TW201037072A - Fuel compositions with improved cloud point and improved storage properties - Google Patents

Abstract

The present invention relates to a fuel composition comprising at least one biodiesel fuel and comprising 0.05 to 5% by weight of at least one polymer comprising ester groups, which comprises repeat units derived from ester monomers having 16 to 40 carbon atoms in the alcohol radical, and repeat units derived from ester monomers having 7 to 15 carbon atoms in the alcohol radical, and the polymer comprising ester groups has a weight-average molecular weight in the range from 5000 to 100 000 g/mol. The present invention further describes the use of polymers comprising ester groups as flow improvers in fuel compositions which comprise at least one biodiesel fuel. Surprising advantages can be achieved especially with regard to the improvement of the cloud point and the low-temperature storability.

Description

201037072 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a fuel composition comprising a renewable raw material, and to a polymer comprising a plurality of ester groups for improving cloud point and The use of biodiesel-based fuel for low temperature storage. [Prior Art] ^ The decline in global mineral oil stocks due to the use of fossil fuels and the discussion of C〇2 imbalances have led to an increasing interest in alternatives based on renewable raw materials. For example, more and more bioethanol is added to commercial petroleum. Taking diesel fuel as an example, so-called biodiesel is used. This can be added to fossil-derived diesel at different levels or in neat form. The advantage of biodiesel is that it has less impact on the global balance of CO 2 . For example, burning these fuels releases as much carbon dioxide as there are already stored 0 biomass. Greenhouse gases derived from the manufacture of these biomass fuels are ignored and they do not affect the C〇2 balance. The advantage of biodiesel is that it can be obtained from a variety of raw materials. Typical raw materials are vegetable oils (eg, triglycerides) such as rapeseed oil, sunflower oil, soybean oil, palm oil, coconut oil, coriander oil, cottonseed oil, castor oil, olive oil 'peanut oil, jatropha oil, Butter (karanji), nahar oil (Mesua ferrea L.), corn oil, almond oil, mustard seed oil, algae oil, and used vegetable oil. Other examples include oils derived from wheat, sesame, sesame, milkwood, peanut oil and flax. Animals can also be used to source oils and fats from -5 to 201037072. Examples are tallow, lard, chicken fat, bone and fish meal, and other fats and oils that can be obtained from slaughtering wild or reared animals. Understanding the so-called "biodiesel" in many cases refers to fatty acid esters of fatty acid components having a chain length of 14 to 24 carbon atoms and having 0 to 3 double bonds (usually fatty acid methyl esters (FAME)). mixture. The higher the number of carbon atoms present and the smaller the number of double bonds, the higher the melting point of FAME. Typical materials are vegetable oils (e.g., triglycerides) such as rapeseed oil, sunflower oil, soybean oil, palm oil, coconut oil, and in the case of isolation, even vegetable oils used. These esterification reactions (usually under alkaline catalysis using methanol) are converted to the corresponding fame. Unlike rapeseed oil methyl ester (RME), which is widely used in Europe and contains essentially 5% (sometimes even more than 6%) C16:0 + C18:0-FAME, palm oil methyl ester (PME) contains about 50 %C16:0 + C18:0-FAME. Similar derivatives of automatic lipids (e.g., tallow) also have similar high C16:0 + C18:0-FAME content. This high wax content can be affected only by the polymeric flow modifier, which is added substantially at a rate of up to 2%. Compared to rapeseed oil, the yield of palm oil produced per hectare is more than three times. This offers great economic advantages. However, one disadvantage is the high pour point of the PME, which is about +12 °C. The poly(meth)acrylate 'PA(M) A has not been established and described for a long time, not with M(M) A (eg, US 3 869 396 by Shell Oil Company) or with M(M) A ( For example, US 5 3 1 2 8 8 4 of Rohm & Haas C ompany as a pour point modifier for mineral oil, or as a pour point modifier for ester-based lubricants (Rohm & -6- 201037072

US 5 696 066) of Haas Company. However, the use of these polymers in fuel compositions comprising at least one biodiesel fuel has not been described. In addition, the publication WO 0 1 /40334 ( RohMax Additives

GmbH) describes polyalkyl (meth) acrylates that can be used in biodiesel fuels. This publication provides a special formulation that imparts special properties to these polymers. However, there is a lack of examples related to biodiesel fuel. Furthermore, the advantages of a polymer having a high proportion of specific repeating units containing a plurality of ester groups are not described.流动 An oil-soluble polymer-based flow improver for use in a mixture of fossil diesel and biodiesel is also known (WO 94/1 0267, Exxon Chemical Patents Inc.). However, the examples only describe ethylene-vinyl acetate copolymer (EVA) and a copolymer having a fumarate C12/C14-alkyl ester and a vinyl acetate unit. There is no comprehensive and clear description of a particular polymer comprising a plurality of ester groups in WO 94/10267.

In addition, the most suitable series of EVA copolymers for diesel/biodiesel blends are known (EP 1 54 1 662 to 664; WO 2008/113735 and DE 103 57 877). For example, EP 1 541 663 describes a mixture comprising 75 vol% of mineral-derived diesel fuel and 25 vol% of biodiesel, which comprises 150 ppm poly(dodecyl methacrylate) and 1 to 200 ppm ethylene - Vinyl acetate copolymer (EVA). However, it describes the use of E V A for the needs of the situation. However, E V A is a relatively expensive additive. According to this, the substitute is intended to avoid the use of EVA. There is no reference in EP 1 54 1 663 for the advantages of a particular polymer comprising a plurality of ester groups. 201037072 In addition, additives for fuel mixtures comprising mineral diesel and biodiesel are described in WO 2007/1 1 3 03 5 . Furthermore, the low temperature properties achievable in diesel/biodiesel blends by the addition of additives are not necessarily available for pure biodiesel fuels due to their boiling behavior, their viscosity and hence their hydrocarbon composition. Therefore. In view of the prior art, it is therefore an object of the present invention to provide a fuel composition that provides a profile of properties substantially corresponding to mineral diesel fuel, which includes the highest proportion of renewable feedstock. At the same time, this fuel must be more particularly characterized by very good low temperature properties. A further object of the present invention is to provide a fuel having high stability to an oxidation reaction. In addition, this fuel must have the highest hexadecane oxime. At the same time, this novel fuel must be made in a simple and inexpensive way. Another object of the present invention is to provide an additive capable of reducing the cloud point of biodiesel. Another object of the invention is to provide a fuel which has a small amount of precipitation when stored below the cloud point. At the same time, the formation of this precipitate can be delayed as much as possible. Other objectives not expressly set forth may be immediately derived or identified by those of the present disclosure by means of a fuel composition having all of the features of the scope of the patent application. Appropriate modifications to the fuel composition of the present invention are protected by the provisions back to item 1 of the scope of the patent application. The use of a polymer comprising a plurality of ester groups as a flow modifier for improving cloud point and low temperature storage provides the answer to this question in the patent application section 1 7 '1 8 and 20. According to the present invention, there is provided a fuel composition comprising at least one biodiesel fuel, characterized in that the fuel composition comprises 0.05 to 5% by weight of at least one polymer comprising a plurality of ester groups, The polymer comprises a repeating unit derived from an ester monomer having an alcohol group of 16 to 40 carbon atoms, and a repeating unit derived from an ester monomer having 7 to 15 carbon atoms of the alcohol group contained, and The weight average molecular weight of the polymer comprising a plurality of ester groups is in the range of 5,000 to 10,000,000 g/mole. [Embodiment] This makes it possible to provide, in an unforeseen manner, a fuel composition comprising at least one biodiesel fuel and including an excellent profile of properties. For example, the present fuel composition has particularly surprisingly low cloud point, very good low temperature storage and excellent low temperature flow properties.

In addition, a very high proportion of palmitol alkyl esters can be used in this fuel. For ecological and economic reasons, palm oil is superior to rapeseed oil that is typically used. For example, the manufacturing yield of palm oil is significantly higher than the manufacturing yield of rapeseed oil. In addition, the production of rapeseed uses a very large amount of chemicals, especially fertilizers and crop protection compositions, which is not conducive to ecology. At the same time, rapeseed is inherently incompatible at the time of production and must be cultivated in a crop rotation system, and rapeseed in the same area must be cultured every 3 to 5 years. Therefore, it is difficult to further improve the production of rapeseed. However, compared with rapeseed oil alkyl ester, palmitol alkyl ester has a significantly higher cloud point (in the case of methyl ester, about + 1 3 °c): rapeseed oil alkyl ester The turbidity of -9-201037072 is significantly lower (in the case of methyl ester, about -7 ° C). In a particular aspect, the invention thus facilitates the use of a particularly high proportion of palmitol alkyl esters to make fuel compositions without unacceptable unacceptable low temperature properties. Similar advantages with respect to other biodiesel fuels having a high proportion of saturated fatty acids can also be achieved. It is also possible in particular to use animal-derived fats which can be obtained in a very inexpensive manner as a fuel source. The fuel composition of the present invention comprises at least one biodiesel fuel component. Biomass diesel fuel is a substance, particularly an oil derived from plant or animal materials or both, or derivatives thereof, which are basically useful as a substitute for mineral diesel fuel. In a preferred system, a biodiesel fuel, also commonly referred to as "biodiesel" or "biomass fuel", comprises a fatty acid having 6 to 30 carbon atoms and preferably 12 to 24 carbon atoms. An alkyl ester and a monohydric alcohol having 1 to 4 carbon atoms. In many cases, some fatty acids may contain one, two or three double bonds. The monohydric alcohol particularly includes methanol, ethanol, propanol and butanol, preferably methanol. Examples of oils derived from animal or plant material and which can be used in accordance with the invention are palm oil, rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, Palm kernel oil, coconut oil, mustard seed oil, oil derived from automatic fats (especially tallow, bone oil, fish oil), and used cooking oil. Further examples include oils derived from cereals, wheat, numb, sesame, rice, jatropha, peanut oil and linseed oil. In particular, the use of palm oil, soybean oil, jatropha oil or tallow (especially tallow, chicken fat or lard) as a reactant for the preparation of raw -10-201037072 quality diesel can achieve surprising advantages. The fatty acid alkyl esters preferably used are obtainable from these oils by methods known in the art. Preferably, the oil according to the invention has a high C16:0/C18:0-glyceride content, such as palm oil and an oil derived from animal fats and derivatives thereof, in particular palmitolenes derived from monohydric alcohols. ester. Palm oil (also: palm fat) is derived from the flesh of palm fruit. This fruit is sterilized and pressed. Due to its high carotene content, the fruit and oil have an orange-red color, which is removed during the refining step. This oil may contain up to 80% C 18:0-glyceride. A particularly suitable biodiesel fuel is a lower alkyl ester of a fatty acid. Examples thereof include fatty acids having 6 to 30 (preferably 12 to 24 and more preferably 14 to 22) carbon atoms (for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, heptadecanoic acid, and the like). Arachic acid, behenic acid, tetracosic acid, citric acid, palmitic acid, stearic acid, oleic acid, petroleum acid, petroselic acid, ricinoleic acid, Ethyl esters of elaeostearic acid, linoleic acid, linoleic acid, arachidic acid, gadoleinic acid, docosicic acid or erucic acid, butyl ester and especially A commercially available mixture of methyl esters. In a particular aspect of the invention, the biodiesel fuel used comprises at least 30% by weight, more preferably at least 5% by weight and at least 40% by weight of the most preferred fatty acid groups having at least 16 carbon atoms. Saturated fatty acid esters. This includes, in particular, palmitate and stearate. The fuel used comprises at least 6% by weight (at least 1% by weight and more preferably at least 40% by weight) of methyl palmitate and/or methyl stearate, particularly to those skilled in the art who have failed to 201037072 Foreseeable advantages. These fatty acid esters are usually used in a mixture due to cost factors. The iodine number of the biodiesel fuel which can be used according to the invention is at most 5 〇, especially at most 125, at most 70 and more preferably at most 60. This iodine number is known to be an indicator of the content of unsaturated compounds in fat or oil, which can be determined in accordance with DIN 53 24 1-1. As a result, the fuel composition of the present invention has a particularly low amount of deposit formed in a diesel engine. Moreover, these fuel compositions have a particularly high hexadecane oxime. In general, the fuel composition of the present invention may comprise at least 40% by weight, especially at least 60% by weight, at least 80% by weight, and preferably at least 5% by weight, more preferably a biodiesel fuel. The fuel composition of the present invention further comprises from 0.05 to 5% by weight, preferably from 8 to 3% by weight, and more preferably from 1 to 1% by weight, based on at least one polymer comprising a plurality of ester groups. It is understood that a polymer comprising a plurality of ester groups herein refers to a polymer obtainable by polymerizing a monomer composition comprising an ethylenically unsaturated compound having at least one ester group, hereinafter referred to as an ester monomer. . Accordingly, these polymers contain an ester group as a part of a side chain. These polymers include, in particular, polyalkyl (meth)acrylates (PAMA), polyalkylene fumarates and/or polyalkyl maleates. The ester monomers themselves are known. They include, in particular, (meth) acrylates, maleic esters and fumarates, which may have different alcohol groups. The term "(meth)acrylate" includes methacrylate and acrylate and mixtures of the two. These monomers are widely known. Here, the alkyl group -12- 201037072 may be a straight chain, a ring or a branch. The alkyl group may also have a known substituent. The polymer containing a plurality of ester groups contains a repeating unit derived from an ester monomer having an alcohol group of 16 to 40 carbon atoms, and an ester sheet derived from an alcohol group having 7 to 15 carbon atoms Repeat unit of body. The term "repeating unit" is widely known in the art. Preferably, a polymer comprising a plurality of ester groups is obtained by radical polymerization of monomers, ATRP, RAFT and NMP methods (explained below, in the present invention, as a free radical method), but it should not Form any restrictions. In these methods, the double 〇 bond is opened to form a covalent bond. According to this, a repeating unit is obtained from the monomer used. The polymer comprising a plurality of ester groups may contain 5 to 99.9% by weight, particularly 20 to 98% by weight and more preferably 30 to 60% by weight, and the repeating unit is derived from the alcohol group having 7 to 15 carbon atoms. Ester monomer. In a particular aspect, the polymer comprising a plurality of ester groups may contain from 0.1 to 90% by weight, preferably from 5 to 80% by weight and more preferably from 40 to 70% by weight. The repeating unit is derived from the alcohol group contained therein. An ester monomer of from 1 to 60 carbon atoms. Further, the polymer comprising a plurality of ester groups may preferably contain 0.1 to 30% by weight, preferably 0.5 to 20% by weight, and the repeating unit is derived from a vinegar monomer having 1 to 6 carbon atoms in the alcohol group contained. The polymer comprising a plurality of ester groups contains at least 40% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight and at least 5% by weight of the repeating unit is derived from the ester monomer. Mixtures 13-201037072 which may be used to obtain the polymer comprising a plurality of ester groups of the present invention may contain 〇 to 40% by weight, particularly oi to 30% by weight and more preferably 5% to 5% by weight. Various ethylenically unsaturated ester compounds of formula (I)

R

0R1 (|)

Wherein R is hydrogen or methyl, and R1 is a straight or branched alkyl group having from 1 to 6 carbon atoms. Each of R2 and R3 is independently a gas or a group of the formula -COOR.', wherein R' is hydrogen or An alkyl group having 1 to 6 carbon atoms. Examples of the component (I) include: (meth) acrylate, fumarate, and maleate derived from a saturated alcohol such as methyl (meth) acrylate or (meth) acrylate Ethyl ester, n-propyl (meth) acrylate 'isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and amyl (meth) acrylate, (A) Ethyl acrylate

a cycloalkyl (meth)acrylate such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate; a (meth) acrylate derived from an unsaturated alcohol, such as 2-(meth)acrylic acid Propargyl ester, allyl (meth)acrylate and ethyl acetonate (meth)acrylate. The composition to be polymerized preferably contains 5 to 98% by weight, particularly 2 to 90% by weight and 30 to 60% by weight, more preferably one or more ethylenically unsaturated ester compounds of the formula (u) -14-

R

201037072 OR4 wherein R is hydrogen or methyl 'R4 is a linear branched alkyl group having 7 to 15 carbon atoms 'R5 and R6 are each independently hydrogen or a group of formula -COOR" wherein R" is hydrogen or An alkyl group of 7 to 15 carbon atoms. Examples of the component (II) include: (meth) acrylate, fumarate, and methic acid ester derived from a saturated alcohol, such as 2-ethylhexyl (meth) acrylate, (A) Heptyl acrylate, 2-tributyl butyl (meth) acrylate, octyl acrylate, 3-isopropyl heptyl (meth) acrylate, decyl acrylate, decyl (meth) acrylate, Methyl) propylene-ester, 5-methyl-monoester (meth)acrylate '(methyl)propanedecyl ester, 2-methyldodecyl (meth)acrylate, tridecyl (meth)ate , 5-methyltridecyl (meth)acrylate, (tetradecyl methacrylate, pentadecyl (meth)acrylate;

U (meth) acrylate derived from an unsaturated alcohol, such as (meth) oleate; cycloalkyl (meth) acrylate, such as 3-ethylcyclohexyl (meth) acrylate, (methyl) ) decyl acrylate; and the corresponding fumaric acid maleate. Further, a preferred monomer composition comprises from 1 to 90% by weight. /. , 8 % by weight, preferably 40 to 70% by weight, more preferably one or more of the ethylenically unsaturated ester compounds (II) or

Cis-butyl)methylmethyl acid decaenoic acid propylene) propylene propylene dilute ester and 5 to (III -15- 201037072

R

Wherein R is hydrogen or methyl, R7 is a straight or branched alkyl group having from 16 to 40 (preferably from 16 to 30) carbon atoms, and each of R8 and R9 is independently hydrogen or a radical of the formula -COOR"' a group, wherein R,, is hydrogen or an alkyl group having 16 to 4 Å (preferably 16 to 30) carbon atoms. Examples of the component (III) include: (meth) acrylate derived from a saturated alcohol For example, hexadecyl (meth) acrylate, 2-methyl hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-isopropyl heptadecyl (meth) acrylate, (a) Base) 4-tert-butyl octadecyl acrylate, 5-ethyl octadecyl (meth) acrylate, 3-isopropyl octadecyl (meth) acrylate, octadecyl (meth) acrylate, ( Ninemethyl methacrylate, hexadecyl (meth) acrylate, whale oxime (meth) acrylate, stearyl epoxide, behenyl (meth) acrylate And/or tetrakisyltrifluoro(meth)acrylate; cycloalkyl (meth)acrylate such as 2,4,5-tri-secondary butyl-3-vinylcyclo(meth)acrylate Hexyl ester, Acrylic acid 2,3,4,5-tetra-tertiary butylcyclohexyl ester; and corresponding fumarate and maleate oxime ester compounds having long-chain alcohol groups, especially groups Parts (II) and (III)' can be obtained, for example, by reacting (meth) acrylate, fumarate, maleate and/or the corresponding acid with a long-chain fatty alcohol.通-16- 201037072 often forms a mixture of esters (for example, (meth) acrylates with different long chain alcohol groups). These fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo A1 coh ο 1 ® 1 1 0 0 ; Alfol® 610,

Alfol® 810, Lial® 125 and Nafol® (Sasol); Alphanol® 79 (ICI); Epal® 610 and Epal® 8 10 (Afton);

Linevol ® 79 ' Linevol® 911 and Neodol® 25E (Shell);

Dehydad® , Hydrenol® and Lorol® ( Cognis ) ;

Acropol® 35 and Exxal® 10 (Exxon Chemicals); K a 1 c o 1 ® 2 4 6 5 (K a o C h e m i c a 1 s ). Among the ethylenically unsaturated ester compounds, (meth) acrylate is particularly superior to maleic acid esters and fumarates, that is, in particularly preferred systems, formulas (I), (II) and Each of R2, R3, R5, R6, R8 and R9 of III) is hydrogen. a unit derived from an ester monomer having 7 to 15 carbon atoms (preferably having the formula (π)) is derived from a unit having an ester monomer having 16 to 40 carbon atoms (preferably, formula (III)) The weight ratio can be in a wide range. The weight ratio of the repeating unit derived from the ester monomer having an alcohol group of 7 to 15 carbon atoms to the repeating unit derived from the ester monomer having an alcohol group of 16 to 40 carbon atoms is from 5:1 to 1:3 0 The range is preferably in the range of 1:1 to 1:3, and 1 · 1 : 1 to 1: 2 is particularly good. Component (IV) particularly contains an ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated ester compound of the formula (I), (II) and/or (III). However, it is particularly suitable for the polymerization according to the present invention. The comonomer-17- 201037072 corresponds to the following formula:

Wherein R1 and R2* are each independently selected from the group consisting of hydrogen; halogen; CN; a linear or branched home having from 1 to 20 (1 to 6 preferably '1 to 4 more preferred) carbon atoms, which may be 1 to ( 2n+l) substituted by a halogen atom, wherein η is the number of carbon atoms of the alkyl group (eg, CF3); unsaturated having 2 to 1 〇 (2 to 6 preferably, 2 to 4 more preferably) carbon atoms a chain or branched alkenyl or alkynyl group which may be substituted by 1 to (2η-1) halogen atoms (preferably chlorine), wherein η is the number of carbon atoms of the alkyl group ', for example, CH 2 = CC 1 ; a cycloalkyl group of 8 carbon atoms which may be substituted by 1 to (2n-1) halogen atoms (preferably chlorine), wherein η is the number of carbon atoms of the cycloalkyl group; C (= Y*) R5* > C ( =Y*) NR6*R7* ' Y*C ( =Y%) R5* > SOR5* ' S02R5*, 0S02R5*, NR8*S02R5*, PR5*2, p (=Y*) R5 , Y*PR5*2, Y*P (=Y*) R5%, NR8%, wherein these additional R8<, aryl or heterocyclic groups are quaternized, wherein y* can be nr^, S or Ο, preferably 0; R5i is an alkyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, OR15 (R15 is hydrogen or an alkali metal), having 1 Alkoxy, aryloxy or heterocyclooxy having 20 carbon atoms; R6* and R" are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, or R6* and R" may be substituted 2 to 7 (preferably 2 to 5) alkyl groups of the carbon atoms 'here' they form a 3- to 8-membered (preferably 3 - to 6 _ member) ring, while R8* is hydrogen or has a linear or branched alkyl or aryl group of 1 to 20 carbon atoms; -18- 201037072 R3 and R4 are independently selected from hydrogen, halogen (alkyl or fluorine to 6 carbon atoms and c〇〇R9*) Or an alkyl group having 1 to 40 carbon atoms, or a group of the formula (CH2) n', which may be substituted by 1 to 2η, a g C4 alkyl group, or a formula c (= Ο ) - Y * ' wherein η' is 2 to 6, preferably 3 or 4, and Y*, such as at least two of the preferred groups (IV) of the groups R", R2*, R_3* and R4*, include: Hydroxyalkyl (meth)acrylate, such as 3,4-dihydroxybutyl methacrylate, 2-hydroxypropyl 2-hydroxy acid, 2,5-dimethyl (meth)acrylate 1,10-decanediol (meth)acrylate; aminoalkyl (meth)acrylate, such as N- ( 3-diyl acrylamide, 3-dibutylamino hexadecyl 3-ethylaminoacrylate; nitriles of (meth)acrylic acid and other nitrogen-containing methyl N-(methyl Propylene oxiranyl ethyl) diisobutyl ketone iridinyloxyethyl) bis(hexadecyl) ketimine, methyl acetonitrile, 2-methyl propylene methoxyethyl methyl cyanamide, methyl ester An aryl (meth) acrylate, such as methacrylic acid phenyl acrylate, wherein the aryl groups may each be unsubstituted or up to a carbonyl containing methacrylate such as methyl propyl g methacrylic acid Carboxymethyl ester, methacrylic acid D azole D is set to / is better, with 1 r9 is hydrogen, alkali metal ^ and ruler" can be avidin atom or C, to -c (= 〇) group Definition; and is hydrogen or halogen. 3-3-propyl ester, methyl ethyl ester, methacryl-1,6-hexanediol methylaminopropyl)methyl amyl ester, (meth) acrylate, such as amine, N-(methyl Propyl propyl decylamino cyanoacrylate or methacrylic acid tetrasubstituted; § 2-carboxyethyl ester, ethyl ethyl ester, N-(methyl-19-201037072-based acryloxy)carbamamine, Propyl methacrylate, N-methylpropenylmorpholine, N-methylpropenyl-2-pyrrolidone, N-(2-methylpropenyloxyethyl)-2-pyrrolidine Ketone, N-(3-methylpropenyloxypropyl)-2-pyrrolidone, N-(2-methylpropenyloxypentadecyl)-2-pyrrolidone, N-( 3- Methyl propylene oxime heptadecyl)-2-pyrrolidone; diol dimethacrylate, such as 1,4-butylene glycol methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate; methacrylate of ether alcohol, such as tetrahydrofurfuryl methacrylate, vinyl methacrylate Oxyethyl ester, methoxyethoxyethyl methacrylate, methacryl 1-butoxypropyl acid ester, 1-methyl-(2-vinyloxy)ethyl methacrylate, cyclohexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate, A Benzyl methacrylate, methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, Allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate; A methacrylate of a halogenated alcohol, such as 2,3-dibromopropyl methacrylate, 4-bromophenyl methacrylate, 1,3-dichloro-2-propyl methacrylate, methacrylic acid 2 - bromoethyl ester, 2-iodoethyl methacrylate, chloromethyl methacrylate; epoxy methacrylate such as 2,3-epoxybutyl methacrylate, methacrylic acid 3,4 - butyl butyl acrylate, methacrylic acid 10,1 epoxide 10-20-201037072 - ester, 10,11-epoxy hexadecyl methacrylate, epoxycyclohexyl methacrylate; Acrylic acid Water glyceride; methacrylate containing phosphorus-, boron- and/or ruthenium, such as methacrylic acid g (dimethyl methacrylate) propyl methacrylate 2-(ethyl phosphite) Dimethylphosphinomethyl acrylate, dimethyl decyl ethyl methacrylate, diethyl methacryl decyl phosphonate, dipropyl methyl decyl phosphate, 2- methacrylate Base phosphinyl) ethyl ester 2,3 -butyl butyl methacrylate oxime ethyl ester, methyl diethoxymethyl decyl ethoxy decane, diethyl methacrylate methacrylate; vinyl halide For example, vinyl chloride, vinyl fluoride, vinylidene chloride and difluoro]heterocyclic (meth) acrylates, such as 2-(azolyl)ethyl (meth)acrylate, (meth)acrylic acid 2 - (4-morpholinyl)ethyl ester (2-methylpropenyloxyethyl)-2-pyrrolidone; vinyl ester, such as vinyl acetate; Q styrene, alkyl substitution in the side chain Substituted styrene (0:-methylstyrene and ethylstyrene), substituted styrene having an alkyl group on the ring (eg, vinyl toluene and p-methylphenylethyl, halogen) Styrene (eg, monochlorostyrene, dichlorostyrene, triethylene, and tetrabromostyrene); heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinyl, 2-methyl -5 -vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-yl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-ethazole, 3-vinylfluorene Oxazole, 4-vinylcarbazole, 1-vinylimidazole 2,3 -indol-2-acid phosphine propylene, boropropene ethylene 1 - silane 1 - such as phenyl bromopyridine 2- -21 - 201037072 Methyl-1 -vinylimidazole, N-vinylpyrrolidone, 2_vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylhexyl Indoleamine, N-vinyl butyrolactam, vinyl oxolane 'vinyl furan, vinyl thiophene, vinyl thiophene, vinyl thiazole and hydrogenated vinyl thiazole, vinyl Carbazole and hydrogenated vinyl Dfazole; vinyl ether and isoprenyl ether; maleic acid and maleic acid different from those mentioned in (I), ( Π ) and (III ) Acid derivatives such as maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide; and (I), (II) and (ΠΙ) Mention of different fumaric acid and fumaric acid derivatives are mentioned. The proportion of comonomer (IV) can vary depending on the use and nature profile of the polymer. Usually, the ratio may be in the range of 〇 to 60% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 10% by weight. Due to the nature of combustion and ecological factors, the proportion of monomers containing aryl, heteroaryl, nitrogen-containing groups, phosphorus-containing groups and sulfur-containing groups can be as small as possible. Therefore, the ratio of these monomers can be limited to 1% by weight, particularly 0.5% by weight, and preferably 0.001% by weight. The comonomer (Iv) and the ester monomers of the formulae (I), (II) and (III) may be used singly or as a mixture. In particular, polymers comprising a plurality of ester groups and comprising only a small proportion, if any, derived from units containing hydroxyl groups, can achieve surprising advantages. The biodiesel fuel has a high proportion of saturated fatty acids and this is especially true when the acid group of the saturated fatty acid-22-201037072 has at least 16 carbon atoms. Included in the fuel mixture of the present invention comprising a plurality of up to 5% by weight, preferably up to 3% by weight, preferably 'preferably and at most 0.1% by weight, optimally derived from hydroxyl groups, including (meth)acrylic acid Hydroxyalkyl esters and vinyl alcohol. This is in the previous section. Similarly, a compound derived from a monomer of the formula (IV') having an oxyhydric alcohol group by a plurality of ester groups and containing only a small ratio can exhibit surprisingly good results: Let R1°

Rll ο where R is hydrogen or methyl, R10 is alkyl substituted with fluorenyl and has a subunit, or an alkoxy group of formula (V) R13 R14 wherein R13 and R14 are each independently hydrogen or methyl, R1 An alkyl group of up to 20 carbon atoms, and η is a total of 1 to 30, and R 1 1 and R 12 are each independently hydrogen or a formula of -C Ο Ο R" ” 3 is hydrogen or substituted with fluorenyl and has 2 to 20 carbon atoms or alkoxylated groups of formula (VI) Accordingly, the preferred base polymer contains more than 1 weight percent per oxime monomer unit. These monomers have been detailed (if any, the poly(IV) to 20 carbon atoms (V) of the repeating unit are hydrogen or have a number of 1, group, wherein R"" alkyl, -23- ( VI) (VI) 201037072 R13 R14 -^CH-CH-O^ Ris wherein R13 and R14 are each independently hydrogen or methyl, R15 is hydrogen or an alkyl group having from 1 to 20 carbon atoms, and η is 1 to An integer of 30. The molecular weight of the polymer comprising a plurality of ester groups used in accordance with the present invention is in the range of 5,000 to 1 Torr, gram/mol, to 1 Torr, 〇〇0 to 7 Torr, It is preferably in the range of 00 g/mole and more preferably in the range of 20,000 to 50,000 g/mole. These tethers are based on the weight average molecular weight Mw of the polydisperse polymer in the composition. The polydispersity Mw/Mn of the preferred copolymer obtainable by polymerizing the unsaturated ester compound is preferably in the range of 1 to 10, preferably 1.05 to 6.0 and preferably 1.2 to 5.0. The parameters can be measured by GPC. For many applications and properties, the structure of a polymer comprising a plurality of ester groups is not critical. Accordingly, a polymer comprising a plurality of ester groups can be a random copolymer. Gradient copolymers, block copolymers and/or graft copolymers. By, for example, changing the monomer composition in a discontinuous manner during chain growth, block copolymers and gradient copolymerization are obtained. The block of the ester compound derived from the formula (I), (11) and/or (111) is preferably one having at least 1 monomer unit and preferably having at least 30 monomer units. The preparation of polyalkyl esters is known per se. Therefore, these polymers are particularly obtainable by free radical polymerization and related methods such as ATRP (= atom transfer radical polymerization) or RAFT (reversible addition split chain transfer). -24- 201037072 Commonly used free radical polymerizations are described in Ullmann's

Encyclopedia of Industrial Chemistry, Sixth Edition. Generally, a polymerization initiator and a chain transfer agent are used for this purpose. Useful initiators include azo initiators (e.g., AIBN and 1,1-azobiscyclohexanecarbonitrile) and peroxy compounds (e.g., methyl ethyl ketone peroxide, peroxidation) well known in the art. Acetylacetone, dilaurin peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tertiary butyl peroctoate, methyl iso-butyl ketone peroxide, cyclohexanone peroxide, Dibenzoyl peroxide, butyl tertiary butyl peroxybenzoate, tertiary butyl peroxy isopropyl carbonate, 2,5-bis(2-ethylhexylperoxy)-2, 5-dimethylhexane, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1 , 1-bis(tertiary butylperoxy)cyclohexane, 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane, cumyl hydroperoxide a mixture of a tertiary butyl hydroperoxide, a bis(4-tert-butylcyclohexyl)peroxydicarbonate, a mixture of two or more of the foregoing compounds, and a compound of the foregoing and a non-previous Q but capable of forming a mixture of free radical compounds. Suitable chain transfer agents are special It is an oil-soluble thiol (such as n-dodecyl thiol or 2-mercaptoethanol) or a chain transfer agent of hydrazine (for example, terpinolene). The ATRP method itself is known. "radical polymerization, but the description of this mechanism should not impose any limitation. In these methods, the transition metal compound reacts with a compound having a transferable atomic group. This causes the transferable atomic group to be transferred to the transition metal compound, which makes Oxidation of the metal. This reaction forms a free radical and is added to the vinyl group. However, the transfer of the atomic group to the transition metal compound is reversible, causing the atomic group to transfer to -25,370,072 to the growing polymer chain, which is controlled. The polymerization system can be used to control the polymer structure, molecular weight and molecular weight distribution. This reaction is, for example, JS. Wang et al., J. Am. Chem. Soc., Vol. l 17, p. 5614-5615 (1) 9 9 5 ) , Matyj aszewski

Macromolecules, vol. 28, p.7901-7910 (1995) is described. In addition, the patent application WO 96/3042 1 , WO 97/47661, WO 97/18247, WO 98/40415 and WO 99/10387 disclose variants of the ATRP explained above. Further, the polymer of the present invention can also be obtained by, for example, the RAFT method. This method is described in detail in, for example, WO 98/0 1 47 8 and WO 2 〇 04/08 3 1 69, which is incorporated herein in its entirety by reference. Furthermore, the polymers of the present invention can be obtained by NMP (polymerization of nitrogen oxide media), which is described in particular in U.S. Patent No. 4,458,429. These methods are described comprehensively, in particular in further references, in particular in K. Matyjaszewski, T.P. Davis, Handbook of Radical Polymerization, Wiley Interscience, Hoboken 020, which is incorporated herein by reference. This polymerization can be carried out under standard pressure, reduced pressure or elevated pressure. The polymerization temperature is also not critical. However, it is usually in the range of · 20 t - 2 0 0 T: preferably from 0 ° C to 130 ° C and more preferably from 60 ° C to 120 ° C. This polymerization can be carried out with or without a solvent. It should be understood that the term solvent herein is used in a broad sense. This polymerization is preferably carried out in a nonpolar solvent. These include hydrocarbon solvents such as 'aromatic solvents (eg, toluene, benzene, and xylene), saturated -26-201037072 hydrocarbons (eg, 'cyclohexane, heptane, octane, decane, decane, dodecane) It can also be in the form of a branch. These solvents may be used singly or in a mixture. Particularly preferred solvents are mineral oils, diesel fuels of mineral origin, natural vegetable oils and animal oils, biodiesel fuels and synthetic oils (e.g., ester oils such as dinonyl adipate) and mixtures thereof. Among them, very particularly good are mineral oil and mineral diesel fuel. The fuel composition of the present invention may contain other additives to achieve a particular solution to the problem. These additives include dispersants (eg, wax dispersants and dispersants for polar polar materials), deemulsifiers, defoamers, lubricating additives, antioxidants, hexadecane oxime modifiers, detergents, dyes, corrosion inhibition. And/or odorant. For example, the fuel composition of the present invention may comprise, for example, the ethylene copolymer of EP-A-1 541 663. These ethylene copolymers may contain from 8 to 21 mol% of one or more vinyl esters and/or (meth) acrylates and from 79 to 92% by weight of ethylene. Particularly preferred are ethylene copolymers containing from 1 to 18 mol% and specifically from 12 to 16 mol% of at least one vinyl ester. Suitable vinyl esters are derived from fatty acids having a straight or branched alkyl group having from 1 to 30 carbon atoms. Examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl laurate and vinyl stearate, and ethylene based on branched fatty acids. Alcohol esters such as vinyl isobutyrate, trimethyl vinyl acetate, vinyl 2-ethylhexanoate, vinyl isophthalate, vinyl neodecanoate, vinyl neodecanoate and neodecanoic acid Vinyl ester. Also suitable for the copolymer system system, the alkyl group has an acrylate and a methacrylate having 1 to 20 carbon atoms, such as (-27-201037072 methyl) acrylate, ethyl (meth) acrylate, Propylene acrylate (meth) acrylate, n-butyl acetonate and isobutyl acetonate, (meth) propyl hexanoate, octyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl ester, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, and these copolymers A mixture of two, three or four or more of the monomers. Particularly preferred three copolymers of vinyl 2-ethylhexanoate, vinyl neodecanoate and ethyl neodecanoate contain 3.5 to 20 mol%, preferably 8 to 15 mol%, in addition to ethylene. ) Vinyl acetate and 〇1 to 12 mol% (especially 0.2 to 5 mol%) special long-chain vinyl esters, and the total comonomer content is between 8 and 21 mol%, to It is preferably between 1 2 and 1 8 mol%. More preferred copolymers contain, in addition to ethylene and from 8 to 8 mole percent of vinyl ester, from 0.5 to 1 mole percent of olefins (e.g., propylene, butene, isobutylene, hexene, 4-methylpentene). , octene, diisobutylene and/or norbornene). The ethylene copolymer has a molecular weight corresponding to 140. (: The melt viscosity is from 20 to 10,000 mPas, especially from 30 to 5000 mPas and especially from 5 to 1 000 mPas. The degree of branching by 1H NMR spectroscopy is between 1 and 9 CH3/100 CH2. Preferably, especially between 2 and 6 CH3/100 CH2 groups, such as 2.5 to 5 CH3/100 CH2 groups, this is not derived from comonomers. This ethylene copolymer is described in detail in DE-A-34 43 475 , ΕΡ-Β-0 203 554, ΕΡ-Β-0 254 284, ΕΡ-Β-0 405 270, ΕΡ-Β-0 463 -28- 201037072 518> ΕΡ-Β-0 493 769, ΕΡ-0 778 875 , DE-A-196 20 118, DE-A-1 96 20 1 1 9 and EP-A-0 926 1 68. Preferred herein are ethylene-vinyl acetate copolymers and tri-copolymers, in addition to ethylene In addition to the vinyl acetate repeating unit, there are also (meth) acrylate repeating units. The configuration of these polymers may be 'for example, a random copolymer, a block copolymer or a graft copolymer. In a preferred system, The fuel composition of the invention may comprise from 0.0005 to 2% by weight, preferably from 0.01 to 0.5% by weight, of the ethylene copolymer. However, in terms of cost factors, it may be dispensed with in further systems. The above-mentioned ethylene copolymer in proportion, in which case, the fuel composition having a low proportion of these ethylene copolymers has excellent properties. In this particular system, the proportion of the ethylene copolymer is preferably at most 〇. 5% by weight, at most 0 · 0 0 1% by weight is more preferably and at most 0.00 1% by weight is optimal. In addition to the aforementioned components, the fuel composition may contain other components. These include, in particular, mineral-derived diesel fuel. The proportion of the diesel fuel of the Q source is preferably limited to at most 60% by weight, preferably at most 40% by weight and preferably at most 15% by weight. The fuel composition of the present invention has excellent low temperature properties. a repeating unit comprising a plurality of ester groups and comprising an unsaturated ester having 7 to 15 carbon atoms derived from an alcohol group contained therein and a repeating ester derived from an unsaturated ester having an alcohol group of 16 to 40 carbon atoms Further use of the polymer of the unit in a fuel composition comprising at least one biodiesel fuel fuel at a concentration of from 0.05 to 5% by weight as a flow modifier constitutes a further feature of the invention. More particularly, The pour point (PP) according to ASTM D97 is preferably lower than -29-201037072 or equal to 12 °c, lower than or equal to 1 (TC is better and lower than or equal to 0 °C. Based on the biodiesel fuel of the polymer used in the present invention, it is unexpectedly possible to achieve a pour point improvement of 1 ° C, preferably 3 ° C and 5 ° C optimum. The cold filter plugging point (CFPP) limit determined according to DIN ΕΝ 1 16 is preferably up to 12 ° C, preferably up to l ° ° C and preferably higher than ° ° C. In addition, it is considered that the preferred fuel composition has a cloud point (CP) 测 measured according to ASTM D2 500 which is preferably lower than or equal to 12 ° C, lower than or equal to 1 (TC is preferred and lower than or equal to More preferably, it is surprisingly possible to reduce the cloud point by using a polymer comprising a plurality of ester groups for use in the present invention. Even if the biodiesel fuel has a particularly high proportion of long chain saturated fatty acid units, this reduction is also As possible, this finding is particularly surprising because of the conventional flow improvers (especially polymers having, for example, ethylene-vinyl acetate (EVA) units) when cooled as fossil diesel fuel or fatty acid alkyl esters as spent fuel. It was developed to affect CFPP) and crystallizes with paraffin. This prevents further aggregation of individual crystals and ensures filterability of the fuel at relatively low temperatures. However, the formation of this primary crystal and their formation temperature are not affected. The effect of this additive. Since the cloud point is defined as the point of crystallization, it is apparent that the cloud point is hardly affected by this additive. Therefore, the present invention also provides to include a plurality of ester groups and is derived from a polymer having an alcohol group having an unsaturated ester of 7 to 15 carbon atoms and a repeating unit derived from an unsaturated ester having an alcohol group having 16 to 40 carbon atoms in an amount of 0.05 to 5% by weight The concentration will contain at least a cloud point of the fuel composition of the biodiesel fuel plus -30-201037072 for improved use. Here the 'cloud point can be reduced by at least 1. (:, to reduce at least 2 t Or at least 3 C is preferred and reduced by at least 5 t: optimal. These numbers are based on the cloud point of the biodiesel fuel without the addition of a polymer comprising a plurality of ester groups used in accordance with the invention. In the case where the amount of polymerization of the ester group is as low as at most 6% by weight, in many cases, the cloud point can be improved by at least 1 r, so that _ less than 3 ° C is preferred. The aspect of the shock is its excellent low temperature storage. Accordingly, the fuel composition of the present invention can be stored at temperatures even below the cloud point without any significant fuel separation or significant formation of precipitates, especially in the short term. In the event of an unexpected low temperature It is essential that the fuel composition of the present invention has a hexadecane oxime according to D IN 5 1 7 7 3 of preferably at least 50, at least 53 is preferred, at least 55 is particularly preferred and at least 58 〇 is optimal. The viscosity of the substance can be in a wide range, which can be adjusted according to the intended use. This adjustment can be carried out by selecting a biodiesel fuel. Further, the viscosity can be changed by the amount and molecular weight of the polymer containing a plurality of ester groups. The preferred fuel composition of the invention has a kinematic viscosity in the range of 1 to 10 square millimeters per second, preferably 2 to 5 square millimeters per second, and particularly preferably 2.5 to 4 square millimeters per second. Measured according to ASTM D445 at 40 °C. The invention will be hereinafter described with reference to the examples and comparative examples, but no limitation is imposed on the invention. EXAMPLES AND COMPARATIVE EXAMPLES General Procedure for Preparing Polymers 600 g of a monomer composition having a detailed composition according to each of the conditions in Table 1 was mixed with n-dodecyl mercaptan (depending on the desired molecular weight, 20 g/2 g). . 4 4.4 grams of this monomer/regulator mixture with 400 grams of oil (eg, 100 N mineral oil, synthetic dinonyl adipate or vegetable oil) - led to a stirrer, condenser, thermometer, In the 2 liter reaction bottle of the equipment for the pump and N2 feeding line. This equipment is inerted and heated to l ° ° C with the aid of an oil bath. The remaining amount of 5 5 5·6 g of the monomer/regulator mixture was blended with K4 g of butyl peroctoate. Once the mixture in the reaction flask reaches a temperature of 1 〇 〇 °C 'Add 〇 · 25 g of butyl peroctoate, while starting to pump the monomer/regulator/initiator mixture. At 1 〇 〇. <3 was added in a consistent manner over 211 minutes. Two hours after the end of the feed, an additional 1.2 grams of tributyl octanoate was added and the mixture was stirred at 1 Torr for an additional 2 hours. A 60% clear concentrate was obtained. The weight average molecular weight Mw and polydispersity index PDI of the polymer were determined by GPC. This assay was carried out in tetrahydrofuran at 35, and the polymethyl methacrylate calibration curve consisted of a group of 225 standards (p〇iymer S tandards S ervice or P 〇1 ymer L ab 〇ratories ), M Peak is distributed in the range of 5x1 06 to 2x1 02 g/mole in logarithmic scale. A combination of /, a column (Polymer Standards Service SDV 10〇A/2x SDV LXL/2x SDV 10〇A/Shodex KF-800D) was used. Record the signal using the -32- 201037072 RI detector (Agilent 1100 Series). Table 1: Properties of the polymer used Polymer monomer composition (weight ratio) Mw [g_] PDI (Mw/Mn) Example 1 SMA-LMA 60-40 98 300 2.25 Example 2 SMA-LMA 60-40 39400 2.12 Example 3 SMA-LMA-BhMA-IDMA 40-40-10-10 44 000 2.25 Comparative Example 1 DPMA-HEMA 90-10 22 000 1.93 Comparative Example 2 DPMA 100 65 600 2.08 SMA: contains 16 to 18 alkyl groups Alkyl methacrylate LMA of carbon atom: an alkyl group having an alkyl group having about 10 carbon atoms, the alkyl group being mainly a linear one

BhMA: an alkyl methacrylate having an alkyl group having about 22 carbon atoms 〇 ID Μ A: an alkyl methacrylate having an alkyl group having about 10 carbon atoms, the alkyl group being mainly a brancher DPMA: an alkyl methacrylate having an alkyl group of 12 to 15 carbon atoms, HEMA: 2 hydroxyethyl methacrylate, which is then obtained from a wide variety of biodiesel compositions. polymer. Here, more particularly, fatty acid methyl ester formed from Indian jatropha oil (having 15.0% by weight of methyl palmitate and 6.8 wt% of methyl stearate) (JME), from North America Produced soybean oil (having -33- 201037072 1 〇. 7 wt% of methyl palmitate and 4.1 wt% of methyl stearate) (SME) formed by fatty acid methyl ester and palm oil from Malaysia ( A fatty acid methyl ester formed by 43.7 wt% of methyl palmitate and 4.4 wt% of methyl stearate (PME). The amount of the polymer used in each case was 600 ppm. To investigate the low temperature properties, the cloud point (CP) of the fuel composition (according to ASTM D25 00) and low temperature storage were measured. To assess the effect of additives on the storage of FAME, samples with or without additives were stored at a temperature below the cloud point for 72 hours (cold storage test, CST). This is done in a Julabo extremely cold thermostat. After 24 and 72 hours, the samples were visually evaluated. The sample was graded to 1-1. Use methyl ester of soy bean oil (SME) from North America and methyl ester of palm oil (PME) from Malaysia. Table 2 Evaluation of biodiesel samples after storage 1 Samples are fully cured 2 A liquid appears on the solid body 3 A significant amount (2 5% · 50%) of the liquid is on the solid layer 4 A large amount of liquefied sample (50%+ ) a solid layer of 5 liquid layers on the solid layer but apparently m. liquid Π2Χ. layer but a small amount, t~T condensed solid layer 7 liquid layer on a small amount of sediment 8 sample liquid slightly turbid with a small amount of solid Sediment 9 Samples are all liquid but turbid. 10 Samples are all liquid but transparent. The results are shown in Tables 3, 4 or Table 4. -34- 201037072

Table 3: Cloud point of the fuel composition (CP) Proportion of polymer polymer used in the mixture [% by weight] Cloud point rc according to ASTM D2500 > JME] Cloud point measured according to ASTM D2500 'PME [ °C] Not added - 5 14 Example 1 0.6 1 11 Example 2 0.6 2 12 Example 3 0.6 1 11 Comparative Example 1 0.6 3 14 Comparative Example 2 0.6 3 14 Table 4: Polymer used for storage of SME at -5 ° C The proportion of polymer in the mixture f weight 24 hours after the cold storage test (CST) evaluation 72 hours after the cold storage test (CST) evaluation is not added - 3 3 Example 1 0.6 8 8 Example 2 0.6 9 9 Example 3 0.6 8 8 Comparative Example 1 0.6 3 3 Comparative Example 2 0.6 3 3 -35- 201037072 Table 5: Proportion of polymer polymer used in the storage of PME at 10 ° C in the mixture [Military halo%] Cold storage test after 24 hours (CST) Evaluation of cold storage test (CST) evaluation after 72 hours without addition - 1 1 Example 1 0.6 6 5 Example 2 0.6 7 6 Example 3 0.6 6 5 Comparative Example 1 0.6 1 1 Comparative Example 2 0.6 1 1 Front The data shown clearly shows that by adding a polymer containing multiple ester groups, The surprisingly low temperature storage of fuel compositions with biodiesel components was surprisingly achieved. -36-

Claims (1)

201037072, VII. Patent application scope: 1. A fuel composition comprising at least one biodiesel fuel, characterized in that the fuel composition comprises 0.05 to 5% by weight of at least one polymer comprising a plurality of ester groups, The polymer comprises a repeating unit derived from a repeating unit of an ester monomer having an alcohol group of *16 to 40 carbon atoms, and an ester monomer derived from an alcohol group having 7 to 15 carbon atoms, and The polymer having a plurality of ester groups has a weight average molecular weight in the range of 5,000 to 100,000 g/mole. The fuel composition of claim 1, wherein the fuel composition contains at least 80% by weight of a biodiesel fuel. 3. The fuel composition of claim 1 or 2, wherein the polymer comprising a plurality of ester groups is selected from the group consisting of polyalkyl (meth)acrylates (PMA), polyalkylene fumarates, and/or Or polyalkyl maleate. 4. The fuel composition according to claim 1 or 2, wherein the polymer comprising a plurality of ester groups contains 40 to 70% by weight of an ester having 16 to 40 carbon atoms derived from the contained q-alcohol group. The unit of the body. 5. The fuel composition according to claim 1 or 2, wherein the polymer comprising a plurality of ester groups contains 30 to 60% by weight of an ester monomer derived from 7 to 15 carbon atoms of the alcohol group contained Unit. 6. The fuel composition of claim 1 or 2, wherein the polymer comprising a plurality of ester groups is obtained by polymerizing a monomer mixture comprising: 〇 to 40% by weight - or a plurality of formulas (I) ethylenically unsaturated ester compound-37- 201037072 Wherein R is hydrogen or methyl, and Ri is a straight or branched group having from 丨 to 6 carbon atoms. Each of R2 and R3 is independently a hydrogen or a group of the formula _c〇〇R, wherein R' is Hydrogen or an alkyl group having 1 to 6 carbon atoms, 1 to 98 parts by weight or a plurality of ethylenically unsaturated ester compounds of the formula (^) OR4 (II) wherein R is hydrogen or methyl 'R4 is a straight or branched alkyl group having 7 to 15 carbon atoms', and each of R5 and R6 is independently hydrogen or a group of the formula _c〇〇R, , wherein R" is hydrogen or an alkyl group having 7 to 15 carbon atoms, and 0.1 to 80% by weight - or a plurality of ethylenically unsaturated ester compounds of the formula (ΠΙ) (III) wherein R is hydrogen or methyl 'R7 is a straight or branched alkyl group having from 16 to 40 carbon atoms', each of R8 and R9 is independently hydrogen or a group of the formula -COOR,,, wherein R " is hydrogen or an alkyl group having 16 to 40 carbon atoms. 7. The fuel composition of claim 1 or 2, wherein the ester group derived from the alcohol group having 7 to 15 carbon atoms is derived. The weight ratio of the repeating unit of the body to the repeating unit of the vinegar monomer having 16 to 40 carbon atoms derived from the alcohol group contained is in the range of 1:1 to 1:3. -38- 201037072 8. Patent application The fuel composition of item 1 or 2, wherein the biodiesel fuel comprises a fatty acid ester derived from a monohydric alcohol having 1 to 4 carbon atoms. 9. The fuel composition of claim 8 Wherein the monoester is a methyl ester. The fuel composition of claim 9, wherein the fuel composition comprises at least 6% by weight of methyl palmitate and/or methyl stearate Q ❹ II. The fuel composition of claim 1 or 2, wherein the biodiesel fuel comprises at least 35% by weight of saturated fat The ester, the fatty acid group of the saturated fatty acid ester having at least 16 carbon atoms. 12. The fuel composition of claim 1 or 2, wherein the biodiesel fuel is derived from palm oil, soybean oil, jatropha oil ( jatropha oil ) or animal fat, in particular tallow, chicken fat or lard. 1 3 The fuel composition of claim 1 or 2, wherein Q the fuel composition comprises at least one additive. The fuel composition of claim 12, wherein at least one additive is selected from the group consisting of a dispersant, a deemulsifier, an antifoaming agent, a lubricating additive, an antioxidant, a hexadecane oxime modifier, a detergent 'dye, a uranium sulphide inhibitor And a odorant. The fuel composition according to claim 1 or 2, wherein the fuel composition contains 〇 1 to 1% by weight of at least one polymer comprising a plurality of vine groups. A fuel composition according to claim 1 or 2, wherein -39-201037072 the fuel composition comprises up to 0.05% by weight of an ethylene copolymer. 1 7. The polymer is contained in at least one biodiesel The fuel composition of the fuel is used as a flow improver at a concentration of from 5 to 5% by weight of the polymer, the polymer comprising a plurality of ester groups and comprising from 7 to 15 carbon atoms derived from the alcohol group contained a repeating unit of a saturated ester and a repeating unit derived from an unsaturated ester having an alcohol group of 16 to 40 carbon atoms. 18. The polymer will contain at least one kind at a concentration of 5 to 5% by weight. A cloud point of a fuel composition of a biodiesel fuel for improved use, the polymer comprising a plurality of ester groups and comprising repeats derived from unsaturated esters having from 7 to 15 carbon atoms in the alcohol group contained The unit and the repeating unit derived from the unsaturated ester having an alcohol group of 16 to 40 carbon atoms. 1 9 . For use in claim 18, wherein the cloud point is reduced by at least 3 °C. 20. Use of a polymer to improve the low temperature storage of a fuel composition comprising at least one biodiesel fuel at a concentration of from 5 to 5% by weight, the polymer comprising a plurality of ester groups and comprising derivatives A repeating unit of an unsaturated ester having 7 to 15 carbon atoms from the alcohol group contained and a repeating unit derived from an unsaturated ester having an alcohol group of 16 to 40 carbon atoms. -40- 201037072 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: none -3- 201037072 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none