CN104204160A

CN104204160A - Use of cold flow improver compositions for fuels, blends thereof with biofuels and formulations thereof

Info

Publication number: CN104204160A
Application number: CN201380017840.2A
Authority: CN
Inventors: J·克耶特; F-O·梅林; R·科沙贝克; S·金策尔
Original assignee: Evonik Rohmax Additives GmbH
Current assignee: Evonik Oil Additives GmbH
Priority date: 2012-04-27
Filing date: 2013-04-22
Publication date: 2014-12-10
Also published as: EP2841538A1; JP2015514853A; KR20150003211A; WO2013160228A1; US20150059238A1; CA2869714A1; SG11201406517UA; RU2014147608A

Abstract

The present invention relates to the use of polyalkyl(meth)acrylates as an additive to fuels, especially middle distillate fuels and blends thereof. The present invention further relates to the use of a composition comprising polyalkyl(meth)acrylates as dispersing species susceptible to disperse waxes and sludgy material at low temperatures and a hydrocarbon solvent/an oil for improving the cold flow properties of fuel oil and fuel oil compositions. The present invention further relates to the use of these compositions as an additive to fuels, especially in the function of paraffin dispersant, to such fuels themselves and to fuel additive concentrates which comprise this composition dissolved in a hydrocarbon solvent or an oil.

Description

Cold flow improver composition is for fuel, itself and the blend of biofuel and the purposes of its preparation

Technical field

The present invention relates to gather (methyl) alkyl acrylate as fuel, particularly the purposes of the additive of midbarrel fuel and its blend.The invention further relates to comprise poly-(methyl) alkyl acrylate as the composition of the dispersed material to dispersing wax and mud shape material sensitivity at low temperatures and hydrocarbon solvent or oil the purposes for improvement of the cold flow properties of oil fuel and fuel oil composition.

The invention further relates to these compositions as fuel dope, particularly serve as the application of paraffinic hydrocarbons dispersion agent, this class A fuel A itself and comprise the fuel additive concentrate that is dissolved in this composition in hydrocarbon solvent or oil.

Background technology

Nowadays fuel obtain from fossil origin conventionally.But these sources are limited, so that seeking sub.Therefore, day by day to can be interested for the preparation of the renewable starting material of fuel.Especially biodiesel fuel of very interesting sub.

Term " biofuel " is interpreted as under many circumstances and refers to fatty acid ester, the mixture of fatty acid methyl ester (FAME) conventionally, and wherein the chain length of lipid acid fraction is 14-24 carbon atom and has 0-3 two key.The carbon number existing is higher and two keys are fewer, and the fusing point of FAME is higher.Typical starting material be vegetables oil (being glyceryl ester) for example rapeseed oil, sunflower oil, soybean oil, plam oil, Oleum Cocois and, in individual other situation, or even with the vegetables oil of mistake.By transesterify, conventionally use methyl alcohol under base catalysis, these starting material are changed into corresponding FAME.

FAME content also affects the cold flow properties of raw material.Carbon number saturation ratio lower and in fatty acid chain is lower, and the cold flow properties of raw material is better.The common method of evaluating cold flow quality is: pour point (PP) mentioned in ASTM D97 is tested, the filterability limit of measuring via cold filter clogging temperature (CFPP) experimental evidence DIN EN 116 or ASTM D6371, and cloud point (CP) test as described in ASTM D2500.

At present, rape-seed oil methyl ester (RME) is the preferred feedstock of Europe for production of biodiesel, because vegetable seed allows preparation to have the biodiesel fuel of better cold flow properties.But, due to the high price level of RME, for example, so also developed RME and other raw material, the mixture of soybean (SME) or palm methyl ester (PME).Soybean is preferred raw material in America, and plam oil is preferred in Asia.Except utilizing 100% biofuel, contain the mixture of fossil diesel fuel (being the middle runnings of crude distillation) and biofuel because improved low-temperature performance is also considered with better combustioncharacteristics.

In view of the ecological quality declining and world's crude stockpile of reducing, using pure biofuel (B100) has been the important goal in many countries.But many problems (corrosion from different combustioncharacteristicss to sealing material) have been reported as the obstruction as fossil diesel fuel sub to biofuel.

The midbarrel fuel of fossil sources, the gas oil particularly obtaining from mineral oil, diesel oil or special light heater oil, the source of based on crude and refinery practice and there are different compositions.

Be known that for a long time applicable additive can change the crystal growth of n-paraffin in midbarrel fuel.Very effective additive prevents that midbarrel fuel from becoming solid, even still like this at the temperature of several degrees Celsius below the temperature out time at the first paraffinic hydrocarbons crystal structure.As an alternative, form the uncrosslinking chain alkane crystal through tiny, the easy crystallization of the strainer in Motor vehicles and heating system, or at least form can be saturating to the liquid portion of middle runnings filter cake so that guarantee without destroying operation.

The validity of cold flow improver represents by measuring cold filter clogging temperature (CFPP) indirectly according to European standard EN 116.

Ethene-vinyl carboxylate copolymer is as cold flow improver (CFI) or middle runnings FLOW IMPROVERS (MDFI) for some time.A shortcoming of these additives is, the paraffinic hydrocarbons crystal of precipitation (due to they higher density compared with liquid portion) tends in storage process in container bottom sedimentation more and more.As a result, homogeneous low alkane hydrocarbon phase forms in bottom in the formation of the top of container and the rich paraffinic hydrocarbons layer of two-phase.

Because the container bottom that fuel is normally just in mineral oil dealer's fuel bath and storage or filling tank is extracted out above, so the risk that exists the solid n-paraffin of high density to cause strainer and metering outfit to be stopped up.Storing temp more lower than the precipitation temperature of paraffinic hydrocarbons and at this kind of temperature storage time longer, this risk becomes larger because precipitation paraffinic hydrocarbons amount along with temperature decline and increase.Especially, the fraction of biofuel also may improve this undesirable of midbarrel fuel and is inclined to n-paraffin sedimentation.

Above-mentioned problem can reduce significantly by means of additionally using paraffinic hydrocarbons dispersion agent or wax anti-settling additive (WASA).

When the temperature of fuel is reduced to below cloud point, for example, while being reduced to cold filter clogging temperature, small-particle appears in fuel, and they tend to agglomeration the large tabular or spherolite precipitation as wax.These wax crystallss increase through the difficulty of pipeline and pump delivery fuel and tend to stop up burning line, screen cloth and strainer.Be mainly nalka chloroflo from the wax of diesel oil fuel, as small thin slices crystallization, and mainly formed by the saturated fatty acid methyl ester (FAME) of cocrystallization from the wax of biofuel.These problems be generally acknowledge and various additives have been proposed.

Some additive, is called middle runnings cold flow improver (MDFI) or biofuel FLOW IMPROVERS (BDFI) and reduces the size of the wax crystalls forming and shape is become to acicular structure from tabular structural modification.The crystal of reduced size is desirable, because their impossible blocking filters, and the structure of needle-like will more may be passed strainer, or on strainer, form the porous layer of crystal.Other additive also may have the wax crystalls of maintenance and suspend in fuel, and therefore minimizing sedimentation also also helps prevent the effect of obstruction.The additive of these types is often called " wax anti-sedimentation agent " (WASA).

Describe in the past few years and avoided the many WASAs of wax crystalls in the inner sedimentation of fuel.

For example, U.S. Patent number 4,400,2708 disclose the efficiency of the single molecule of the dialkylamine derivatives (PA derivative) based on phthalic acid.That especially mention is N, N-bis-(octadecyl) phthalamidic acid, N, two-bis-(octadecyl) acid amides of N-bis-(eicosyl) phthalamidic acid and phthalic acid.

Another example, it is the oil soluble polarity nitrogen that its substituting group can be cationic form that the EP patent No. 1935968 has been described applicable wax anti-sedimentation agent.WASA is carboxylic acid or their acid anhydrides and contains at least one straight chain C _8-40the uncle of alkyl segment or the condenses of secondary amine.Especially, preferred compound is Tetra hydro Phthalic anhydride by making 1 molar ratio reacts formation acid amides-amine salt with two (hydrogenated tallow) amine of 2 molar ratios.

In WO International Publication 2007/147753 (BASF), use the blend of 2 to 3 kinds of components that the wax crystalls in the mixture of fuel and itself and biofuel (from B0.1 to B75) is stablized.Described blend is by the polar molecule of 5 % by weight-95 % by weight one of (its be not following), 1-50 % by weight by polyamine structure (containing 2-1000 N-atom) and C _8-30the amide molecule composition that the condensation of lipid acid is manufactured, this amide molecule can with the α of 0-50 % by weight, the condenses mixing of β-di-carboxylic acid (containing 4-300 C-atom) and primary amine.Provide as an example and the amino tetraacethyl of ethylene (EDTA) of the condenses (37.5mol%) of diethylenetriamine and oleic acid and condenses (12.5mol%) blending of maleic anhydride and tridecyl amine and the condenses (50mol%) of two tallow base amine.

EP patent 1 451 271 has been described by making aliphatic series or aromatic amine and aliphatic series or aromatics list, two, three or the application of the oil soluble nitrogen compound that obtains of tetracarboxylic acid or their anhydride reaction.Especially, two kinds of dissimilar WASA chemical substances are cited as a part (wax anti-settling and FLOW IMPROVERS) for WAFI preparation.Thiazolinyl-the spironolactone of one of described chemistry based on reacting with the secondary aliphatic amide that contains 8-36 carbon atom.Example is by providing with the dodecenyl succinic-spirodilactone of primary and secondary tallow amine condensation.The second chemistry is by providing with the terpolymer of the vinyl monomer of allyl group polyglycol ether and the copolymerization merging of maleic anhydride statistics and primary amine and/or fatty alcohol condensation.In order to illustrate this patent, the C reacting with 2 mole of two tallow amine ₁₄/ C ₁₆the terpolymer of-alpha-olefin, maleic anhydride and allyl group polyglycol is mentioned as useful wax stabilizer.

Summary of the invention

Because the blend of most of business WASA based on single modification molecule (as NTA, EDTA and PSA) or the poly-alpha-olefin based on modification, so we have proposed to have the PAMA based polyalcohol material (for example, for monomer dimethylaminoethyl methacrylate (DMAEMA) or dimethyl propyl Methacrylamide (DMAPMAm)) of amido functional group as new WASA.The handling property that these compounds have had compared with prior art component and can be used in addition makes the wax in fuel or its blend stable.

Summary of the invention

According to a first aspect of the invention, provide poly-(methyl) alkyl acrylate of comprising following monomeric unit purposes for improvement of the cold flow properties of fuel oil composition:

(a) the ethylenic unsaturated ester compound of one or more formulas (I) of 0 % by weight-40 % by weight

Wherein

R is H or CH ₃,

R ¹representative is containing the straight or branched of 1-9 carbon atom, saturated or unsaturated alkyl or contain the cycloalkyl of 3-9 carbon atom,

R ²and R ³represent independently the group of H or formula-COOR', wherein R' is H or containing the straight or branched of 1-9 carbon atom, saturated or unsaturated alkyl or contain the cycloalkyl of 3-9 carbon atom,

(b) the ethylenic unsaturated ester compound of one or more formulas (II) of 20-98 % by weight

Wherein

R is H or CH ₃,

R ⁴representative contains straight or branched, the saturated or unsaturated alkyl of 10-22 carbon atom,

R ⁵and R ⁶" group, wherein R " is H or straight or branched, saturated or unsaturated alkyl containing 10-22 carbon atom to represent independently H or formula-COOR,

(c) the ethylenic unsaturated ester compound of one or more formulas (III) of 0 % by weight-10 % by weight

Wherein

R is H or CH ₃,

R ⁷representative contains straight or branched, the saturated or unsaturated alkyl of 23-40 carbon atom,

R ⁸and R ⁹represent independently H or formula-COOR " ' group, wherein R " ' be H or straight or branched, saturated or unsaturated alkyl containing 23-40 carbon atom,

(d) vi-ny l aromatic monomers of 0 % by weight-30 % by weight, and

(e) at least one N-dispersion agent monomer of 2-80 % by weight,

Wherein component (a)-(e) total 100 % by weight.

Detailed Description Of The Invention

Within the scope of the present invention, term " (methyl) alkyl acrylate " refers to alkyl acrylate and alkyl methacrylate material or their mixture.Alkyl methacrylate is preferred.

The limiting examples of component (a) comprises (methyl) acrylate derived from saturated alcohol, fumarate and maleic acid ester, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate and (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid cycloalkyl ester, as (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate and (methyl) vinylformic acid 3-vinyl cyclohexyl, derived from (methyl) acrylate of unsaturated alcohol, as (methyl) vinylformic acid 2-propynyl ester, (methyl) allyl acrylate and (methyl) vinyl acrylate, with corresponding fumarate and maleic acid ester.

Monomer (a) is by 0 % by weight-40 % by weight, and preferably the amount of 0 % by weight-20 % by weight exists, based on component (a), (b), (c), (d) and gross weight (e).

In one embodiment, the amount of monomer (a) is at least 0.1 % by weight, preferably at least 0.5 % by weight.

In a preferred embodiment, the amount of monomer (a) is 0%.

The limiting examples of component (b) comprises (methyl) acrylate derived from saturated alcohol, fumarate and maleic acid ester, for example (methyl) vinylformic acid 2-tertiary butyl heptyl ester, (methyl) vinylformic acid 3-sec.-propyl heptyl ester, (methyl) vinylformic acid 2-n-propyl heptyl ester, (methyl) decyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) vinylformic acid 5-methyl undecyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid 2-methyl dodecyl ester, (methyl) tridecyl acrylate, (methyl) vinylformic acid 5-methyl tridecyl ester, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid 2-methyl cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid 5-sec.-propyl heptadecyl ester, (methyl) vinylformic acid 4-tertiary butyl stearyl, (methyl) vinylformic acid 5-ethyl stearyl, (methyl) vinylformic acid 3-sec.-propyl stearyl, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester or (methyl) vinylformic acid docosyl ester, derived from (methyl) acrylate of unsaturated alcohol, for example (methyl) vinylformic acid oil alkene ester, (methyl) vinylformic acid cycloalkyl ester, for example (methyl) vinylformic acid norbornene ester, (methyl) vinylformic acid 2,4,5-tri--tertiary butyl-3-vinyl cyclohexyl, (methyl) vinylformic acid 2,3,4,5-tetra--tertiary butyl cyclohexyl, methacrylic acid epoxy alkyl ester, for example methacrylic acid 10,11-epoxy group(ing) cetyl ester, with corresponding fumarate and maleic acid ester.

Monomer (b) is by 20 % by weight-98 % by weight, preferably 50 % by weight-95 % by weight, more preferably the amount of 70 % by weight-90 % by weight exists, based on component (a), (b), (c), (d) and gross weight (e).

In a preferred embodiment, monomer (b) is (methyl) vinylformic acid C _8-15-alkyl ester, preferably commercialization (methyl) lauryl acrylate, or (methyl) vinylformic acid C _10-15-alkyl ester fraction.More preferably, backbone monomers is methacrylic acid C _8-15-alkyl ester, preferably commercialization lauryl methacrylate(LMA) or methacrylic acid C _10-15-alkyl ester fraction.

The limiting examples of component (c) comprises (methyl) acrylate derived from saturated alcohol, for example (methyl) vinylformic acid hexadecyl eicosyl ester, (methyl) stearyl acrylate base eicosyl ester and/or (methyl) vinylformic acid eicosyl-tetratriacontane base ester; And corresponding fumarate and maleic acid ester.

According to the present invention, aromatic group represents containing preferred 6-20, the more particularly monocycle of 6-12 C atom or the group of polynuclear aromatic compound, for example phenyl, naphthyl or xenyl, preferably phenyl.

Heteroaromatic group refers to that wherein at least one CH base is replaced by N, and/or at least two adjacent CH bases are by the aryl of S, NH or O replacement.These groups especially comprise derived from following group: thiophene, furans, pyrroles, thiazole, azoles, imidazoles, isothiazole, different azoles, pyrazoles, 1,3,4- diazole, 1,3,4-thiadiazoles, 1,3,4-triazole, 1,2,4- diazole, 1,2,4-thiadiazoles, 1,2,4-triazole, 1,2,3-triazoles, pyrrotriazole, benzo [b] thiophene, benzo [b] furans, indoles, benzo [c] thiophene, benzo [c] furans, isoindole, benzo azoles, benzothiazole, benzoglyoxaline, benzisoxa azoles, benzisothiazole, benzopyrazoles, diazosulfide, benzotriazole, diphenylene-oxide, dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-triazine, quinoline, isoquinoline 99.9, quinoxaline, quinazoline, cinnolines, 1,8-naphthyridines, 1,5-naphthyridines, 1,6-naphthyridines, 1,1'-naphthyridines, phthalazines, Pyridopyrimidine, purine, pteridine or 4H-quinolizine.

Preferred alkyl comprises methyl, ethyl, propyl group, sec.-propyl, 1-butyl, 2-butyl, 2-methyl-propyl, the tertiary butyl, amyl group, 2-methyl butyl, 1,1-dimethyl propyl, hexyl, heptyl, octyl group, 1,1,3,3-tetramethyl butyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and eicosyl.

Preferred cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group, and they are not replace or replaced by side chain or non-branched-chain alkyl.

Preferred thiazolinyl comprises vinyl, allyl group, 2-methyl-2-propylene, crotyl, pentenyl, 2-decene base and 2-eicosylene base.

Monomer (c) exists by the amount of 0 % by weight-10 % by weight, based on component (a), (b), (c), (d) and gross weight (e).

In one embodiment, the amount of monomer (c) is at least 0.1 % by weight, preferably at least 0.5 % by weight.

Monomer (d) can be the vinylbenzene of for example vinylbenzene of vi-ny l aromatic monomers and replacement in the time existing, but also can use other vinyl monomer.The vinylbenzene replacing comprises the vinylbenzene being replaced by one or more substituting groups, and described substituting group is selected from halogen, amino, in alkyl residue containing the alkoxyl group of 1-12 carbon atom, carboxyl, hydroxyl, alkylsulfonyl, contains the alkyl of 1-12 carbon atom and other substituting group.The cinnamic example that alkyl replaces is alpha-methyl styrene, p-tert-butylstyrene, α-ethyl styrene and the p-lower alkoxy vinylbenzene containing 1-12 carbon atom.Can use the mixture of two or more vinyl monomers.Vinylbenzene is preferred.

The amount of the vinyl monomer using is 0 % by weight-30 % by weight, and in the time existing, be preferably 5 % by weight-25 % by weight, more preferably 10 % by weight-20 % by weight, based on component (a), (b), (c), (d) and gross weight (e).

Monomer (e) is that at least one is selected from following monomer: the N-vinyl containing dispersed structure division in each comfortable side chain belongs to monomer, (methyl) acrylic acid series ester, (methyl) acrylamide and (methyl) acrylimide, and can be the N-dispersion agent monomer of formula (IV)

Wherein

R ¹⁰, R ¹¹and R ¹²be independently H or containing the straight or branched of 1-5 carbon atom, saturated or unsaturated alkyl and

R ¹³or be selected from-C (O)-O-R ¹⁴,-C (O)-NH-R ¹⁴,-C (NR ¹⁵)-O-R ¹⁴,-C (NR ¹⁵)-NH-R ¹⁴with-C (O)-[NH-C _2-10-alkylidene group] _x-NR ¹⁶r ¹⁷group, wherein

R ¹⁵representative is containing straight or branched, the saturated or unsaturated alkyl of 1-5 carbon atom, or aryl with

R ¹⁴representative do not replace or by group-NR ¹⁶r ¹⁷the straight or branched alkyl containing 1-20 carbon atom replacing, wherein R ¹⁶and R ¹⁷represent independently H or containing the straight or branched alkyl of 1-8 carbon atom, or R wherein ¹⁶and R ¹⁷be a part for or unsaturated ring saturated containing one or more heteroatomic 4-8 units that are selected from nitrogen, oxygen or sulphur optionally, wherein said ring can further be replaced by alkyl or aryl, and x represents numerical value 1,2,3 or 4,

Or,

R ¹³group-NR ¹⁸r ¹⁹, wherein R ¹⁸and R ¹⁹be a part for the saturated or unsaturated ring of 4-8 unit, contain at least one carbon atom as forming the part of the ring of two keys with the heteroatoms that is selected from nitrogen, oxygen or sulphur, wherein said ring can further be replaced by alkyl or aryl.

In one embodiment, R ¹⁴represent H or the straight or branched alkyl containing 2-6 carbon atom.

The limiting examples of N-dispersion agent monomer comprises and is selected from those in following material: the nitrogen heterocyclic monomer of vinyl substituted, the nitrogen heterocyclic monomer of for example vinyl pyridine and N-vinyl substituted, for example, N-vinyl imidazole, NVP (NVP), methacrylic acid morpholino ethyl ester and N-caprolactam, propenoic acid dialkyl aminoalkyl ester and methacrylic acid dialkyl aminoalkyl ester monomer, for example (methyl) vinylformic acid N, N-dialkyl aminoalkyl ester, for example methacrylic acid N, N-dimethylaminoethyl (DMAEMA), methacrylic acid tertiary butyl ammonia ethyl ester, dialkyl aminoalkyl acrylamide and methyl acrylamide monomer, for example two-low-grade alkyl amino alkyl acrylamide, particularly wherein each alkyl or aminoalkyl group contain 1-8 carbon atom, particularly 1-3 carbon atom, for example N, N-bis-low alkyl groups, especially, N, N-dimethylaminopropyl Methacrylamide (DMAPMAm), dimethylaminopropyl acrylamide, dimethyl aminoethyl acrylamide, N-tertiary alkyl acrylamide and corresponding Methacrylamide, for example N-tert-butyl acrylamide, the amine of vinyl substituted, with for example NVP of N-vinyl lactam (NVP).

Owing to there being basic nitrogen group in polymkeric substance, so it is evident that can be by changing into salt form with acid-respons by some or all nitrogen-atoms.Therefore, polymkeric substance can be by reacting with acidic cpd partially or completely neutralization and still within the scope of the present invention.

In another embodiment, N-dispersion agent monomer can comprise the combination of following material

(i) the N-dispersion agent monomer based on acrylamide of formula (IV)

Wherein

R ¹³be selected from-C (O)-O-R ¹⁴,-C (O)-NH-R ¹⁴,-C (NR ¹⁵)-O-R ¹⁴,-C (NR ¹⁵)-NH-R ¹⁴with-C (O)-[NH-C _2-10-alkylidene group] _x-NR ¹⁶r ¹⁷group, wherein

R ¹⁵alkyl or aryl, R ¹⁴representative do not replace or by group-NR ¹⁶r ¹⁷the straight or branched alkyl containing 1-20 carbon atom replacing, wherein R ¹⁶and R ¹⁷represent independently H or containing the straight or branched alkyl of 1-8 carbon atom, or R wherein ¹⁶and R ¹⁷be a part for or unsaturated ring saturated containing one or more heteroatomic 4-8 units that are selected from nitrogen, oxygen or sulphur optionally, wherein said ring can further be replaced by alkyl or aryl, and it is several 1,2,3 or 4 that x represents, and

(ii) the N-dispersion agent monomer of formula (IV)

Wherein

R ¹⁰, R ¹¹and R ¹²h or the alkyl containing 1-5 carbon atom independently,

Described N-dispersion agent monomer can be that at least one is selected from NVP, methacrylic acid N especially, N-dimethylaminoethyl and N, the monomer in N-dimethylaminopropyl Methacrylamide or their mixture.

The amount of N-dispersion agent monomer is generally 2 % by weight-80 % by weight, preferably 5 % by weight-50 % by weight, even more preferably 10 % by weight-30 % by weight, based on component (a), (b), (c), (d) and gross weight (e).

It may be useful using at least two kinds of N-dispersion agent monomers, particularly when the total amount of N-dispersion agent monomer is prescribed a time limit in the lower of listed scope.

Poly-(methyl) alkyl acrylate conventionally has by size exclusion chromatography and measures, for the 1000-1000000g/mol of polystyrene standard sample calibration, preferably 2000-100000g/mol, more preferably 2500-100000g/mol, even more preferably 2500-50000g/mol, particularly preferably the number-average molecular weight M of 4000-20000g/mol _n.

The polymolecularity M of described poly-(methyl) acrylic acid alkyl ester polymer _w/ M _npreferably at 1-8, particularly 1.05-6.0, more preferably 1.1-5.0, most preferably in the scope of 1.3-2.5.Described weight-average molecular weight M _w, number-average molecular weight M _nwith polymolecularity M _w/ M _ncan use methyl methacrylate polymer to measure by GPC as standard model.

As preferred first aspect of the present invention, provide poly-(methyl) alkyl acrylate of comprising following monomeric unit purposes for improvement of the cold flow properties of fuel oil composition:

(a) the ethylenic unsaturated ester compound of one or more formulas (II) of 20 % by weight-98 % by weight

Wherein

R is H or CH ₃,

(b) the ethylenic unsaturated ester compound of one or more formulas (III) of 0 % by weight-10 % by weight

Wherein

R is H or CH ₃,

(c) vi-ny l aromatic monomers of 0 % by weight-30 % by weight, and

(d) at least one N-dispersion agent monomer of 2-80 % by weight,

Wherein component (a)-(e) total 100 % by weight.

The system structure of described poly-(methyl) acrylic acid alkyl ester polymer is not crucial for many application and performance.Therefore, these polymkeric substance can be random copolymers, gradient copolymer, segmented copolymer and/or graft copolymer.Segmented copolymer and gradient copolymer can for example, obtain by change discontinuously monomer composition in propagation process.According to the present invention, polymkeric substance is random copolymers preferably.

Combination according to the present invention is suitable for fuel, particularly the additive of midbarrel fuel.Midbarrel fuel is often called oil fuel.They are especially applied in gas oil, oil, diesel oil or diesel oil fuel or lightweight and Ultralight heater oil and generally have the boiling point of 150 DEG C-400 DEG C.

Can be directly and undiluted ground or as at suitable solvent, normally the enriched material in hydrocarbon solvent (solution) adds in fuel according to combination of the present invention.

Another embodiment of the invention comprises that the enriched material that comprises following component is as fuel, and particularly the additive of midbarrel fuel is for improvement of the purposes of the cold flow properties of fuel oil composition:

(A) poly-(methyl) alkyl acrylate of 30 % by weight-90 % by weight, this poly-(methyl) alkyl acrylate comprises following monomeric unit:

Wherein

R is H or CH ₃,

(b) the ethylenic unsaturated ester compound of one or more formulas (II) of 20 % by weight-98 % by weight

Wherein

R is H or CH ₃,

Wherein

R is H or CH ₃,

(d) vi-ny l aromatic monomers of 0 % by weight-30 % by weight, and

(e) at least one N-dispersion agent monomer of 2-80 % by weight,

Wherein component (a)-(e) total 100 % by weight; With

(B) hydrocarbon solvent/oil of 10 % by weight-70 % by weight.

Conventional hydrocarbon solvent is aliphatic series or aromatic hydrocarbon in this article, such as solvent naphtha of the mixture of for example dimethylbenzene or high boiling aromatic substance.Midbarrel fuel itself also can be as the solvent of such enriched material.

Described enriched material can comprise 10 % by weight-70 % by weight, preferably 30 % by weight-65 % by weight, and more preferably poly-(methyl) alkyl acrylate of the present invention as above of 45 % by weight-60 % by weight, based on the total amount of described enriched material.

In a preferred embodiment, enriched material of the present invention is as the additive of fuel, and this fuel is composed of the following components:

(i) 0 % by weight-99 % by weight, preferably biofuel oil based on fatty acid ester of at least one of 0.5 % by weight-75 % by weight and

(ii) 1 % by weight-100 % by weight, the preferably middle runnings of the fossil sources of 25 % by weight-99.5 % by weight and/or plant and/or animal-origin, it is hydrocarbon mixture and not fatty acid esters substantially.

Fuel element (i) is to be understood that and refers to the midbarrel fuel of boiling point in the scope of 120 DEG C-450 DEG C.This kind of midbarrel fuel is especially as diesel oil fuel, heater oil or kerosene.Preferably diesel oil fuel and heater oil.

Fuel composition of the present invention can comprise the diesel oil fuel in mineral source, i.e. diesel oil (diesel), gas oil or diesel oil (diesel oil).Mineral diesel fuel is that itself is known and commercially available.This is interpreted as the mixture that refers to the different hydrocarbon that are suitable as diesel motor fuel.Diesel oil can be used as middle runnings, especially obtains by crude distillation.The main component of diesel oil fuel preferably includes alkane, naphthenic hydrocarbon and the aromatic hydrocarbon of per molecule containing an about 10-22 carbon atom.

The diesel oil fuel boiling point in preferred mineral source is at 120 DEG C-450 DEG C, more preferably in the scope of 170 DEG C-390 DEG C.Preferably use and contain 0.2 % by weight sulphur and still less, be preferably less than 0.05 % by weight sulphur, more preferably less than 350ppm sulphur, be especially less than 200ppm sulphur, under special circumstances, be less than 50ppm sulphur, for example, be less than those middle runningss of 10ppm sulphur.They have preferably experienced the refining under hydroconversion condition, and therefore only contain those middle runningss of many aromatics of small proportion and the compound of polarity.They preferably have and are less than 370 DEG C, are especially less than 350 DEG C, under special circumstances, are less than those middle runningss of the 95% distillation point of 330 DEG C.

The also suitable diesel oil fuel as mineral source of synthol that can for example obtain by Fischer-Tropsch process or gas to liquid method (GTL).

The kinematic viscosity for the treatment of the diesel oil fuel in the mineral source preferably using records at 0.5-8mm according to ASTM D 445 at 40 DEG C ²/ s, more preferably 1-5mm ²/ s, particularly preferably 2-4.5mm ²/ s or 1.5-3mm ²in the scope of/s.

Fuel composition of the present invention can comprise at least 20 % by weight, especially at least 30 % by weight, preferably at least 50 % by weight, more preferably at least 70 % by weight, the most preferably diesel oil fuel in the mineral of at least 80 % by weight source.

In addition, fuel composition of the present invention can comprise at least one biodiesel fuel component.Biodiesel fuel is from plant or animal material or the two material obtaining, particularly oil, or their derivative that can be used as in principle the sub of mineral diesel fuel.

In a preferred embodiment, biodiesel fuel (it is often also referred to as " biofuel " or " biofuel ") comprises by containing preferred 6-30, the fatty acid alkyl ester that more preferably lipid acid of 12-24 carbon atom and the monohydroxy-alcohol containing 1-4 carbon atom form.Under many circumstances, some lipid acid can contain one, two or three two keys.Monohydroxy-alcohol especially comprises methyl alcohol, ethanol, propyl alcohol and butanols, particular methanol.

Derived from animal or plant material and oily example that can be used according to the invention be plam oil, rapeseed oil, Fructus Coriandri oil, soybean oil, cotton seed oil, sunflower oil, Viscotrol C, sweet oil, peanut oil, Semen Maydis oil, Prunus amygdalus oil, palm-kernel oil, Oleum Cocois, canola, derived from Tallow, beef particularly tallow oil, animal oil, fish oil and with the culinary art oil of crossing.Other example comprises the oil derived from cereal, wheat, jute, sesame, rice husk, Jatropha, algae, peanut oil and Toenol 1140.Treat that the fatty acid alkyl ester preferably using can obtain from these oil by method well known in the prior art.

According to the present invention, preferred heights is containing the oil of C16:0/C18:0-glyceryl ester, and for example plam oil and the oil derived from Tallow, beef, and their derivative, particularly derived from the plam oil alkyl ester of monohydroxy-alcohol.Plam oil (also claiming: palm fat) is to obtain from the pulp of palm fruit.By fruit sterilization and compacting.Due to their high carotene content, fruit and oil have orange red color, and this color is removed in refining.Described oil can contain 80%C18:0-glyceryl ester at the most.

Especially applicable biodiesel fuel is the lower alkyl esters of lipid acid.Containing 6-30 at this useful example, preferably 12-24, more preferably the ethyl ester of the lipid acid of 14-22 carbon atom, propyl diester, butyl ester, the particularly commercial mixture of methyl ester, described lipid acid is sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, pearly-lustre resin acid, stearic acid, eicosanoic acid, docosoic, lignoceric acid, cerinic acid, Zoomeric acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinolic acid, eleostearic acid, linolic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosoic acid or erucic acid for example.

In aspect one of the present invention is specific, uses and preferably comprise at least 10 % by weight, more preferably at least 30 % by weight, most preferably at least 40 % by weight are derived from the biodiesel fuel of the polyunsaturated fatty acid ester of methyl alcohol and/or ethanol.Especially, these esters have at least 16 carbon atoms in fatty acid part.These especially comprise palmitinic acid and stearic ester.

Fuel composition of the present invention can comprise other additive to realize the particular solution to problem.These additives comprise and are different from above-mentioned those other cold flow improver, dispersion agent, for example dispersing agent for wax and the dispersion agent for polar material, electric conductivity improving agent, demulsifying compound, defoamer, oiliness additive, additional antioxidant, cetane number improver, purification agent, dyestuff, corrosion inhibitor, metal passivator, metal passivator and/or odorant.

Another object of the present invention relates to the method for the cold flow properties that improves fuel oil composition, comprise the following steps: add at least one poly-(methyl) alkyl acrylate mentioned above to fuel, particularly in midbarrel fuel and its blend, and mix the composition of gained.Described interpolation is preferably carried out at the temperature more than the cloud point of used fuel.

Another object of the present invention relates to the method for the cold flow properties that improves fuel oil composition, comprises the following steps:

The enriched material of following component will be comprised

(i) at least one poly-(methyl) alkyl acrylate mentioned above and

(ii) hydrocarbon solvent/oil

Add fuel to, particularly in midbarrel fuel and its blend; And

(finally) reduces the tendency of the sedimentation of paraffin wax in fuel at low temperatures and mud shape material.

Prepare the method for PAMA

Monomer mixture mentioned above can be by method polymerization as known in the art.Multipolymer of the present invention can exist down and optionally under chain-transfer agent exists by being included in radical initiator, makes monomer (a)-(e) method preparation of reaction.Can make monomer simultaneous reactions.

Conventional radical initiator can be used for carrying out typical radical polymerization.These initiators are as known in the art.The example of these radical initiators be azo initiator as 2,2'-Diisopropyl azodicarboxylate (AIBN), 2,2'-azo two (2-methylbutyronitrile) and 1,1-azo bis cyclohexane nitriles, peralcohol, as methyl ethyl ketone peroxide, diacetone peroxide, dilauroyl peroxide, cross the 2 ethyl hexanoic acid tert-butyl ester, ketone peroxide, peroxidation methyl iso-butyl ketone (MIBK), cyclohexanone peroxide, dibenzoyl peroxide, t-butylperoxyl benzoate, tert-butylperoxy isopropyl carbonate, 2, two (the 2-ethyl hexyl acyl group-peroxides)-2 of 5-, 5-dimethylhexane, the peroxide 2 ethyl hexanoic acid tert-butyl ester, peroxide-3, 5, the 5-tri-methyl hexanoic acid tert-butyl ester, peroxidation two cumenes, 1, two (t-butyl peroxy) hexanaphthenes of 1-, 1, two (t-butyl peroxy) 3 of 1-, 3, 5-trimethyl-cyclohexane, di-t-butyl peroxide, cumene hydroperoxide and t-butyl hydroperoxide.

Poly-(methyl) acrylate of lower molecular weight can be by using chain-transfer agent to obtain.This technology be common general knowledge and for the practice of polymer industry and be described in the Principles of Polymerization (Principles of Polymerization) of Odian, 1991.The example of chain-transfer agent is aldehyde or such as mercaptan of sulfocompound, for example just with tertiary dodecyl mercaptans, 2 mercapto ethanol and mercapto-carboxylic ester, for example 3-mercapto-propionate.Preferred chain-transfer agent contains at the most 20, and particularly at the most 15, more preferably 12 carbon atoms at the most.In addition, chain-transfer agent can contain at least 1, especially at least 2 Sauerstoffatoms.

In addition, new polymerization technique can be used for obtaining available poly-(methyl) acrylate as ATRP (atom transfer radical polymerization) and/or RAFT (the reversible chain that fragmentates that adds shifts).These methods are known.For example, the people such as J-S.Wang are at J.Am.Chem.Soc., the 117th volume, 5614-5615 page (1995), with Matyjaszewski at Macromolecules, the 28th volume, 7901-7910 page has been described ATRP reaction method in (1995).In addition, patent application WO 96/30421, WO 97/47661, WO 97/18247, WO 98/40415 and WO 99/10387 disclose the various change programmes of above-mentioned ATRP, clear and definite with reference to being used for object of the present disclosure to above-mentioned document.RAFT method is for example extensively described in WO98/01478, clear and definite with reference to being used for object of the present disclosure to the document.

Polymerization can be carried out under the pressure of normal pressure, decompression or rising.Polymerization temperature neither be crucial.But generally speaking, it is-20 DEG C to 200 DEG C, preferably 0 DEG C to 130 DEG C, particularly preferably in the scope of 60 DEG C to 120 DEG C, but do not wish that this causes any restriction.

The in the situation that can or not having solvent at solvent, polymerization carries out.Term " solvent " is wanted broad understanding at this.

Preferably, be aggregated in non-polar solvent and carry out.These solvents comprise hydrocarbon solvent, for example for example toluene, benzene and dimethylbenzene of aromatic solvent, and stable hydrocarbon, for example hexanaphthene, heptane, octane, nonane, decane, dodecane, they can also be branching form.These solvents can use separately and use as mixture.Particularly preferred solvent is mineral oil and synthetic oil and their mixture.Mineral oil most preferably in them.

Mineral oil is known and commercially available on substantially.They generally by oil or crude oil by distillation and/or refining and, optionally, extra purifying and working method obtain, and especially fall into crude oil under the concept of mineral oil or the higher cut of oil.Generally speaking,, under 50 millibars, the boiling point of mineral oil is higher than 200 DEG C, preferably higher than 300 DEG C.By the low-temperature distillation of shale oil, the coking of hard coal, the distillation of brown coal under the condition of excluding air, and hard coal or brown hydrogenation of coal to be prepared be possible equally.In little degree, mineral oil also for example, for example, is prepared by the starting material of plant origin (Jojoba, rapeseed oil) or animal-origin (neat's-foot oil).Therefore,, in each case according to source, mineral oil shows the hydrocarbon of aromatics, ring-type, branching and the straight chain of different amounts.

Natural oil comprises animal oil and vegetables oil (for example Viscotrol C, lard); Liquid petroleum, and hydrofining, solvent treatment or the acid-treated mineral oil of paraffinic hydrocarbons, naphthenic hydrocarbon and combination chain alkane-naphthenic hydrocarbon type.

These solvents can be by 1 % by weight-99 % by weight except alternate manner, preferably 5 % by weight-95 % by weight, particularly preferably 5 % by weight-60 % by weight, most preferably the amount of 10 % by weight-50 % by weight is used, with respect to the gross weight of mixture, but this does not imply and wishes to carry out any restriction.

In one embodiment, described method comprises the mixture reaction that makes monomer, often first heat a part for described mixture, often about 20%-about 60%, until significant reaction, conventionally by noting heat release, then by part, or add in a lump the rest part of monomer mixture and make it reaction.

Embodiment

Experimental section

Carry out settling test with prior art WASA (based on the amino tetraacethyl of ethylene (EDTA), Tetra hydro Phthalic anhydride (PA) or alpha-olefin) with product of the present invention.Being listed below of tested WASA component.For all polymkeric substance that use in this research, the number-average molecular weight M of polymkeric substance _nfor the matter average molecular weight M of about 5000g/mol and polymkeric substance _wfor about 9000g/mol.If molecular weight aspect exists any exception, WASA uses ^(*)mark.

Component A: in solvent naphtha (Naphta) with the EDTA of 4 moles of two-tallow amine condensations;

Product content=70%

B component: in solvent naphtha with the Tetra hydro Phthalic anhydride of 2 moles of two-tallow amine condensations;

Product content=70%

Component C: in solvent naphtha with alpha-olefin-statistics copolymerization (the stat)-MA of two-tallow amine condensation;

Polymer content=70%

Component D: methacrylic acid dodecyl/pentadecyl ester

In Shellsol A 150ND, polymer content=70%

Component E: methacrylic acid dodecyl/pentadecyl ester-statistics copolymerization-methacrylic acid 2-dimethylamino ethyl ester (70/30 % by weight);

In Shellsol A 150ND, polymer content=70%

Component F: methacrylic acid dodecyl/pentadecyl ester-statistics copolymerization-methacrylic acid 2-dimethylamino ethyl ester (85/15 % by weight);

In Shellsol A 150ND, polymer content=70%

Component G: lauryl methacrylate(LMA)/methacrylic acid stearyl-statistics copolymerization-dimethylaminoethyl methacrylate (70/30 % by weight);

In Shellsol A 150ND, polymer content=70%

Component H: methacrylic acid dodecyl/pentadecyl ester-statistics copolymerization-dimethylaminopropyl Methacrylamide (70/30 % by weight);

In Shellsol A 150ND, polymer content=70%

Following table 1 has provided the summary of tested different WASA combinations.

?

W1

W2

W3

W4

W5

W6

W7

W8

Component A

100

?

B component

?

100

?

Component C

?

100

?

Component D

?

100

?

Component E

?

100

?

Component F

?

100

?

Component G

?

100

?

Component H

?

100

Table 1: as the composition of WASA test.Value provides with % by weight.

W1-W4 represents comparative example, and W5-W8 represents embodiments of the invention.

Component preparation

Component A:

At the temperature of 150 DEG C, make 12.5g EDTA, 77.5g bis-tallow amines and the melting of 0.014g tosic acid.Allow reaction to carry out during 30 minutes, after cooling, in solvent naphtha, be diluted to 70 % by weight.

B component:

At the temperature of 150 DEG C, make 35.0g PSA, 213.2g bis-tallow amines and the melting of 62.1g solvent naphtha.Allow reaction to carry out during 180 minutes, after cooling, in solvent naphtha, be further diluted to 70 % by weight.

Component C:

By 88.1g solvent naphtha, 10.5g maleic anhydride and 11.1g C _16/18-alpha-olefin adds in still and heats until 140 DEG C.In 3.5h, add continuously by C _16/18-alpha-olefin (188.4g), with 2,2-two-mixture that 50% strong solution of (t-butyl peroxy) butane (3.8g) forms.After 1.5h, temperature is reduced to 100 DEG C, now add 0.42g mistake-2 ethyl hexanoic acid tert-butyl ester.At 100 DEG C, stirring this batch of material spends the night.In inert gas atmosphere, carry out in steps.Then, by 150g C _16/18-alpha-olefin-copolymer-maleic anhydride adds in 59.6g bis-tallow amines and 25.5g solvent naphtha.By the heating of described solution until 140 DEG C and stir and spend the night.Directly remove the water just forming with lasting inert gas flow.

Component D:

107.5g solvent naphtha is added in still and heated until 140 DEG C.In 5h, add continuously by methacrylic acid dodecyl/pentadecyl ester (262.5g), with 2,2-two-mixture that 50% strong solution of (t-butyl peroxy) butane (10.0g) forms.After 1.5h, temperature is reduced to 100 DEG C, now add 0.5g mistake-2 ethyl hexanoic acid tert-butyl ester.At 100 DEG C, stirring this batch of material spends the night.In inert gas atmosphere, carry out in steps.

Component E:

143.4g solvent naphtha is added in still and heated until 140 DEG C.In 5h, add continuously by methacrylic acid dodecyl/pentadecyl ester (245.0g), methacrylic acid 2-dimethylamino ethyl ester (105.0g), with 2,2-two-mixture that 50% strong solution of (t-butyl peroxy) butane (13.3g) forms.After 1.5h, temperature is reduced to 100 DEG C, and adds 0.7g mistake-2 ethyl hexanoic acid tert-butyl ester.At 100 DEG C, stirring this batch of material spends the night.In inert gas atmosphere, carry out in steps.

Component F:

143.4g solvent naphtha is added in still and heated until 140 DEG C.In 5h, add continuously by methacrylic acid dodecyl/pentadecyl ester (297.5g), methacrylic acid 2-dimethylamino ethyl ester (52.5g), with 2,2-two-mixture that 50% strong solution of (t-butyl peroxy) butane (13.3g) forms.After 1.5h, temperature is reduced to 100 DEG C, and adds 0.7g mistake-2 ethyl hexanoic acid tert-butyl ester.At 100 DEG C, stirring this batch of material spends the night.In inert gas atmosphere, carry out in steps.

Component G:

143.4g solvent naphtha is added in still and heated until 140 DEG C.In 5h, add continuously by lauryl methacrylate(LMA)/methacrylic acid stearyl (245.0g), methacrylic acid 2-dimethylamino ethyl ester (105.0g), with 2,2-two-mixture that 50% strong solution of (t-butyl peroxy) butane (13.3g) forms.After 1.5h, temperature is reduced to 100 DEG C, and adds 0.7g mistake-2 ethyl hexanoic acid tert-butyl ester.At 100 DEG C, stirring this batch of material spends the night.In inert gas atmosphere, carry out in steps.

Component H:

143.4g solvent naphtha is added in still and heated until 140 DEG C.In 5h, add continuously by methacrylic acid dodecyl/pentadecyl ester (245.0g), dimethylaminopropyl Methacrylamide (105.0g), with 2,2-two-mixture that 50% strong solution of (t-butyl peroxy) butane (13.3g) forms.After 1.5h, temperature is reduced to 100 DEG C, and adds 0.7g mistake-2 ethyl hexanoic acid tert-butyl ester.At 100 DEG C, stirring this batch of material spends the night.In inert gas atmosphere, carry out in steps.

Handling property:

Compare handling property by measuring cloud point and pour point (respectively according to ASTM D97 and D2500), processed the temperature limitation of different WASA.For described test, WASA is dissolved in (as above described in " component " part) in Shellsol A 150N D by the concentration with 70%.

In following table 2, can clearly be seen that W1-W4 (reference WASA) shows than the much higher CP of the product of the present invention W5 and W8 and PP, and therefore show worse handling property.In addition, the embodiment of the present invention is clarified, and without any turbidity, and reference embodiment is at room temperature muddy or solid.

Table 2: the cold flow properties of WASA 70% in Shellsol A 150ND

Anti-settling performance

In the B0 based on three kinds of different fossil diesel fuel fuel and B10 diesel oil, carry out settling test (referring to the characteristic showing) below.

DK1:CP (ISO 3015)=-3.3 DEG C; CFPP (EN 116)=-10 DEG C; Density d 15 (DIN 51577)=0.8257g/ml; Distillation starts 364 DEG C of finish=163 DEG C of & of &; N-paraffin content=25 % by weight.

DK2:CP (ISO 3015)=-2.3 DEG C; CFPP (EN 116)=-5 DEG C; Density d 15 (DIN 51577)=0.8284g/ml; Distillation starts 356 DEG C of finish=170 DEG C of & of &; N-paraffin content=18 % by weight.

DK3:CP (ISO 3015)=-8.1 DEG C; CFPP (EN 116)=-12 DEG C; Density d 15 (DIN 51577)=0.8282g/ml; Distillation starts 340 DEG C of finish=245 DEG C of & of &; N-paraffin content=25 % by weight.

In typical settling test, the 500mL glassware containing with the fuel of additive to be tested (250ppm EVA base MDFI and 150ppm WASA) blending is dropped in ethanol bath.Before sedimentation, the CP of measure sample, CFPP and PP.The CP of based on fuel+additive and PP are down to certain temperature by cooling ethanol bath, because sample should not freeze (temperature is far away higher than PP and lower than CP).Rate of cooling is 0.24 DEG C/min and allows sample in lower 16 hours of temperature.After this period, remove carefully 80% (top phase) of the top volume being included in glassware and for remaining 20% (bottom phase), after homogenizing, measure CP.

Δ CP describes the difference between CP " 20% residue " and CP " initially ".Δ CP is less, and wax anti-sedimentation agent is more effective.Be generally expected that, good WASA provides 2 DEG C or following Δ CP.

Table 3: the B0 processing with WASA comparative example (W1 and W3) and product of the present invention (W5-8) and the Δ CP of B10DK1.Have ^*wASA there is the M of about 24000g/mol _n.

Obviously find out from table 3, product of the present invention, W5-W8 shows the performance similar to comparative example in B0DK1.In addition, W8 even shows the better efficiency than W1-3.The even more WASA of high molecular, W5 ^*and W8 ^*(M _napproximately 24000g/mol) show extraordinary anti-settling performance.

In the blend of being made up of the RME of DK1 and 10%, WASA of the present invention shows the performance identical with EDTA base reference sample, and interestingly, and all new WASA are better than comparative example W3 (based on alpha-olefin).

Table 4: the B0 processing with WASA comparative example (W1-W4) and product of the present invention (W5-W8) and the Δ CP of B10DK2.Have ^*wASA component there is the M of about 24000g/mol _n.

In table 4, show the Δ CP value obtaining during the settling test in the blend of fuel DK2 and itself and 10%RME.In B0, product of the present invention shows the Δ CP value of 2.2 DEG C to 2.8 DEG C, this with use the performance respectively with 2.3 DEG C and 3.7 DEG C of comparative example W2 and W3 acquisition suitable.In such fuel, W8 provides best wax stabilization, because measure the Δ CP of 1.4 DEG C.

In B10RME, W1-W4 shows the efficiency of non-constant unlimitedly.Interestingly notice, reference WASA W4 is different from the embodiment of the present invention, because it does not have N-dispersion agent functionality.On the contrary, WASA W7 of the present invention, W8 and W8 ^*show much better Δ CP value, be 1.2 and 1.0 DEG C and be 2.3 DEG C for 24000g/mol for the number-average molecular weight of 5000g/mol.

Table 5: the B0 processing with WASA comparative example (W1, W3 and W4) and product of the present invention (W5-W8) and the Δ CP of B10DK3.Have ^*wASA component there is the M of about 24000g/mol _n.

In DK3B0, reference WASA, W3 and W4, show respectively the Δ CP of 5.4 and 4.1 DEG C, and in the time using W7 and W8 (being respectively DMAEMA and DMAPMAm), records average low more than the clean improvement of 1 DEG C.

The settling test carrying out at-11 DEG C in RME/DK3 blend shows identical evaluation rank, and the even more significant Δ CP value with average 2 DEG C reduces.When again, by cooling identical blend while being low to moderate-8 DEG C, W7 and W8 are better than the result that is greater than 5 DEG C by using W1 (EDTA base WASA) to obtain significantly.

Claims

1. comprise poly-(methyl) alkyl acrylate of following monomeric unit for improvement of the purposes of the cold flow properties of fuel oil composition:

Wherein

R is H or CH ₃,

Wherein

R is H or CH ₃,

Wherein

R is H or CH ₃,

(d) vi-ny l aromatic monomers of 0 % by weight-30 % by weight, and

(e) at least one N-dispersion agent monomer of 2-80 % by weight,

Wherein component (a)-(e) total 100 % by weight.

2. according to the purposes of claim 1, it is characterized in that described poly-(methyl) alkyl acrylate has the number-average molecular weight M of 2500-100000 _n.

3. according to the purposes of claim 1, it is characterized in that described poly-(methyl) alkyl acrylate has the number-average molecular weight M of 4000-20000 _n.

4. according to the purposes of claim 1, it is characterized in that the polymolecularity M of described poly-(methyl) alkyl acrylate _w/ M _nin the scope of 1-8.

5. according to the purposes of claim 1, it is characterized in that the polymolecularity M of described poly-(methyl) alkyl acrylate _w/ M _nin the scope of 1.3-2.5.

6. according to the purposes of claim 1, it is characterized in that described vi-ny l aromatic monomers (d) is selected from the vinylbenzene of vinylbenzene and replacement.

7. according to the purposes of claim 1, it is characterized in that the N-dispersion agent monomer of component (e) is the monomer with following formula (IV)

Wherein

R ¹⁵representative containing the straight or branched of 1-5 carbon atom, saturated or unsaturated alkyl or aryl and

R ¹⁴representative is containing the straight or branched alkyl of 1-20 carbon atom, and it is not replace or by group-NR ¹⁶r ¹⁷replace wherein R ¹⁶and R ¹⁷represent independently H or containing the straight or branched alkyl of 1-8 carbon atom, or R wherein ¹⁶and R ¹⁷be a part for or unsaturated ring saturated containing one or more heteroatomic 4-8 units that are selected from nitrogen, oxygen or sulphur optionally, wherein said ring can further be replaced by alkyl or aryl, and it is several 1,2,3 or 4 that x represents,

Or,

8. according to the purposes of claim 1, it is characterized in that the described N-dispersion agent monomer of component (e) is selected from amine and the N-vinyl lactam of the nitrogen heterocyclic monomer of the nitrogen heterocyclic monomer of vinyl substituted, N-vinyl substituted, propenoic acid dialkyl aminoalkyl ester and methacrylic acid dialkyl aminoalkyl ester monomer, methyl acrylamide monomer, N-tertiary alkyl acrylamide and corresponding Methacrylamide, vinyl substituted.

9. comprise the enriched material of following component as fuel, particularly the additive of midbarrel fuel is for improvement of the purposes of the cold flow properties of fuel oil composition:

Wherein

R is H or CH ₃,

Wherein

R is H or CH ₃,

Wherein

R is H or CH ₃,

(d) vi-ny l aromatic monomers of 0 % by weight-30 % by weight, and

(e) at least one N-dispersion agent monomer of 2-80 % by weight,

Wherein component (a)-(e) total 100 % by weight; With

(B) hydrocarbon solvent/oil of 10 % by weight-70 % by weight.

10. comprise the fuel of following component for improvement of the purposes of cold flow properties:

(a) at least one of 0 % by weight-99 % by weight biofuel oil based on fatty acid ester,

(b) middle runnings of the fossil sources of 1 % by weight-100 % by weight and/or plant and/or animal-origin, it is hydrocarbon mixture and not fatty acid esters substantially, and

(c) according to the enriched material of claim 9.

11. according to the purposes of claim 14, it is characterized in that existing one or more to be selected from following additive: additional cold flow improver, dispersion agent, electric conductivity improving agent, demulsifying compound, defoamer, oiliness additive, antioxidant, cetane number improver, purification agent, dyestuff, corrosion inhibitor, metal passivator, metal passivator and/or odorant.