably 25000 to 700000 g / mol and more preferably 40000 to 600000 g / mol and most preferably 60000 to 300000 g / mol; No restrictions shall be imposed. These values are based on the weight average molecular weight M _w of the polydisperse polymer of the composition. This parameter can be determined by GPC.

Preferred copolymers obtainable by polymerizing unsaturated ester compounds are polydisperse M _w / M of 1 to 10, more preferably 1.05 to 6.0 and most preferably 1.2 to 5.0. It is preferable to have _n . This parameter can be determined by GPC.

  The construction of ester-containing polymers is not critical for many applications and properties. Thereby, the ester-containing polymer may be a random copolymer, a gradient copolymer, a block copolymer and / or a graft copolymer.

  Block copolymers and gradient copolymers can be obtained, for example, by modifying the monomer composition discontinuously during chain growth. The block derived from the ester compound of formula (I), (II) and / or (III) preferably has at least 30 monomer units.

  The preparation of polyalkyl esters derived from the above compositions is known per se. Thus, these polymers can be obtained in particular by free radical polymerization and related methods such as ATRP (= atom transfer radical polymerization) or RAFT (= reversible addition-fragmentation chain transfer).

  Conventional free radical polymerization is described in particular in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition. Generally, polymerization initiators and chain transfer agents are used for this. Initiators which can be used are azo initiators widely known in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile and also peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert- Butyl-per-2-ethylhexanoate, ketone peroxide, tert-butyl-peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl-peroxybenzoate, tert-butyl-peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butyl-peroxy-2-ethylhexanoe Tert-butyl-peroxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl-hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, a mixture of two or more of the above compounds and the above compounds but not Similarly, it includes a mixture of compounds capable of forming free radicals. Suitable chain transfer agents are in particular oil-soluble mercaptans, for example dodecyl mercaptan or 2-mercaptoethanol or chain transfer agents from the terpene class, for example terpineol.

  The ATRP method is known per se. Assuming it is a “living” free radical polymerization, the explanation of the mechanism is not constrained. In these methods, a transition metal compound is reacted with a compound having a mobile atomic group. This transfers the mobile group to the transition metal compound, which oxidizes the metal. This reaction forms a group that is added to the ethylenic group. However, the transfer of the atomic group to the transition metal compound is reversible, so that the atomic group is returned to the growing polymer chain, which forms a controlled polymerization system. The structure, molecular weight and molecular weight distribution of the polymer can be correspondingly controlled. This reaction is described, for example, by JS. Wang, et al. , J. et al. Am. Chem. Soc. , Vol. 117, p. 5614-5615 (1995), Matyjaszewski, Macromolecules, vol. 28, p. 7901-7910 (1995). In addition, the patent applications international application 96/30421, international application 97/47661, international application 97/18247, international application 98/40415 and international application 99/10387 are described above. A modification of ATRP is disclosed.

  Furthermore, the polymers of the present invention can be obtained, for example, via the RAFT method. This method is detailed, for example, in International Application No. 98/01478 and International Application No. 2004/083169, which are specifically referenced for disclosure.

  Furthermore, the polymers of the invention can also be obtained by the NMP method (nitroxide mediated polymerization), which is described in particular in US Pat. No. 4,581,429.

  These methods are described in particular in further references, in particular in K.C. Matyjazewski, T .; P. Davis, Handbook of Radical Polymerization, Wiley Interscience, Hoboken 2002. Are comprehensively described in this application and are specifically referred to for disclosure.

  The polymerization can be carried out at standard pressure, reduced pressure or high pressure. The polymerization temperature is not critical. However, in general, it is −20 ° to 200 ° C., preferably 0 ° to 130 ° C. and more preferably 60 ° to 120 ° C.

  The polymerization can be carried out with or without a solvent. The term solvent is understood in the broad sense herein.

  The polymerization is preferably carried out in a nonpolar solvent. These include hydrocarbon solvents such as aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, dodecane, which are also present in branched chain form can do. These solvents can be used individually and as a mixture. Particularly preferred solvents are mineral oils, mineral-derived diesel fuels, natural plant and animal oils, biodiesel fuels and synthetic oils (eg ester oils such as dinonyl adipate) and also mixtures thereof. Of these, mineral oil and mineral diesel fuel are very particularly preferred.

  In order to specifically solve the problems, the fuel composition of the present invention may contain additional additives. These additives are dispersants such as wax dispersants and dispersants for polar substances, demulsifiers, antifoaming agents, lubricating additives, antioxidants, cetane improvers, surfactants, dyes, Contains corrosion inhibitor and / or odorant.

  For example, the fuel composition of the present invention can include, for example, an ethylene copolymer described in European Patent Application Publication No. 541663 (A1). These ethylene copolymers can contain one or more vinyl and / or (meth) acrylic acid esters of 8 to 21 mol% and ethylene of 79 to 92% by mass. Particular preference is given to ethylene copolymers containing from 10 to 18 mol% and in particular from 12 to 16 mol% of at least one vinyl ester. Suitable vinyl esters are derived from fatty acids having linear or branched alkyl groups having 1 to 30 carbon atoms. Examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl octoate, vinyl laurate and vinyl stearate and also esters of branched fatty acid vinyl alcohols such as vinyl isobutyrate, pivalin. There are vinyl acid, vinyl 2-ethylhexanoate, vinyl isononanoate, vinyl neononanoate, vinyl neodecanoate and vinyl neoundecanoate. Likewise suitable comonomers are esters of acrylic and methacrylic acid having 1 to 20 carbon atoms in the alkyl group, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and Isobutyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, There are octadecyl (meth) acrylate and also a mixture of 2, 3 or 4 or more of these comonomers.

  Particularly preferred terpolymers of vinyl 2-ethylhexanoate, vinyl neononanoate and vinyl neodecanoate, apart from ethylene, are preferably 3.5 to 20 mol%, in particular 8 to 15 mol% vinyl acetate and 0.1 to 0.1 mol. It contains 12 mol%, especially 0.2-5 mol% of a particular long chain vinyl ester, and the total amount of comonomer is 8-21 mol%, preferably 12-18 mol%. Further preferred copolymers are in addition to ethylene and 8 to 18 mol% of vinyl esters, further 0.5 to 10 mol% of olefins, such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene. Containing.

The ethylene copolymer preferably has a molecular weight corresponding to a melt viscosity of 140 ° C., 20 to 10000 mPa, in particular 30 to 5000 mPa and especially 50 to 1000 mPa. ^The degree of branching determined by ¹ H NMR spectroscopy is preferably 1-9CH ₃ / 100CH ₂ groups, in particular 2-6CH ₃ / 100CH ₂ groups, for example 2.5-5CH ₃ / 100CH ₂ groups, Not from comonomer.

  Such ethylene copolymers are described in particular in DE 34 43 475 (A), EP 0203554 (B), EP 0254284 (B), EP 0405270 (B), EP No. 0463518 (B), European Patent No. 0493769 (B), European Patent No. 0778875, German Patent Application Publication No. 19620118 (A), German Patent Application Publication No. 19620119 (A) and European Patent Application Publication No. No. 0926168 (A) is described in detail.

  With respect to the ethylene vinyl acetate copolymer and the ternary polymer, it is preferable to have (meth) acrylic acid ester repeating units in addition to ethylene and vinyl acetate repeating units. These polymers may be structured, for example, as random copolymers, as block copolymers, or as graft copolymers.

  In a preferred embodiment, the fuel composition of the present invention may comprise 0.0005-2% by weight ethylene copolymer, preferably 0.01-0.5% by weight.

  However, in terms of cost, the proportions of the above ethylene copolymers can be omitted in further embodiments, in which case these fuel compositions that are free of high ethylene copolymers have excellent properties. In this embodiment, the proportion of ethylene copolymer may preferably be at most 0.05% by weight, more preferably at most 0.001% by weight and most preferably at most 0.0001% by weight.

Preferred fuel compositions are
Mineral diesel fuel 20.0-97.95% by weight, in particular 70-94.95% by weight,
Biodiesel fuel 2.0-79.95% by weight, in particular 5.0-29.95% by weight,
Ester-containing polymer 0.05-5% by mass, especially 0.1-1% by mass
And additives 0-60% by weight, in particular 0.1-10% by weight
Consists of.

  The fuel composition of the present invention preferably has an iodine number of at most 30, more preferably at most 20, and most preferably at most 10.

  Furthermore, the fuel composition of the present invention has excellent low temperature characteristics. In particular, the pour point (PP) according to ASTM D97 is preferably 0 ° C. or lower, preferably −5 ° C. or lower, and more preferably −10 ° C. or lower. The filterability limit (clogging point, CFPP) measured by DIN EN116 is preferably at most 0 ° C., more preferably at most −5 ° C. and more preferably at most −10 ° C. Furthermore, the cloud point (CP) according to ASTM D2500 of the preferred fuel composition can be assumed to be 0 ° C. or lower, preferably −5 ° C. or lower, and more preferably −10 ° C. or lower.

  The cetane number according to DIN 51773 of the fuel composition according to the invention is preferably at least 50, more preferably at least 53, in particular at least 55 and most preferably at least 58.

The viscosity of the fuel composition of the present invention may be within a wide range, which can be adjusted for the intended use. This adjustment can be made, for example, by selecting biodiesel fuel or mineral diesel fuel. Furthermore, the viscosity can be varied by the amount and molecular weight of the ester-containing polymer used. Kinematic viscosity of preferred fuel compositions of the present invention was measured by ASTM D445 at 40 ° C., 1 to 10 mm ² / s, more preferably 2 to 5 mm ² / s and especially preferably 2.5~4mm ² / s.

  Unsaturated ester having 7 to 15 carbon atoms in an alcohol group at a flow improver concentration of 0.05 to 5% by weight of a fuel composition comprising at least one mineral-derived diesel fuel and at least one biodiesel fuel The use of an ester-containing polymer comprising a repeating unit derived from and a repeating unit derived from an unsaturated ester having 16 to 40 carbon atoms in the alcohol group thereby provides a fuel composition with exceptional properties, As a result, known diesel engines can be driven in a simple and inexpensive manner.

  The present invention is illustrated in detail below with reference to examples and comparative examples, without any restrictions.

Examples and Comparative Examples General Methods of Polymer Preparation In each case, 600 g of the monomer composition in the composition detailed in Table 1 and n-dodecyl mercaptan (20 g to 2 g depending on the desired molecular weight) are mixed. 44.4 g of this monomer / regulator mixture was combined with 400 g of carrier oil (eg 100N mineral oil, synthetic dinonyl adipate or vegetable oil) with a saber stirrer, condenser, thermometer, feed pump and N ₂ feed line. Place in the 2 liter reaction flask of the apparatus. The device is inertized and heated to 100 ° C. using an oil bath. The remaining 555.6 g of monomer / regulator mixture is mixed with 1.4 g of tert-butyl peroctanoate. When the reaction flask mixture reaches 100 ° C., 0.25 g of tert-butyl peroctanoate is added and the pumping of monomer / regulator / initiator mixture is started simultaneously. Add uniformly at 100 ° C. over 210 minutes. Two hours after the end of feeding, an additional 1.2 g of tert-butyl peroctanoate is added and the mixture is stirred for a further 2 hours at 100 ° C. A 60% clear concentrate is obtained.

The polymer weight average molecular weight M _w and polydispersity index PDI were determined by GPC. Measurements were made in tetrahydrofuran at 35 ° C. against a polymethylmethacrylate calibration curve consisting of a series of ≧ 25 standards (Polymer Standard Services or Polymer Laboratories), and in a logarithmically uniform manner, this M _peak is 5 × The distribution was from 10 ^{6 to} 2 × 10 ² g / mol. A combination of 6 columns (Polymer Standards SDV 100Å / 2xSDV LXL / 2xSDV 100Å / Shodex KF-800D) was used. An RI detector (Agilent 1100 series) was used to record the signal.

Table 1 Characteristics of the polymers used

DPMA: Alkyl methacrylate having 12 to 15 carbon atoms in the alkyl group SMA: Alkyl methacrylate having 16 to 18 carbon atoms in the alkyl group MMA: Methyl methacrylate Subsequently, the polymer thus obtained is used as a mineral diesel / biodiesel. In an 80/20 mixture. The amount of polymer used is shown in Table 2. The mineral diesel used was an Austrian summer diesel with a pour point of -9 ° C. Palm oil methyl ester (PME) (coconut oil raw material country: Malaysia) having a pour point + 12 ° C. was used as biodiesel. The 80/20 mixture of mineral diesel / biodiesel exhibited a pour point of 0 ° C.

  In order to study low temperature properties, the pour point (PP) of the mixture according to ASTM D97 and mineral diesel fuel was determined. The results obtained are shown in Table 2.

  Table 2: Properties of mineral diesel fuel and properties of mixtures comprising approximately 80% by weight of mineral diesel and approximately 20% by weight of biodiesel, each containing an ester-containing polymer.

  In the examples detailed above, the ester-containing polymer containing repeating units derived from ester monomers having 16 to 40 carbon atoms in the alcohol group is a mixture of biodiesel, in particular coconut oil ester and mineral diesel. It shows very good low temperature properties.

  Particularly surprisingly, compared to pure mineral diesel fuels without additives, preferred mixtures containing certain ester-containing polymers improve the pour point, and this improved pour point also adds biodiesel. Also retained in case.

Claims (25)

  A fuel composition comprising at least one mineral-derived diesel fuel and at least one biodiesel fuel, said fuel composition comprising at least 20% by weight of mineral-derived diesel fuel and 16 to 40 carbon atoms in alcohol groups It contains 0.05 to 5% by mass of at least one ester-containing polymer containing a repeating unit derived from an ester monomer having 1 and a repeating unit derived from an ester monomer having 7 to 15 carbon atoms in an alcohol group. And a fuel composition.   The fuel composition according to claim 1, characterized in that the ester-containing polymer is selected from polyalkyl (meth) acrylate (PAMA), polyalkyl fumarate and / or polyalkyl maleate.   The fuel composition according to claim 1 or 2, wherein the ester-containing polymer contains 0.5 to 60% by mass of a unit derived from an ester monomer having 16 to 40 carbon atoms in the alcohol group. .   The said ester containing polymer contains 0.1-30 mass% of units derived from the ester monomer which has 1-6 carbon atoms in the said alcohol group, The any one of Claim 1 to 3 characterized by the above-mentioned. The fuel composition as described in 2. The ester-containing polymer has the formula (I)

Wherein R is hydrogen or methyl, R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are each independently hydrogen or formula —COOR ′ (wherein R ′ is hydrogen or an alkyl group having 1 to 6 carbon atoms)]
1 to 40% by mass of one or more ethylenically unsaturated ester compounds
Formula (II)

[Wherein R is hydrogen or methyl, R ⁴ is a linear or branched alkyl group having 7 to 15 carbon atoms, and R ⁵ and R ⁶ are each independently hydrogen or formula − COOR ″ (wherein R ″ is hydrogen or an alkyl group having 7 to 15 carbon atoms)]
One or more ethylenically unsaturated ester compounds of 10 to 98% by weight and formula (III)

Wherein R is hydrogen or methyl, R ⁷ is a linear or branched alkyl group having 16 to 40 carbon atoms, and R ⁸ and R ⁹ are each independently hydrogen or formula COOR ′ ″ (wherein R ′ ″ is hydrogen or an alkyl group having 16 to 40 carbon atoms)]
0.1 to 80% by mass of one or more ethylenically unsaturated ester compounds
5. The fuel composition according to claim 1, wherein the fuel composition is obtained by polymerizing a monomer mixture containing   The fuel composition according to any one of claims 1 to 5, wherein the ester-containing polymer contains a maximum of 3 mass% of units derived from a hydroxyl-containing monomer. The ester-containing polymer has the formula (IV ′)

[Where:
R is hydrogen or methyl, R ¹⁰ is an alkyl group substituted with an OH group and having 2 to 20 carbon atoms, or a compound of formula (V)

Wherein R ¹³ and R ¹⁴ are each independently hydrogen or methyl, R ¹⁵ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 30. And R ¹¹ and R ¹² are each independently hydrogen or the formula —COOR ″ ″ (where R ″ ″ is substituted by hydrogen or an OH group, A group of ˜20 alkyl groups, or an alkoxylated group of formula (V) shown above]]
The fuel composition according to any one of claims 1 to 6, comprising a repeating unit derived from an ester-containing monomer having an acid-containing alcohol group at a maximum of 3% by mass.   The fuel composition according to any one of claims 1 to 7, wherein the ester-containing polymer has a molecular weight of 40,000 to 600,000 g / mol.   The fuel composition according to any one of claims 1 to 8, wherein the ester-containing polymer has a polydispersity index of 1.0 to 10.0. 10. The fuel composition according to claim 1, wherein the ester-containing polymer has a thickening efficiency TE100 measured at 100 ° C. at 7.5 to 29 mm ² / s. .   11. The fuel composition according to claim 1, wherein the mineral-derived diesel fuel has a boiling point of 120 ° C. to 450 ° C. 11. 12. The fuel composition according to claim 1, wherein the mineral-derived diesel fuel has a kinematic viscosity measured at 40 [deg.] C. at 1-5 mm < ² > / s according to ASTM D445. .   The fuel composition according to any one of claims 1 to 12, wherein the biodiesel fuel comprises a monohydric alcohol-derived fatty acid ester having 1 to 4 carbon atoms.   The fuel composition according to claim 13, wherein the monoester is a methyl ester.   The fuel composition according to any one of claims 1 to 14, wherein the biodiesel fuel contains at least 35% by mass of a saturated fatty acid ester having at least 16 carbon atoms in a fatty acid group.   The fuel composition according to any one of claims 1 to 15, wherein the biodiesel fuel is derived from coconut oil or tallow.   The fuel composition according to claim 1, wherein the fuel composition comprises at least one additive.   At least one additive is selected from the group of dispersants, demulsifiers, antifoaming agents, lubricity additives, antioxidants, cetane improvers, surfactants, dyes, corrosion inhibitors and / or odorants 18. The fuel composition according to claim 17, wherein:   The fuel composition according to any one of claims 1 to 18, wherein the fuel composition contains at least 80% by mass of a mineral-derived diesel fuel.   The fuel composition according to any one of claims 1 to 19, wherein the fuel composition contains 0.1 to 1% by mass of at least one ester-containing polymer. The fuel composition is 20.0 to 97.95% by mass of a mineral-derived diesel fuel,
Biodiesel fuel 20-79.95% by mass
0.05-5% by mass of ester-containing polymer and 0-60% by mass of additives
The fuel composition according to any one of claims 1 to 20, wherein the fuel composition comprises:   The fuel composition according to any one of claims 1 to 21, characterized in that the fuel composition comprises 0.01 to 0.5% by weight of an ethylene copolymer.   23. A fuel composition according to any one of the preceding claims, characterized in that the fuel composition comprises up to 0.05% by weight of ethylene copolymer.   7 to 15 carbon atoms in the alcohol group at a concentration of 0.05 to 5% by weight as a flow improver of a fuel composition comprising at least one mineral-derived diesel fuel and at least one biodiesel fuel Use of an ester-containing polymer comprising a repeating unit derived from an unsaturated ester and a repeating unit derived from an unsaturated ester having 16 to 40 carbon atoms in the alcohol group.   A method for driving a diesel engine, wherein the fuel composition according to any one of claims 1 to 23 is used.