BRPI0821204B1 - Biodiesel fuel composition, and method for improving the cold flow properties of a biodiesel fuel composition - Google Patents

Description

"BIODIESEL FUEL COMPOSITION AND METHOD FOR IMPROVING COLD FLOW PROPERTIES OF A BIODIESEL FUEL COMPOSITION" The present invention is directed to the use of controlled free radical polymerization (meth) acrylate polymers or copolymers mediated by nitroxyl as cold flow enhancers in biodiesel (or biofuel) fuel and biodiesel compositions incorporating said polymers or copolymers.

Biodiesel is an alternative renewable fuel made from vegetable oils, fats, greases or other sources of triglycerides. It is a non-toxic and biodegradable substitute and supplement for petroleum diesel.

Biodiesel fuels comprise lower alkyl fatty acid esters, prepared for example by transesterifying triglycerides with lower alcohols, for example methanol or ethanol. A typical biodiesel fuel is rapeseed or soybean oil fatty acid methyl ester. Biodiesel fuel and its preparation are shown for example in the descriptive reports in U.S. Patent Nos. 5,578,090, 5,713,965, 5,891,203, 6,015,440, 6,174,501 and 6,398,707.

One of the main problems associated with the use of biodiesel is its poor cold flow properties that result from crystallization of saturated fatty compounds under cold conditions.

A 20 ° C reduction in the cold filter plugging point is required for some biodiesel fuels to find utility in colder climates such as those of the United States and Europe in winter. It is known to add pour point reducers or cold flow additives to conventional petroleum based fuel oil in order to improve its cold flow properties.

Long chain poly (meth) alkyl acrylates are a class of petroleum based pour point reducing additives. These compounds are described, for example, in U.S. Patent Specification Reports Nos. 2,091,627, 2,100,993, 2,114,233 and 4,867,894.

Attempts have been made to apply the same long chain polyalkyl (meth) acrylates to improve the cold flow properties of biodiesel fuels.

U.S. Patent Nos. 6,203,585 and 6,391,996 describe a biodiesel fuel composition having a low pour point comprising a copolymer additive formed from long chain alkyl (meth) acrylate monomers.

Many different well-established methods are available for polymerizing these long chain polyalkyl (meth) acrylates. Most methods have the disadvantage that uncontrollable initiator radical recombination reactions can occur immediately after their formation with the effect that variable ratios of initiator radicals and stable free radicals are produced. Consequently, in some cases there is inefficient control of the polymerization process.

Group Transfer Polymerization (GTP) is a well-established method for producing A-B block copolymers of defined structure from methacrylate monomers. Despite its wide applicability and usefulness the GTP method still has several disadvantages. Polymerization initiators used in this method, such as the silyl ketene acetals described in US Patent Specification No. 4,656,226, for example 1-trimethylsilyloxy-1-isobutoxy-2-methylpropene, are highly reactive and difficult to prepare in a multiple step synthesis. This requires the use of carefully dried and purified reagents, which limit this method in large scale industrial applications.

US Patent Specification Nos. 5,763,548 and 6,407,187 describe a controlled or "live" polymerization process of ethylenically unsaturated polymers, such as styrene or (meth) acrylates, using the Atomic Transfer radical polymerization method. (ATRP). This method produces defined oligomeric homopolymers and copolymers, including block copolymers. Primers are used which generate radical atoms such as 'Cl' in the presence of a transition metal redox system of different oxidation states, for example Cu (I) and Cu (II) providing 'live' radical polymerization. or controlled. U.S. Patent Specification No. 6,391,996 uses only such a system for the production of polyalkyl (meth) acrylates for biodiesel applications.

A general disadvantage of this prior art method is that the ATRP prepared polymer chains contain halogen as the terminal fragment, which was transferred from the polymerization initiator. Halogen content is undesirable in polymers. Halogen, especially chlorine and bromine, is subject to removal as hydrogen halide depending on temperature, especially above 150 ° C. The double bond thus formed is subjected to a reaction with atmospheric oxygen, which decreases the antioxidant resistance of the polymer. In addition, hydrogen halide released from the polymer reacts with other functional groups present in the polymer, such as ester groups present in acrylates. Depending on the type of polymer, chlorine is also removed as a radical, which could initiate undesirable chain reactions in the polymer structure. Removal of halogen from the polymer backbone, especially from the terminal position of the polymer chain, and its replacement with suitable substituents in a subsequent process step is described in U.S. Patent No. 6,433,100. Another disadvantage for ATRP is the removal of the copper catalyst from the final product. Copper is a pro-oxidant and should be avoided for fuel and lubricant applications because it can catalyze rapid oxidation. In applications such as biodiesel, the presence of copper is especially affected because biodiesel is less stable with respect to oxidation than conventional petroleum diesel. U.S. Patent No. 4,581,429 describes a free radical polymerization process by the controlled or "live" growth of polymer chains. One specific embodiment of the process is the use of primers of the partial formula R'R 'N-0-X. In the polymerization process, the free radical species R'R ”N-0 · and · Χ are generated. X is a free radical group, for example a tert-butyl or cyanoisopropyl radical, capable of polymerizing monomeric units containing ethylene groups. Monomeric units A are replaced by the R'R ”N-0 · and 'X primer fragments and polymerize to structures of the type: R'R” N-0-A-X (A: polymer block). Specific N-O-X R'R primers mentioned are derived from cyclic structures such as 2,2,6,6-tetramethylpiperidine, or open-chain molecules such as di-tert-butylamine.

Recently some alternative polymerization regulators have been published. WO 98/30601 describes heterocyclic> N-O-R compounds suitable for controlled polymerization processes. WO 98/13392 describes open chain alkoxyamines, which are derived from NO gas or nitrous compounds. The advantage of these prior art polymerization methods over the ATRP method is that no subsequent substitution of terminal groups of the polymer chains is required.

The preparation of alkyl (meth) acrylate polymers or copolymers by nitroxyl-controlled free radical polymerization (CFRP) has been found to provide well-controlled (co) polymers of molecular weight and polydispersibility without problematic end groups or contamination by copper produced by ATRP methods. In addition, CFRP polymeric (meth) acrylates are effective as cold flow enhancers for biofuels. The invention encompasses a biodiesel fuel composition comprising A polymer or copolymer of formula (I) (I) obtained by nitroxyl-controlled free radical polymerization wherein In is the initiator fragment starting from the polymerization reaction; E is a group carrying at least one stable free nitroxyl radical which is attached via an oxygen atom to the polymer or copolymer; or a group resulting from a substitution or elimination reaction of the bound stable free nitroxyl radical;

Poly is any polymer or copolymer formed from ethylenically unsaturated monomer (s); Y is a number 1 or greater than 1 indicating the average number of end groups E attached to Poly. The final group E is preferably. Biodiesel fuel will normally comprise about 2.0 to about 99.8% by weight of the biodiesel fuel composition. The polymer or copolymer will in particular constitute about 0.05 to about 20.0% by weight of the composition. The wt% is based on the total biodiesel fuel composition, preferably about 0.1 to about 15.0 wt%, most preferably about 0.5 wt% to about 10.0 wt%. The total biodiesel fuel composition may optionally contain other additives. The invention also includes a method for improving the cold flow properties of a biodiesel fuel composition, which steps comprise adding to a biodiesel fuel at least 0.05% by weight of the polymer of formula (I) described above, where the% by weight is based on the total biodiesel fuel composition. The term (meth) acrylate or (meth) acrylic within its scope includes methacrylate, acrylate and acrylic, methacrylic acid.

Monomer refers to an ethylenically unsaturated compound prior to polymerization. Once the monomer is polymerized, the monomer becomes a monomeric unit or monomeric repeating unit constituting the polymers.

Biodiesel fuel refers to renewable fuel made from vegetable or animal oils, fats, greases or other sources of triglycerides. Most commonly, biodiesel fuels comprise lower alkyl fatty acid esters, prepared for example by transesterifying triglycerides with lower alcohols, for example methanol or ethanol. A typical biodiesel fuel is rapeseed or soybean oil fatty acid methyl ester. A non-exhaustive list of vegetable or animal oils may include rapeseed, soybean, palm oil, palm olein, palm stearin, palm kernel oil, coriander oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow, bone oil, fish oils, used cooking oils and mixtures thereof.

Biodiesel fuels can also be esterified with alternative alcohols such as butyl, isopropyl, 2-butyl and tert-butyl. U.S. Patent Specification No. 5,520,789 describes such liquid fatty acid esters combined with petroleum distilled fuel. The combination is supposed to reduce the crystallization temperature of the combination.

Thus the present invention also includes combinations of biodiesel fuel with petroleum distillates and the polymer described above by formula (I).

Poly in formula (I) above refers to any polymer or copolymer formed by controlled nitroxyl-mediated free radical polymerization. Poly can be of any architecture such as block, random, honeycomb, star or gradient. The term block copolymer comprises random, multiblock, stellar or gradient block copolymers.

All possible polymeric chain structures are comprised: for example linear or branched. If the monomers are selected from chemically different monomers, all possible monomeric sequence structures are comprised, for example, randomized, block-like, multiblock, tapered, or gradient arrangement of the different monomers.

Under gradient polymers or gradient arrays there are comprised block copolymers which are prepared in such a way that the intersection between the two blocks is not a sharp boundary, but represents a continuous transition from one type of monomer to another type. monomer, that is, both monomers extending to both blocks. These types of polymer can be obtained when the polymerization process is carried out for example in one step using monomers of different copolymerization parameters or by a multi-step procedure, wherein the monomer composition is gradually changed by adding appropriate amounts of another one. monomer type. Another preferred procedure for the synthesis of gradient polymers is by the use of continuous feed processes, where for example controlled polymerization is initiated with a first monomer and before completing conversion a second monomer is continuously fed to the reaction mixture. thereby making a continuous transition along the polymer chains.

Because nitroxyl-mediated controlled free radical polymerization is a “near live” polymerization, it can be started and stopped almost at will. In addition, the polymeric product retains the functional alkoxyamine group allowing for further polymerization in a living matter. Thus, since the first monomer is consumed in the initial radical polymerization step, a second monomer can then be added to form a second block in the growing polymer chain in a second polymerization step. Therefore it is possible to perform additional polymerizations with the same or different monomer (s) to prepare multiblock copolymers.

Since this is an “almost alive” radical polymerization, the blocks can be prepared in essentially any order. One is not necessarily restricted to the preparation of block copolymers where the sequential polymerization steps must flow from the less stabilized polymer intermediate to the most stabilized polymer intermediate, as is the case with ionic polymerization. Thus it is possible to prepare a multiblock copolymer wherein a polyacrylonitrile or a poly (meth) acrylate block is prepared first, then a styrene or butadiene block is attached thereto, and so on.

Random copolymers, tapered or gradient copolymer structures can be synthesized equally using a mixture of monomers or by adding a second monomer before the first one is completely consumed.

Thus the Poly for example may be a block copolymer A and B comprising at least two different repeating units of polymerizable ethylenically unsaturated monomers.

These ethylenically unsaturated monomers are characterized by the presence of at least one group> C = C <. Representative monomers are styrenes, substituted styrenes, (meth) acrylic acid, (meth) acrylic acid (C1-C36) alkyl esters, (C1-C30) hydroxyalkyl esters or (meth) acrylic acid (C1-C30) polyhydroxy, (meth) acrylic esters of alkoxylated alcohols such as ethoxylated fatty alcohols, C2 -C4 polymethylene glycol esters (meth) acrylics, (meth) acrylic esters of alkoxylated phenols such as ethoxylated nonylphenol, (meth) C1-6 alkyl esters acrylic esters which are substituted by amino, (C1-C30) N-monoalkyl (meth) acrylamide, Ν, (C1-C30) dialkyl (meth) acrylamide, (C1-C30) alkyl mono- or disubstituted groups (meth) ) acrylamides which may be further unsubstituted or substituted by amino or mixtures thereof.

Suitable styrenes may be substituted on the phenyl group by one to three additional substituents selected from the group consisting of hydroxy, C1-C4 alkoxy, for example methoxy or ethoxy, halogen, for example chlorine, and C1-C4 alkyl, for example methyl or methyl . Suitable (meth) acrylic acid (C1 -C36) alkyl esters for example may be methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl (meth) acrylates. , isobomyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl n-octadecyl. Also envisioned are (meth) acrylate long chain alkyl esters such as stearyl (meth) acrylate, octadecyl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, (meth) henicosyl acrylate, (meth) docosyl acrylate, (meth) tricosyl acrylate, (meth) tetracosyl acrylate, (meth) pentacosyl acrylate, (meth) hexacosyl acrylate, (meth) octacosyl acrylate, ( nonacosyl methacrylate, triacontyl methacrylate, beenyl methacrylate and mixtures thereof.

(Meth) acrylate esters may be branched or unbranched. (C 1 -C 30) hydroxyalkyl esters of (meth) acrylic acid are for example C 1 -C 4 alkyl hydroxyl (meth) acrylates such as (meth) acrylic-2-hydroxyethyl esters (HEA, HEMA) or (meth) acrylic acid 2 -hydroxypropylester (ΗΡΑ, HPMA). Suitable (meth) acrylic acid (C1 -C30) polyhydroxy esters are for example C3 -C6 (meth) acrylic acid C3 -C6 polyhydroxy alkyl esters such as ethylene glycol or glycerol esterified (meth) acrylic acid .

Representative C1-C4 (meth) acrylic acid esters having C2-C4 polyalkylene glycol ester groups, wherein the ester groups may be substituted with C1-C24 alkoxy groups, are illustrated by the formula given below: wherein n represents a numeral from one to 100; preferably 2 to about 20.

R 1 and R 2 independently of each other represent hydrogen or methyl; and R3 represents C1-C24 alkyl, for example methyl, ethyl, n- or isopropyl, n-, iso-, or tert-butyl, n- or neopentyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl . Representative (meth) acrylic acid (C1-C30) alkyl esters which amino-substituted esters are for example C1-C4 dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, (dimethylaminopropyl (meth) acrylate, ( diethylaminoethyl methacrylate and diethylaminopropyl (meth) acrylate.

Representative examples of (C1 -C30) N-monoalkyl (meth) acrylamide, or α, α-dialkyl (C1-C30) acrylamide, mono- or disubstituted (C1 -C30) alkyl groups which may additionally be substituted by amino are for example N- (C 1 -C 4) monoalkyl or N, N-C 1-4 dialkyl (meth) acrylamide such as 2-dimethylaminoethyl (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide, 2-diethylaminoethyl (meth) acrylamide, (meth) ) 2-t-butylaminoethyl acrylate and 3-diethylaminopropyl (meth) acrylamide.

Representative mono and N-disubstituted (C1-C30) (meth) acrylamides may be for example (C1-C4) alkyl, (meth) acrylamide, such as N-ethyl (meth) acrylamide, Ν, Ν-dimethyl, (meth) ) acrylamide and N, N-diethyl (meth) acrylamide.

Poly may be for example a mono, di, tri or tetra block copolymer or higher. Each block may be formed of one or more monomers but each block will differ in at least one characteristic. For example, each block may contain different comonomers, different comonomer contents, molecular weights and / or degrees of branching.

Representative examples include mono block nitroxyl-mediated controlled free radical polymerization polymers of the formula (li) In- (A) n- (E) y (10, wherein E and In are defined as above and y is a number 1 or greater than 1 indicating the average number of end groups E attached to (A) n, n is a number from 1 to 5000 and A is a polymer block.

Examples such as n-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, of stearyl, 2-hydroxypropyl (meth) acrylate and α, β-dimethyminopropyl (meth) acrylamide are envisioned.

Representative examples include diblock nitroxyl-mediated controlled free radical polymerization polymers of the formula (I '). In- (A) „(B) m- (E) y (I2), wherein a and B are polymer blocks, E , In, n, y are defined as above and n is a number from 1 to 5000.

Diblock nitroxyl-controlled controlled free radical polymerization polymers such as 2-hydroxyethyl n-ethylhexyl-b- (meth) acrylate, n-ethylhexyl-b- (meth) acrylate (meth) acrylate 2-dimethylaminoethyl, n-ethylhexyl-b- (meth) acrylate, 2-hydroxypropyl (meth) acrylate, n-ethylhexyl-b- (meth) acrylate t-butyl (meth) acrylate b-acrylic acid-ethylhexyl, n-ethylhexyl-b-β (meth) acrylate, 2-hydroxyethyl n-butyl-b- (meth) acrylate (meth) acrylate, ( n-ethylhexyl-b- (meth) acrylate lauryl methacrylate and 2-hydroxyethyl b-(meth) acrylate la-methacrylate.

Corresponding random copolymers should also be mentioned as another possible class of copolymers. In this case “-co-” would apply instead of “-b-” as above. Yet another class of copolymers would be "gradient" copolymers. In this case “-grad-” would apply instead of “-b-” as above. The diblock may contain a single homopolymer block and a random copolymer such as n-ethylhexyl-b-block (2) -hydroxyethyl (meth) acrylate (meth) acrylate (meth) acrylate. The block copolymer may be modified after the blocks are formed. For example, a t-butyl (meth) acrylate block can be easily hydrolyzed to produce a (meth) acrylic acid block. An n-butyl (meth) acrylate block could be transesterified with a long chain alcohol such as stearyl, lauryl alcohol or n-ethylexyl alcohol. Transesterification long chain alcohols may be branched or unbranched.

Transesterification reactions may be performed by known methods. For example a polymer block containing lower C1-C4 alkyl (meth) acrylate may be treated with a transesterification catalyst such as well-known catalysts selected for example from tetraisopropylthitanate, tetra-butyltitanate, alkaline or alkaline earth alcoholates such as NaOMe or LiOMe in the presence of a long chain alcohol such as C8 -C36 alcohols.

Representative examples of long chain alcohols and reaction conditions for such transesterification reactions in preformed polymers manufactured by nitroxyl mediated polymerization can be found in W02006 / 074969.

Thus the biodiesel composition wherein the polymer of formula I is obtained by free radical nitroxyl mediated polymerization can be subsequently modified by a transesterification reaction.

Representative examples include triblock nitroxyl-mediated controlled free radical polymerization polymers of the formula (I3) (I3), wherein A, B and C are polymer blocks and E, In, n, m, y are as defined above and p is a number from 1 to 5000.

Representative examples of triblock may be n-butyl-b- (meth) acrylate stearyl-bN (meth) acrylate, N-dimethylpropylamino (meth) acrylamide and n-butylbutyl (meth) acrylate lauryl-bN, N dimethylpropylamino (meth) acrylamide.

Representative examples include tetrablock nitroxyl-mediated controlled free radical polymerization polymer of formula (I4) (I4), wherein A, B, C and D are polymer blocks and E, In, n, m, yep are defined as above and o is a number from 1 to 5000.

Examples of tetrablock are n-butyl-n- butyl-b- (meth) acrylate n-hexylethyl-b- (meth) acrylate stearate-bN, N-dimethylpropylamino (meth) acrylamide, n-butyl methacrylate n-lauryl butyl-b- (meth) acrylate stearyl-b- (meth) acrylate, β-dimethylpropylamino (meth) acrylamide and n-butyl-b- (meth) acrylate (meth) acrylate polyethylene glycol b- (meth) acrylate.

Polymer or copolymers of formula (I), component ii) are prepared by controlled nitroxyl-mediated free radical polymerization (CFRP) as described in U.S. Patent No. 4,581,429.

This reference describes a controlled or "live" growth free radical polymerization process of polymer chains which produces defined oligomeric homopolymers and copolymers, including block and graft copolymers. The use of primers of the partial formula R 'R' N-0-X is described. In the polymerization process the free radical species R'R ”N-0 · and 'X are generated. · Χ is a free radical group, for example a tert-butyl or cyanoisopropyl radical, capable of polymerizing monomeric units containing ethylene groups.

A variation of the above process is described in US Patent Specification No. 5,322,912 wherein the combined use of a free radical initiator and a stable free radical agent of the basic structure R'R ”N-0 for the synthesis of homopolymers and block copolymers are described.

These processes are useful for preparing homogeneous, random, tapered, graft, block or alveolar (co) polymers which have a narrow molecular weight distribution and consequently a low polydispersibility index. Thus the polydispersibility index ranges from about 1.1 to about 2.5.

The polymers or copolymers are obtained by nitroxyl-controlled free radical polymerization (CFRP). There are essentially two suitable routes: bl) Polymerization in the presence of alkoxyamine initiator / regulator compounds having the structural element and b2) Polymerization in the presence of a stable nitroxyl free radical having the structural element and a radical initiator (free radical source) ).

For example, the structural member may be part of a cyclic ring system or substituted to form an acyclic structure.

Suitable nitroxyl ethers and nitroxyl radicals are principally known from US-A-4,581,429 or EP-A-621,878, incorporated herein entirely by reference. Particularly useful are the open chain compounds described in WO 98/13392, WO 99/03894 and WO 00/07981, the piperidine derivatives described in WO 99/67298 and GB 2335190 or the heterocyclic compounds described in GB 2342649 and WO 96 / 24620.

Other suitable nitroxyl ethers and nitroxyl radicals are described in WO 02/4805 and WO 02/100831.

Nitroxyl ethers and nitroxyl radicals with more than one nitroxyl group in the molecule are for example described in U.S. Patent Specification 6,573,347, WO 01/02345 e. These compounds are ideally suited when branched, stellar or alveolar (co) polymers are prepared. In this case y in formula (I) above is greater than 1.

In the context of the description of the present invention the terms alkoxyamine and nitroxylether are used as equivalents.

Stable free radicals having a structural element are for example described in EP-A-621 878.

Examples such as are given in WO 96/24620.

Preferably the structural elements are part of a 5- or 6-membered heterocyclic ring, which optionally has an additional nitrogen or oxygen atom in the ring system. Substituted piperidine, morpholine and piperazine derivatives are particularly useful. Preferably the structural element is a structural element of formula (II) and the structural element is a structural element of formula (ΙΓ) wherein Gu G2, G3, G4 are independently C1 -C6 alkyl or Gi and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5 -C12 cycloalkyl group; G 5, G 6 independently are H, C 1 -C 6 alkyl, phenyl, naphthyl or a COOC 1 -C 8 alkyl group; X is selected from the group consisting of -CH2-phenyl, CH3CH-phenyl, (CH3) 2C-phenyl, (C5-C6 cycloalkyl) 2CCN, (CH3) 2CCN, -CH2CH = CH2, CH3CH-CH = CH2 (C-alkyl) , -C4) CR20-C (= O) -phenyl, (C1 -C4) alkyl-CR20-C (= O) -C (C1 -C4) alkoxy, (C1-C4) alkyl-CR20-C (= O) alkyl (C1 -C4) alkyl (C1 -C4) CR20 -C (= O) -N (C1 -C4) dialkyl, (C1 -C4) alkyl-CR20 -C (= O) -NH (C1 -C4) alkyl, (C1-C4) alkyl-CR20-C (= O) -NH2, where R2o is hydrogen or (C1 -C4) alkyl and * denotes a valence.

In particular the structural element of formula (II) is of formula A, B or O, where m is 1, R is hydrogen, C1 -C8 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical of an aliphatic carboxylic acid having 2 to 18 C atoms, a cycloaliphatic carboxylic acid having 7 to 15 C atoms, or an α, α-unsaturated carboxylic acid having 3 to 5 C atoms or one aromatic carboxylic acid having 7 to 15 C atoms; foot 1;

R 10 is C 1 -C 6 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 18 alkanoyl, C 3 -C 5 alkenyl or benzoyl; R102 is C1 -C18 alkyl, C5 -C7 cycloalkyl, C2 -C8 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH (OH) -Z or the formula -CO- Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; G is hydrogen and G5 is hydrogen or C1 -C4 alkyl, G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl; and X is selected from the group consisting of -CH 2 -phenyl, CH 3 CH-phenyl, (CH 3) 2 C-phenyl, (C 5 -C 6 cycloalkyl) 2CCN, (CH 3) 2 CCN, -CH 2 CH = CH 2, CH 3 CH-CH = CH 2 (alkyl (C 1 -C 4) CR 20 -C (= O) -phenyl, (C 1 -C 4) alkyl-CR 20 -C (= O) -C 1 -C 4 alkoxy, (C 1 -C 4) alkyl-CR 20 -C (= O) - (C1 -C4) alkyl, (C1 -C4) alkyl CR2 -C (O) -N-dialkyl to (C1 -C4), (C1 -C4) alkyl-CR20 -C (= O) -NH (C1 -C4) alkyl , (C1 -C4) alkyl-CR20 -C (= O) -NH2, where R20 is hydrogen or (C1 -C4) alkyl.

The above compounds and their preparation are described in GB 2,335,190 and GB 2,361,235.

Another preferred group of nitroxyl ethers are those of formula (IIc), (Ild), (Ile), (Ilf), (Ilg) or (Ilh) wherein R201, R220, R203 and R210 independently of each other are C1-6 alkyl. C18, C3 -C18 alkenyl, C3 -C18 alkynyl, C1 -C18 alkyl, C3 -C18 alkenyl, C3 -C18 alkynyl which are substituted by OH, halogen or a group -OC (= O) -R205, C2 -C18 alkyl is interrupted by at least one O and / or NR205 group, C3 -C12 cycloalkyl or C0 -C10 aryl or R210 aryl and R202 and / or R203 and R204 together with the bonding carbon atom form a C3 -C12 cycloalkyl radical; R2os; R206 and R207 independently are hydrogen, C1 -C8 alkyl or C6 -C10 aryl; R208 is hydrogen, OH, C1 -C8 alkyl, C3 -C18 alkenyl, C3 -C18 alkynyl, C1 -C18 alkyl, C3 -C18 alkenyl, C3 -C8 alkynyl which are substituted by one or more OH, halogen or a -OC group (= O) -R205, C2 -C18 alkyl which is interrupted by at least one O atom and / or group NR203, C3 -C2 cycloalkyl or C6 -C10 aryl, C7 -C9 phenylalkyl, C5 -C10 heteroaryl, - C (= O) C 1 -C 18 alkyl, C 1 -C 8 alkyl or C 1 -C 8 alkyl; R209, R210, R211 and R212 are independently hydrogen, phenyl or C1 -C8 alkyl; and X is selected from the group consisting of -CH 2 -phenyl, CH 3 CH-phenyl, (CH 3) 2 C-phenyl, (C 5 -C 6 cycloalkyl) 2CCN, (CH 3) 2 CCN, -CH 2 CH = CH 2, CH 3 CH-CH = CH 2 (alkyl (C 1 -C 4) CR 20 -C (= O) -phenyl, (C 1 -C 4) alkyl-CR 20 -C (= O) -C 1 -C 4 alkoxy, (C 1 -C 4) alkyl -CR 20 C (= O) (C 1 -C 4) alkyl, (C 1) alkyl -C4) -CR20 -C (= O) -N-C 1-4 dialkyl, (C1 -C4) alkyl-C20 -C (= O) -NH (C1 -C4) alkyl, (C1 -C4) alkyl-CR20 -C (= O) -NH 2, where R 20 is hydrogen or C 1 -C 4 alkyl.

More preferably in formula (Ic), (Id), (Ie), (If), (Ig) and (Ih) at least two of R20i, R2021, R203 and R204 are ethyl, propyl or butyl and the remainder is methyl; or R201 and R202 or R203 and R210 together with the bonding carbon atom form a C5 -C6 cycloalkyl radical and one of the remaining substituents is ethyl, propyl or butyl. Most preferably X is CH 3 CH-phenyl.

The above compounds and their preparation are described in GB 2 342 64 9. Other suitable compounds are 4-imino compounds of formula (III) (III) wherein Gn, G 1 2, Gi 3 and G] 4 are independently C 1 -C 4 alkyl. or G11 and Gi? together and Gn and Gn together, or Gn and Gi-> together or Gn and Gn together are 11 l ^ J J ν '1 1? pentamethylene; G) 5 and G16 are all independently of each other hydrogen or C1 -C4 alkyl; X is as defined above; k is 1, 2, 3, or 4 Y is -O-, -NR 302- or when n is 1 and R 30i represents alkyl or aryl Y is additionally a direct bond; R302 is H, C1 -C8 alkyl or phenyl; if k is 1 R30i is H, straight or branched C1 -C18 alkyl, C3 -C18 alkenyl or C3 -C18 alkynyl, which may be unsubstituted or substituted by one or more OH, C1 -C8 alkoxy, carboxy, C1 -C8 alkoxycarbonyl; C5 -C12 cycloalkyl or C5 -C12 cycloalkenyl;

Phenyl, C7 -C9 phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1 -C8 alkyl, halogen, OH, C1 -C6 alkoxy, carboxy, C1 -C8 alkoxycarbonyl; -C (= O) -C 1 -C 36 alkyl, or an acyl moiety of an α, β-unsaturated carboxylic acid having 3 to 5 C atoms or an aromatic carboxylic acid having 7 to 15 C atoms; -SO3 -Q +, -P0 (0-Q +) 2j -P (= O) (OR2) 2, -SO2-R2, -CO-NH-R2, -CONH2, COOR2, or Si (Me) 3, wherein Q + is Ff, ammonium or an alkali metal cation; if k is 2 R30] is C1 -C6 alkylene, C3 -C18 alkenylene or C3 -C18 alkynylene which may be unsubstituted or substituted by one or more OH, C1 -C8 alkoxy, carboxy, C1 -C8 alkoxycarbonyl; or xylene; or R 301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 C atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8 to 14 C atoms; if k is 3, R 30i is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and if k is 4, R 301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

Preferably Gi6 is hydrogen and Gi5 is hydrogen or C1 -C4 alkyl, in particular methyl, and Gn and G13 are methyl and G12 and GJ4 are ethyl or propyl or G1. 1 and Gi2 are methyl and G13 and Gi4 are ethyl or propyl.

The 4 imino compounds of formula V may be prepared for example according to E.G. Rozantsev et al. Izv. Akad Nauk SSSR, Ser. Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxide in a condensation reaction with hydroxylamine and subsequent reaction of the OH group. The compounds are described in WO 02/100831.

Preference is given to compounds wherein the structural element of formula (ΙΓ) is of formula A ', B' or O ', where m is 1, R is hydrogen, C1 -C6 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovaienyl radical of an aliphatic carboxylic acid having 2 to 18 C atoms, of a cycloaliphatic carboxylic acid having 7 to 15 C atoms, or an α, β-unsaturated carboxylic acid having 3 at 5 C atoms or an aromatic carboxylic acid having 7 to 15 C atoms; p is 1;

R 10 is C 1 -C 7 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 18 alkanoyl, C 3 -C 5 alkenyl or benzoyl; R102 is C1 -C8 alkyl, C5 -C7 cycloalkyl, C2 -C8 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group, or is glycidyl, a group of the formula -CH2CH (OH) -Z or of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; G6 is hydrogen and G5 is hydrogen or C1 -C4 alkyl, G1 and G3 are methyl and G2 and G4 are ethyl or propyl or G1 and G2 are methyl and G3 and G4 are ethyl or propyl.

Also suitable are compounds wherein the structural element is of formula (ΙΙΓ) wherein Gn, G12, G13 and G1 4 are independently C1 -C4 alkyl or Gn and G12 together and G13 and G] 4 together, or Gn and Gi2 together or Gn and Gi4 together are pentamethylene; G15 and Gi6 are all independently of each other hydrogen or C1 -C4 alkyl; k is 1, 2, 3, or 4 Y is O, NR 302 or when n is 1 and R 30i represents alkyl or aryl Y is additionally a direct bond; R302 is H, C1 -C18 alkyl or phenyl; if k is 1 R 30i is H, straight or branched C 1 -C 6 alkyl, C 3 -C 18 alkenyl or C 3 -C 18 alkynyl which may be unsubstituted or substituted by one or more OH, C 1 -C 8 alkoxy, carboxy, C 1 -C 8 alkoxycarbonyl, C 5 cycloalkyl -C12 or C5 -C12 cycloalkenyl;

Phenyl, C7 -C9 phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1 -C8 alkyl, halogen, OH, CpC alkoxy, carboxy, CpC8 alkoxycarbonyl; -C (= O) -C 1 -C 36 alkyl, or an acyl moiety of an α-unsaturated carboxylic acid having 3 to 5 C atoms or an aromatic carboxylic acid having 7 to 15 C atoms; -SO03'Q +, -PO (O'Q +) 2, -P (= O) R2) 2, -so2-r2, -co-nh-r2, -CONH2, COOR2, or Si (Me) 3, wherein Q + is H +, ammonium or an alkali metal cation; if k is 2, R 301 is C 1 -C 18 alkylene, C 3 -C 18 alkenylene or C 3 -C 18 alkynylene which may be unsubstituted or substituted by one or more OH, C 1 -C 6 alkoxy, carboxy, C 1 -C 8 alkoxycarbonyl; or xylene; or R 301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 C atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8 to 14 C atoms; if k is 3, R 301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and if k is 4, R 30i is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

The alkyl radicals in the various substituents may be straight or branched. Examples of alkyl containing 1 to 18 C atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylexyl, t-octyl , nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.

Alkenyl of 3 to 18 C atoms is a straight or branched radical such as propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl , n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.

Preferred is 3 bis 12 alkenyl, particularly preferred with 3 to 6 C atoms.

3-18 alkynyl is a straight or branched radical such as propynyl, 2-butynyl, 3-butynyl, n-2-octinyl, or n-2-octadecinyl. Preferred is 3 to 12 alchemy, particularly preferred with 3 to 6 C atoms.

Examples for hydroxy substituted alkyl are hydroxypropyl, hydroxybutyl or hydroxyhexyl. Examples for halogen substituted alkyl are dichloropropyl, monobromobutyl or trichloroexyl.

C2 -C18 alkyl interrupted by at least one O atom is for example -CH2-CH2-O-CH2-CH3, -CH2-CH2-0-CH3- or -CH2-CH2-0-CH2-CH2-CH2-O- CH2-CH3-. It is preferably derived from polyethylene glycol. A general description is - ((CH2) a-0) b-H / CH3, where a is a number from 1 to 6 and b is a number from 2 to 10.

C2 -C18 alkyl interrupted by at least one NR5 group can be described as - ((CH2) a-NR5) b-H / CH3, wherein a, b and R5 are as defined above.

C3 -C12 cycloalkyl is typically cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcycloexyl or trimethylcycloexyl.

C 6 -C 10 aryl is for example phenyl or naphthyl, but also include C 1 -C 4 alkyl substituted phenyl, C 1 -C 4 alkoxy substituted phenyl, hydroxy substituted, halogen or nitro phenyl. Examples for phenyl substituted alkyl are ethylbenzene, toluene, xylene and their isomers, mesitylene or isopropylbenzene. Halogen substituted phenyl is, for example, dichlorobenzene or bromotoluene.

Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy and their corresponding isomers.

C7 -C9 phenylalkyl is benzyl, phenylethyl or phenylpropyl.

C5-C10 heteroaryl is for example pyrrol, pyrazol, imidazole, 2,4, dimethylpyrrole, 1-methylpyrrole, thiophene, fiirane, furfural, indole, coumarone, oxazole, thiazole, isoxazole, isothiazole, triazole, pyridine, α-peakin, pyridazine pyrazine or pyrimidine.

If R is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl, acryloyl, methacryloyl, benzoyl, cinnamoyl or radical [3- (3,5-di -tert-butyl-4-hydroxyphenyl) propionyl.

C 1 -C 6 alkanoyl is for example formyl, propionyl, butyryl, octanoyl, dodecanoyl but preferably acetyl and C 3 -C 5 alkenyl and in particular acryloyl.

In the particular polymerization process b1) is more suitable. When process b1) nitroxyl ether according to the structures outlined above is used, it divides between the O-X bond. The fragment (E) in formula (I) then corresponds to the ON fragment and the initiation fragment (In) corresponds to the group C centralized radical. N Particularly suitable nitroxyl ethers and nitroxyl radicals are those of the formulas. In one embodiment Very specific to the invention, the polymeric or copolymeric biodiesel flow enhancer is prepared with a compound of formula (Ol) (01).

In this case the initiation fragment (In) in formula (I) is and the group (E) is When the process according to route b2) is chosen, the initiation fragment (In) corresponds to the radical derived from the free radical initiator. . The free radical initiator of route b2) is preferably an azo compound, a peroxide, perester or a hydroperoxide.

Suitable azo compounds are commercially available, for example 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4 -methoxy-2,4-dimethylvaleronitrile), 1,2'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (isobutyramide) dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2 ' dimethyl-azobisisobutyrate, 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 2,2'-azobis (N, N '-dimethyleneisobutyramine) as free base or hydrochloride, 2,2'-azobis (2-amidinopropane) as free base or hydrochloride, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethylethyl) propionamide or 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide.

Suitable peroxides and hydroperoxides are commercially available, for example acetylcycloexanesulfonyl peroxide, diisopropyl peroxydicarbonate, tert-amylpemeodecanoate, tert-butylperpivalate, tert-butylperpivalate, tert-amylperpivalate, bis (2,4-dichloro peroxide) -isononanoyl, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis (2-methylbenzoyl) peroxide, disuccinoyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethylexanoate, bis ( 4-chlorobenzoyl), tert-butyl perisobutyrate, tert-butyl permaleate, 1,1-bis (tert-butylperoxy) -3,5,5-trimethylcycloexane, 1,1-bis (tert-butylperoxy) cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl perisononate, 2,5-dimethylexane 2,5-dibenzoate, tert-butyl peracetate, tert-amylperbenzoate, tert-butyl perbenzoate, 2,2-bis (tert-butylperoxy) butane, 2,2-bis (tert-butylperoxy) propane, per dicumyl oxide, 2,5-dimethylexane 2,5-di-tert-butylperoxide, 3-tert-butylperoxy-3-phenyl phthalate, di-tert-amyl peroxide, a, a'-bis (tert-butylperoxyisopropyl ) benzene, 3,5-bis (tert-butylperoxy) -3,5-dimethyl-1,2-dioxolane, di-tert-butyl peroxide, 2,5-dimethylexino 2,5-di-tert-butyl peroxide , 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-methane hydroperoxide, pinane hydroperoxide, diisopropylbenzene monohydrate, cumene hydroperoxide or hydroperoxide of tert-butyl.

Since the polymer or copolymer of the biodiesel fuel composition is a near-live polymerization the polydispersibility will fall between about 1.1 and 2.5, preferably a polydispersity index of 1.0 to 2.2, more preferably 1, 1 to 1.9 and more preferably from 1.1 to 1.5.

EXAMPLES

Compound 01 is prepared from Example 24 of GB 2 335 190 Example 1 Preparation of nitroxyl-mediated CFRP-formed poly 2-ethylexylacrylate 50 g of ethylexylacrylate are added to a 200 ml flask. 0.57 g of nitoxyl compound 01 is added. The clear mixture is degassed under vacuum for 1 minute followed by degassing with N 2 for 2 minutes (3 cycles). The degassed mixture is heated and stirred at 135 ° C. The reaction is followed by monitoring the solids content (SC). After 270 minutes the solid content is "50% and the molecular weight is determined using GPC with standard polymethyl methacrylate (PMMA). Mn is about 14500 or n = 77.

Example 2 Preparation of Poly (2-ethylexylacrylate-b-laurylacrylate) 49.98 g of polymer formed in Example 1 is combined with 33.19 g of lauryl acrylate (FLUKA) in a 200 ml flask to form a clear yellowish mixture. homogeneous. The clear mixture is degassed under vacuum for 1 minute followed by degassing with N 2 for 2 minutes (3 cycles). The degassed mixture is heated and stirred at 135 ° C. The reaction is followed by monitoring the solids content (SC). After 90 minutes, the reaction temperature is raised to 140 ° C and the SC is tested after 150 minutes. The temperature is then raised to 145 ° C and the SC is then tested every 30 minutes on an 80% SC target that is obtained. GPC using THF and PMMA standard. Mn = 12,980 g / mol; PD = 1.35), clear amber liquid. Additional polymers and copolymers similarly prepared as in Examples 1 and 2 'ran means random block formed of 2-hydroxyethylacrylate and 2-ethylexylacrylate. This random block is equivalent to m.

Example 16 Preparation of poly (n-butylacrylate-b-dimethylaminopropyl methacrylamide) 2460 g of poly (n-butyl acrylate) (Mn: 5800) are prepared in a similar manner as in Example 1, are added to a 5 1 reactor followed by per 1700 g of dimethylaminopropyl methacrylamide. The clear mixture is degassed under vacuum followed by degassing with? N 2 (3 cycles). The degassed mixture is heated and stirred at 145 ° C. The reaction is followed by monitoring the solids content (SC). When the solids content reaches 75% the reaction is stopped and the molecular weight is measured by GPC. Mn = 7500.

Transesterification Modifications of Example 16: The polymers according to Examples 17 to 22 are formed from the starting block copolymer of Example 16 by transesterifying the butylacrylate monomer units with various alcohols or alcohol mixtures as described in Example 17.

Example 17 The block copolymer of the polymer of Example 16 is transesterified with pure stearyl alcohol at 150 ° C / 50 mbar in the presence of titanium di (IV) bis (acetylacetonate) catalyst forming a poly [(butylacrylate) terpolymer. (stearylacrylate) -b-dimethylaminopropyl methacrylate]. 29.7 g of the polymer formed in Example 16 and 27, 22 g of stearyl alcohol are added to a 100 ml flask. The homogeneous yellow mixture is heated under vacuum for 1 hour at 140 ° C to remove traces of water. 0.6683 g of Ti catalyst is added and the reaction temperature is raised to 150 ° C. After 1 hour, 0.6450 g of titanium catalyst is additionally added and the reaction is continued. After the second hour, an additional 0.645 g of titanium catalyst is added and the reaction continued for a total of three hours. Η = 11,700.

Example 18 The copolymer of Example 16 is transesterified with stearyl alcohol (NAFOL 1618s) to provide the copolymer of Example 18.

Examples 19 to 21 The copolymer of Example 16 is transesterified with mixtures of partially branched C12 -C15 alcohol (LIAL 125A and stearyl alcohol (NAFOL 1618s)) to provide the copolymers of Examples 19 to 21. The copolymers differ by molar amounts of alcohol. C 12 -C 15 (LIAL 125A) and stearyl alcohols (n: o ratio).

Example 22 The copolymer of Example 16 is transesterified with C12 -C15 alcohol (LIAL 125A) to provide the copolymer of Example 22.

Examples 23 to 26 Preparation of The above polybutyl acrylate (n = 77) is transesterified with mixtures of C 1 -C 2 alcohol (NEODOL 25E), stearyl alcohol (AFOL 1618s) and monomethyl polyethylene glycol (MW = 500) in varying ratios. to provide the copolymers of Examples 23 to 26. The reaction conditions are virtually the same as those described in Example 17. 29.95 g poly n-butyl acrylate, 9.27 g stearyl alcohol, 23.73 g Neodol 25E and 8.87 g M (PEG 500) are added to a 100 ml round bottom flask. The homogeneous yellow mixture is heated under vacuum for 1 hour at 140 ° C to remove trace amounts of water. 0.8214 g (1 mol%) of Ti catalyst is added and the reaction temperature is raised to 150 ° C. After 1 and 2 hours of reaction an additional 1 mol% Ti catalyst is added (total 3 mol%). The mixture is allowed to react for a total of 3 hours.

Table 2 Table 2 cont.

Table 2 cont.

Table 2 cont.

Application Results A representative number of the polymers formed above are tested for their efficiency as cold flow enhancers in biodiesel. Untreated treated biodiesel is derived from soybean oil and typically has a cold filter plugging point of 0 ° to 3 ° C. Table 3 shows the change in degrees centigrade to the cold filter plugging point for soybean-derived biodiesel treated with 2% by weight of the polymers of the invention. The control is an untreated soy-based biodiesel oil. The clogging point of the cold filter is determined by standard ASTM D6371. It should be expected that the polymers tested below on soybean biodiesel would also be effective on other biodiesel sources such as rapeseed and palm.

Table 3 CLAIMS

Claims (11)

Biodiesel fuel composition, characterized in that it comprises The polymer or copolymer of formula (I) In-Poly- (E) y (I) obtained by nitroxyl-controlled free radical polymerization, where In is the initiator fragment starting from the polymerization reaction; E is an end group carrying at least one free and stable nitroxyl radical which is attached via an oxygen atom to the polymer or copolymer; or a group resulting from a stable or bound free nitroxyl radical substitution or removal reaction; Poly is any polymer or copolymer formed from ethylenically unsaturated monomer (s); y is a number 1 or greater than 1 indicating the average number of end groups E attached to Poly. Composition according to Claim 1, characterized in that the final group E is Composition according to Claim 2, characterized in that the end-group nitrogen is part of a 5- or 6-membered heterocyclic ring, which optionally has an additional nitrogen or oxygen atom in the ring system. Composition according to any one of Claims 1 to 3, characterized in that the polymer or copolymer makes up from about 0.05 to about 20% by weight of the total weight of the biodiesel fuel composition. Composition according to any one of Claims 1 to 3, characterized in that the biodiesel fuel is prepared from oil derived from rapeseed, soybean, palm, palm olein, palm stearin, palm kernel oil. coriander oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm seed oil, coconut oil, mustard seed oil , beef tallow, bone oil, fish oils, used cooking oils and mixtures thereof. Composition according to any one of Claims 1 to 5, characterized in that the ethylenically unsaturated monomers are styrenes, substituted styrenes, (meth) acrylic acid, (C1 -C36) alkyl esters of (meth) acrylic acid, esters. (C1-C30) hydroxyalkyl (C1-C30) alkyl or polyhydroxy (meth) acrylic acid, (meth) acrylic esters of alkoxylated alcohols such as ethoxylated fatty alcohols, (meth) C2-C4 polyalkylene glycol esters, (meth) esters alkoxylated phenol acrylics such as ethoxylated nonylphenol, (C1 -C36) alkyl esters of (meth) acrylic acid which esters are substituted by amino, N-mono (C1 -C30) alkyl (meth) acrylamide, Ν, dial-dialkyl (C1 -C30) (meth) acrylamide, mono or disubstituted (C1 -C30) (meth) acrylamide alkyl groups which may additionally be unsubstituted or substituted by amino or mixtures thereof. Composition according to any one of Claims 1 to 5, characterized in that the Poly polymer or copolymer is a block, random, honeycomb, star or gradient architecture. Composition according to any one of Claims 1 to 7, characterized in that In of formula (I) is selected from the group consisting of -CH 2 -phenyl, CH 3 CH-phenyl, (CH 3) 2 C-phenyl, ( C5 -C10 cycloalkyl: C'CN (CM.); CCN .ClCl: C'H-C11: CIRCIC -Cll · (C1 -C' alkyl) CR; uC (-0) - phenyl (C 1 -C 6) alkyl-C 1 R 2 -C (- (.)) - (C 1 -C 6) alkyl (C 1 -C 6) alkyl-C 1 -C 6 - (C ()) - (C 1 -C 6) alkyl, (C 1 -C 6) alkyl-CR 1, (C 1 -C 6) -N-dialkyl (C 1 -C 6) · (C 1 -C 6) alkyl-CR: mC ( - (..)) - NI (C 1 -C 6) alkyl and (C 1 -C 6) alkyl-CR 1, r C (~ ()) -NI 1: where R 2 is hydrogen or alkyl (CrC |). Method for Improving the Flow Properties of a Biodiesel Fuel Composition, as determined by the steps that comprise adding to a biodiesel fuel at least 0.1 "by weight of the polymer or copolymer of formula (I) as defined in claims 1 to 6 to 8. wherein by weight is based on the total biodiesel fuel composition. Method according to claim 0, characterized in that the composition contains from about 5 to about 0.00% by weight of biodiesel fuel. Composition according to any one of Claims 1 to 8, characterized in that the polymer of formula (1) is obtained by nitroxyl-mediated free radical polymerization and subsequently modified by a transesterillation reaction.