CN1644662A

CN1644662A - Method for the reduction of deposits in jet engine

Info

Publication number: CN1644662A
Application number: CNA2004101047711A
Authority: CN
Inventors: D·M·斯潘塞; R·D·泰克
Original assignee: Infineum International Ltd
Current assignee: Infineum International Ltd
Priority date: 2003-10-15
Filing date: 2004-10-15
Publication date: 2005-07-27
Also published as: KR20050036784A; JP2005120380A; CA2484836A1; US20050086855A1

Abstract

A method for reducing the level of deposits in a jet engine, the method comprising supplying to the jet engine a jet fuel composition comprising a jet fuel and at least one hydrocarbyl comb polymer; wherein the at least one hydrocarbyl comb polymer has a number average molecular weight, as measured by Gel Permeation Chromatograph y against polystyrene standards, of less than 5,500, preferably less than 5,000. The low temperature properties of the jet fuel are also improved.

Description

Be used for reducing the sedimental method of jet engine

The present invention relates to the method that a kind of settling that reduces in jet engine and the jet fuel composition forms.Especially, the present invention relates to be applicable to jet fuel composition under the low temperature (for example being lower than-40 ℃ or-50 ℃).

The most frequently used jet fuel is Jet A and Jet A-1, and zero pour maximum in the specification of these fuel is respectively-40 ℃ to-47 ℃.When temperature was lower than the zero pour of jet fuel, hydrocarbon molecule generation crystallization also was precipitated out.N-paraffin in the jet fuel has the highest Tc, therefore at first separates out from solution with the form of wax crystalls.Along with the crystallization of hydrocarbon molecule, the viscosity of jet fuel increases, and this will make the mobile reduction of fuel.At Boeing ^On the aircraft, the temperature of fuel must remain on and be higher than at least 3 ℃ at specification zero pour, and passenger vehicle aloft ^On the aircraft, fuel temperature must remain on and be higher than at least 4 ℃ at specification zero pour.If fuel temperature begins near this specification zero pour, then must take measures to prevent its further cooling.This measure generally includes: walk around cold zone flight, thereby the speed that makes aircraft be reduced to warmer temperature flight or increase aircraft increases the aerodynamics heating.Under extreme case, need gather way and reduce aircraft altitude simultaneously.A kind of shortcoming of this measure is that it often increases fuel consumption.Carried out the fuel container of various researchs, yet this will increase the weight and the fuel consumption of flying machine to consider that employing is heated.

The zero pour of jet fuel is controlled in still-process in refinery at present.The reduction zero pour can be reduced to needed any level by the last running that will comprise wax slop and realize, still, reduces last running utilizability is had significant negative effect.The someone points out that changing JetA-1 into from Jet A can reduce amount usable 8%.

Jet A-1 is the standard specifications jet fuel in Europe, and normally for the situation in winter and desired such as the path of crossing the polar region.Jet A normally uses in U.S.'s domestic flight.

In addition or on this basis, the zero pour of jet fuel also is subjected to the control of employed additive.Yet known some additive can produce undesirable combustion deposit on the surface of jet engine.These settlings are harmful to the performance of engine.

The temperature that is lower than 0 ℃ also can make the water in the fuel freeze, and this meeting blocking filter and other little hole, and can make flame-out of engine once in a while.Use based on the water separator on ground and control water content in the fuel, and, importantly, add various additives in the jet fuel to and do not stop up the various strainers in these separators or make it and lost efficacy.ASTM D 3948-93 is used for determining that strainer-separator isolates the test method of the ability of free water from fuel.

US5807949 has described the low-temperature performance that the multipolymer that uses two kinds of alhpa olefins improves lubricated and fuel oil.The multipolymer of preferred n-octyl alkene and n-tetradecane alkene or n-hexadecane alkene.

EP1357169A2 has described the jet fuel composition with good low-temperature performance.These compositions can comprise preferably from C ₄-C ₆1-alkene and C ₁₀-C ₁₄The various comb shaped polymers that 1-alkene forms.

The purpose of this invention is to provide can be in jet engine the jet fuel composition that produces of still less settling.

Another object of the present invention provides and is suitable for low temperature, for example is lower than-40 ℃, preferably is lower than-50 ℃ jet fuel composition.Especially, the purpose of this invention is to provide the jet fuel composition that is adapted at the following temperature use of specification zero pour.

Another object of the present invention provides the additive that can effectively improve the low temperature operability of jet fuel.

Content according to a first aspect of the invention, a kind of method that is used for reducing the jet engine sediment yield is provided, this method comprises: the jet fuel composition is offered jet engine, and this jet fuel composition comprises jet fuel and at least a alkyl comb shaped polymer; Wherein, when with respect to polystyrene standard during by gel permeation chromatography measurement, the number-average molecular weight that at least a alkyl comb shaped polymer is had is less than 5500, preferably less than 5000.

Comb shaped polymer is the polymkeric substance with main chain and side chain.

Preferably, when relative polystyrene standard during by gel permeation chromatography measurement, this alkyl comb shaped polymer has less than 4800, preferably less than 4500 number-average molecular weight.More preferably, when with respect to polystyrene standard during by gel permeation chromatography measurement, this alkyl comb shaped polymer has less than 4300, preferably less than 4000 number-average molecular weight.Even more preferably, when with respect to polystyrene standard during by gel permeation chromatography measurement, this alkyl comb shaped polymer has less than 3800, preferably less than 3500 number-average molecular weight.Most preferably, when with respect to polystyrene standard during by gel permeation chromatography measurement, this alkyl comb shaped polymer has less than 3000, preferably less than 2800 number-average molecular weight.

Preferably, this hydro carbons comb shaped polymer is C ₃-C ₉1-alkene and C ₁₀-C ₁₄1-alkene, preferred C ₄-C ₈1-alkene, more preferably C ₆-C ₈1-alkene and C ₁₀-C ₁₄The hydrocarbon polymer of 1-alkene or multipolymer.Even more preferably, this comb shaped polymer is C ₆-C ₈1-alkene and C ₁₂The hydrocarbon polymer of 1-alkene or multipolymer.Most preferably, this alkyl comb shaped polymer is C ₈1-alkene and C ₁₂The hydrocarbon polymer of 1-alkene or multipolymer.

This hydro carbons comb shaped polymer or multipolymer the amount in this jet fuel of adding should be 10-20000ppm, preferred 100-10000ppm, 500-5000ppm (umber of additive in per 1,000,000 parts of fuel) most preferably.

Jet fuel can be chosen from following fuel: Jet A, Jet A-1, Jet B, MILJP 5, MIL JP 7, MIL JP 8 and MIL JP 4.Preferred Jet A, Jet A-1 and MIL JP 8.

The contriver is surprised to find the method that limits above and causes the low sediment in the jet engine to form, and uses the fuel element of this method also to demonstrate good low temperature operability simultaneously, that is, the depression of pour point of jet fuel.

Content according to second aspect present invention, it provides the purposes of at least a alkyl comb shaped polymer, when relative polystyrene standard during by gel permeation chromatography measurement, this comb shaped polymer has less than 5500, preferably less than 5000 number-average molecular weight, this comb shaped polymer is as the additive that is used for jet fuel, so that reduce the sedimental amount of supplying with the jet engine that this jet fuel is arranged.

Comb shaped polymer is discussed in the article " polymkeric substance of comb shaped polymer, structure and performance " that is published in by N.A.Plat é and V.P.Shibaev on J.Poly.Sci.Macromolecular Revs. the 8th volume 117-253 page or leaf (1974).

Usually, comb shaped polymer all is to be made of such molecule, promptly in this molecule, optional interrupt and have 6-30, a long-chain side chain of a for example 8-20 carbon atom by one or more Sauerstoffatoms and/or carbonyl group, alkyl side chain for example, be suspended on the main polymer chain, described side chain is linked on this main chain by direct key.Usually comb shaped polymer is to be distinguished by the unitary minimum molar ratio that contains this long-chain side chain.

Therefore in various application, for example jet fuel, the heteroatomic polymkeric substance of polarity that contains such as oxygen has attractability to glassware for drinking water, can make during the aircraft fuel feeding shipwreck to separate from jet fuel.For fear of this water attractability, the comb shaped polymer among the present invention only is an alkyl, and promptly it comprises carbon and hydrogen atom.These comb shaped polymers are long-chain 1-alkene, for example the polymkeric substance or the multipolymer of 1-decene, 1-laurylene, 1-tridecylene, 1-tetradecylene or 1-hexadecylene (hesiadecene).Therefore the repeating unit of this polymkeric substance is 1, the disubstituted positive alkene of 2-:

Wherein R generally is meant n-C ₈H ₁₁(being derived from the polymerization of 1-decene) is to n-C ₁₄H ₂₉The alkyl group of (polymerization of cetene).The ideal structure of this comb shaped polymer is (only showing the C-C key):

The choosing of the length of this positive pendent alkyl groups make its can be at low temperatures with isolated wax from jet fuel in normal alkane have best interaction.Have been found that they mainly are C ₁₀To C ₁₄Positive alkyl.

This polymkeric substance can be easily made by metallocene (for example zirconocene (the zirconocene)) polymerization of 1-alkene, and this can guarantee the handiness of molecular weight.Yet these polymkeric substance have the upright structure systematicness of height, therefore have high fusing point (with respect to lower regular texture) and limited low temperature solubility in hydro carbons.Low temperature in the jet fuel (low to-50 to-60 ℃) solubility is necessary in this application, so, the low molecular moiety of short chain 1-alkene (or its mixture), preferably less than 40 moles of %, be more preferably less than 30 moles of %, 10-30 mole % most preferably, produce copolymerization with long-chain 1-alkene.This will bring increases under the low temperature effect of the solubility of comb shaped polymer in the liquid hydrocarbon, keeps cooperating of isolated nalka chloroflo in the positive alkyl of side group long-chain and the jet fuel simultaneously.

In this application, have been found that this long-chain 1-alkene preferably includes more than 8 carbon atoms and 20 carbon atoms at the most.This long-chain 1-alkene preferably includes 1-decene, the C of 1-laurylene and 1-tetradecylene (referring to the embodiment of WO93/19106) ₁₀-C ₁₅1-alkene.This comb shaped polymer is preferably by at least a long-chain 1-alkene, 1-laurylene for example, with at least one short chain 1-alkene, for example 1-butylene is pressed the comb shaped polymer of the short chain 1-alkene of the long-chain 1-alkene of the short chain 1-alkene of the long-chain 1-alkene of 60-90 mole % and 40-10 mole %, preferred 70-85 mole % and 30-15 mole %.Have been found that this short chain 1-alkene can be the C on the 1-octene ₃To C ₉, for example 1-butylene, 1-hexene.

According to the content of the third aspect, a kind of jet fuel composition is provided, said composition comprises jet fuel and at least a alkyl comb shaped polymer; Wherein at least a comb shaped polymer is C ₈1-alkene and C ₁₂The hydrocarbon polymer of 1-alkene or multipolymer, and when with respect to polystyrene standard during by gel permeation chromatography measurement, its number-average molecular weight are less than 5500, preferably less than 5000.

The size of the wax crystalls that the jet fuel composition that limits above forms in the time of being reduced in the jet fuel cooling also changes its shape, increases thereby make jet fuel not form gel and produce undesirable viscosity.Standard pour point testing method ASTM D97 can be used for determining the point of fuel generation gel.Other relevant test is zero pour, cloud point, variable temp viscometer and DSC, their details can obtain from following document: by S.Zabarnick and M.Vangsness, Petroleum Chemistry Division preprints, 2002 the 47th (1) phases, " effect of the performance of jet fuel and additive under the low temperature "; J.S.Manka, the content of wax jet fuel of describing in SAE technical article 2002-01-1650 " jet fuel low temperature operability " literary composition keeps test; C.Obringer, ' Over view of JP 8+100 LowTemperature Program ', 2001, Co-coordinating Research Council, AviationMeeting, Low Temperature Performance group (May calendar year 2001).

Wonderful characteristics of the present invention are that the described jet fuel composition of third aspect content has beyond thought good low temperature properties.The applicant has been found that from C ₈1-alkene and C ₁₂The specific comb shaped polymer that 1-alkene forms is better than even very relevant polymer material.For example by C ₈1-alkene and C ₁₀The polymkeric substance that 1-alkene forms reaches by C ₈1-alkene and C ₁₄The polymkeric substance that 1-alkene forms all can not show good like this low-temperature performance.Except that the characteristic that settling is reduced (this specific character is that described polymkeric substance of third aspect content and the described polymkeric substance of the first and second aspect contents are total), this advantage additionally has.

According to the content of fourth aspect, the method that is used to reduce the jet fuel pour point also is provided, this method comprises the following steps:

A) provide a kind of jet fuel; With

B) polymkeric substance that the content by the third aspect is limited adds in this jet fuel.

According to the content of the 5th aspect, provide the purposes of the polymkeric substance of third aspect content qualification, to reduce the low temperature operability of jet fuel.

The jet fuel cold-flow test or the content of wax jet fuel retention test that are undertaken by the variable temp viscometer, all support use with the 1-laurylene of the 1-octene copolymer of 20-30 mole %, with the improvement that obtains cold flow properties in the wide molecular weight scope (for example, the polymkeric substance of number-average molecular weight Mn the highest 20000 being tested) (promptly comparing the available flowability when having) at low temperature more with untreated fuel when relative polystyrene standard during by gel permeation chromatography measurement.Yet, have been found that more high molecular weight polymers (Mn is at least 5500) can stay undesirable deposits when jet engine is in idling.Have been found that molecular weight of copolymer is reduced to less than 5500 and can alleviates this settling formation problem.In addition, the low viscosity of polymkeric substance can make low-molecular-weight polymkeric substance easily with 100% polymkeric substance pumping during low temperature, therefore makes the needs to the transportation of dilution in advance and a large amount of solvents and polymkeric substance all reach minimum.

Another advantage of the present invention is that this jet fuel composition can not block the strainer in the water separator or make it inefficacy.

This jet fuel composition can also comprise at least a following additional additive:

(i) multipolymer of ethene and at least a unsaturated ester;

The (ii) multipolymer of ethene and alkene;

(iii) nucleator;

(iv) wax

(v) a large amount of branched-alkyl phenolic condensation compounds (being referred to as APFC);

(the vi) comb shaped polymer of from the polymkeric substance of unsaturated ester or multipolymer or alkene copolymer-maleic anhydride, choosing; With

(vii) polar nitrogen compounds.

This jet fuel composition preferably also comprise at least a from (i) or the multipolymer of choosing (ii) and at least a polar nitrogen compounds (vi), and optional at least a nucleator (iii).

This jet fuel composition preferably also comprise at least a from (i) or the multipolymer of choosing (ii) and at least a comb shaped polymer (vi), and optional at least a nucleator (iii).

This jet fuel composition preferably also comprise at least a polar nitrogen compounds (vii) with at least a comb shaped polymer (vi).

This jet fuel composition preferably also comprise at least a polar nitrogen compounds (vii) and a large amount of branched-alkyl phenolic condensation compounds (v).

This jet fuel composition preferably also comprise at least a polar nitrogen compounds (vii) with at least a nucleator (iii).

Describe these extra additives below in detail.

(i) multipolymer of ethene and at least a unsaturated ester class

This unsaturated ester class can be a vinyl acetate, (methyl) vinylformic acid hydrocarbyl carbonate, dialkyl fumarate and dialkyl maleate.

This vinyl acetate unit preferably has following formula:

-CR ¹R ²-CHR ³-

R wherein ²Expression hydrogen or methyl group; R ¹Expression-OOCR ⁴Group, wherein R ⁴Expression C ₁To C ₂₈, more preferably C ₁To C ₁₆, more preferably C ₁To C ₉Straight chain or branched-alkyl group; R ³The expression hydrogen or alkyl.

This vinyl acetate is preferably chosen from following material: propionate, vinyl butyrate, vinyl caproate, 2 ethyl hexanoic acid vinyl acetate, sad vinyl acetate and vinyl benzoate.Also can be with new vinyl acetate, for example new n-nonanoic acid vinyl acetate and new vinyl acetate acid.

This unsaturated ester preferably less than the vinyl-acetic ester of 15 moles of %, preferably less than 14 moles of %, be more preferably less than the vinyl-acetic ester of 12 moles of %.When by gel permeation chromatography measurement, preferably the number-average molecular weight of this multipolymer is 1000-10000, more preferably 2000-5000.

Should preferably have following molecular formula by (methyl) vinylformic acid hydrocarbyl carbonate:

-CR ⁵R ⁶-CHR ⁷-

R wherein ⁶Expression hydrogen or methyl group; R ⁵Expression-COOR ⁸Group, wherein R ⁸Expression C ₁To C ₂₈, preferred C ₁To C ₁₆, more preferably C ₁To C ₉Straight chain or branched chain alkyl group; R ⁷The expression hydrogen or alkyl.

Used term " (methyl) acrylate " had both comprised that acrylate also comprised methacrylic ester.

(methyl) alkyl acrylate preferably from: (methyl) 2-EHA, (methyl) ethyl propenoate, (methyl) vinylformic acid just-, exclusive OR uncle-butyl ester, (methyl) Ethyl acrylate, (methyl) isopropyl acrylate and (methyl) lauryl acrylate.

Dialkyl fumarate is preferably represented by following formula:

R wherein ⁹And R ¹⁰From alkyl group, choose independently with 1-9 carbon atom, preferred 1-8 carbon atom.

Dialkyl fumarate is selected from DEF, dibutyl fumarate and fumaric acid two (2-ethyl-hexyl) ester.

Dialkyl fumarate is preferably represented by following formula:

R wherein ¹¹And R ¹²Be independently selected from have 1-9 carbon atom, the alkyl group of preferred 1-8 carbon atom.

Dialkyl maleate is preferably selected from ethyl maleate and dibutyl maleinate.

When by gel permeation chromatography measurement, the preferred 1000-20000 of the number-average molecular weight of this multipolymer, preferred 1000-10000, more preferably 2000-5000.

If desired, this multipolymer can be by other comonomer-derived, for example they can be trimer or tetramer or high-grade polymkeric substance more, and for example described other comonomer is 1-butylene, propylene or diisobutylene or other unsaturated ester class that constitutes different units in the above-mentioned molecular formula.

In addition, this multipolymer can also be included in spendable chain-transfer agent and/or molecular weight regulator (for example acetaldehyde or propionic aldehyde) than small proportion in the polymerization process that generates this multipolymer.

These multipolymers can be obtained by the comonomer direct polymerization.These multipolymers also can be made by the transesterify of ethene unsaturated ester analog copolymer or hydrolysis and resterification, thereby obtain different ethene unsaturated ester analog copolymers.For example, ethene-vinyl caproate and ethene-sad vinyl ester copolymers can for example be made by ethylene-ethyl acetate copolymer by this method.

For example, methyl group on the comonomer ester and the non-end-blocking methyl group, when by the nucleus magnetic resonance spectrometry, per 100 main polymer chain methylene groups of multipolymer have 15 or still less, preferred 10 or still less, more preferably 6 or still less, 2-5 methyl blocking side chain most preferably.

This multipolymer can have the distribution of polymerization degree of 1-6, preferred 1.5-4; Distribution of polymerization degree is the ratio of weight-average molecular weight and number-average molecular weight when using polystyrene standard by gel permeation chromatography measurement.

The preferred 50-95 mole of the ethene molar content % of this multipolymer.The preferred 55-90 mole of ethylene content %, more preferably 60-90 mole %, 70-90 mole % most preferably.

The (ii) multipolymer of ethene and alkene

Alkene preferably includes 20 carbon atoms at the most.This alkene preferably has the 1-alkene of 20 carbon atoms at the most.This 1-alkene is preferably chosen from following material: propylene, 1-butylene, 1-hexene, 1-octene, Methyl-1-pentene, 1-decene, 1-laurylene, 1-tridecylene, 1-tetradecylene, 1-ten pentaenes, the 1-hexadecylene, 1-octadecylene, 1-icosa alkene and vinyl-hexanaphthene, and their mixture.

But this multipolymer also can comprise on a small quantity, for example be at most the monomer of other copolymerization of 10 weight %.

When polystyrene standard was measured by gel permeation chromatography (GPC) relatively, the molecular weight that this multipolymer can have was 1000-50000, preferred 1000-20000, most preferably 1000-10000.

The preferred 50-90 mole of the molar ethylene content % of this polymkeric substance.The preferred 55-85 mole of this ethylene content %, more preferably 60-85 mole %, 70-85 mole % most preferably.

This multipolymer can be produced by any in the art known method, for example uses the catalyzer of choosing from following material to produce: Ziegler-Natta type catalyzer and metallocene catalyst.

(iii) nucleator

The preferred polyoxy olefin(e) compound of nucleator.Example comprises polyoxy alkene ester, ether, ester/ether and its mixture, particularly those comprise at least one, preferred at least two C ₁₀To C ₃₀The straight chained alkyl group and one or more molecular weight is the highest by 5000, the polyoxy alkene ethylene glycol group of preferred 200-5000, described in EP-A-61895 and US4491455, the alkylene group in the described polyoxy alkene ethylene glycol contains 1-4 carbon atom.

Ethylene glycol is preferred to be straight chain polyoxyethylene glycol (PEG) and polypropylene glycol (PPG) substantially, and its molecular weight is about 100-5000, preferably approximately 200-1500.Ester also is preferred, and the lipid acid that contains 10-30 carbon atom can be used to react to form various ester class additives with glycol.The preferred C that uses ₁₂-C ₁₈Lipid acid, particularly tetradecanoic acid, palmitinic acid and stearic acid.The ester class also can be utilized polyoxyethylene fatty acid, and Volpo S 10 or polyvalent alcohol carry out esterification and prepare.

Polyoxy alkene two fat, diether, ether/ester and its mixture all are suitable as additive, also can have a spot of monoether and monoesters (they usually form in manufacturing processed) this moment.Especially, myristinate, cetylate or the stearate of polyoxyethylene glycol, polypropylene glycol or poly-second/polypropylene glycol mixture, all be preferred.

The example of other compound in this big class is those at those and the ring-type esterification ethoxylate described in EP-A-356256 described in Japanese patent laid-open publication gazette 2-51477 and 3-34790 and EP-A-117108 and the EP-A-326356.

Other suitable ester class is the ester class that can be obtained by the reaction of following material:

(i) have 10-30 carbon atom the fatty group monocarboxylic acid and

(ii) alkoxylated fats list alcohol, wherein the carbonatoms that had before alkoxylate of alcohol is greater than 12, and oxyalkylated degree is that every mol of alcohol has 3-25 mole alkylene oxide.

This ester can (ii) be formed by only a kind of acid reaction (i) and only a kind of ethanol synthesis thing, perhaps by the mixture of acid (i) or alcohol (ii) mixture or both mixtures form.For the latter, generate the mixture of ester products, if desired,, described mixture separates usefulness even can not adding, perhaps separate before use to obtain isolating product.

These materials also can be by the alkoxylate preparation (for example ethoxylation dehydrated sorbitol ester of three stearic acid of the commodity TWEEN 65 by name that can obtain from the Uniqema that ICI (ICI) has) of the fatty acid ester of polyvalent alcohol.

The preferred every mol of alcohol 3-25 mole of oxyalkylated degree of the single alcohol of fat, more preferably 3-10 mole alkylene oxide.Although propoxylation or butoxyization also can successfully be used, preferably this alkoxylate is ethoxylation.Mixed oxyalkylization, for example ethoxylation and propenoxylated mixing also can be adopted.

Acid reaction (i) preferably has 12-30 carbon atom, more preferably 12-18 carbon atom, for example 14 or 16 carbon atoms.The preferred saturated fatty acid of this acid, more preferably paraffinic acid.The paraffinic acid of 12-30 carbon atom is useful especially.Preferred normal chain alkanoic acid.This acid comprises tetradecanoic acid, palmitinic acid and stearic acid, preferred tetradecanoic acid and palmitinic acid.Using under the situation of acid mixture, preferably the carbon atom mean number of this acid mixture is in the above-mentioned scope, and preferably in this mixture the carbonatoms between the single acid differ and be no more than 8, more preferably 4 carbon atoms.

Before alkoxylate, this alcohol reactant is (ii) preferably derived from the fatty single alcohol with no more than 28, more preferably no more than 18 (or being no more than 16 better) carbon atoms and is obtained.For obtaining good wax crystallization modifying function, the scope of 12-18 carbon atom is superior especially.This Fatty Alcohol(C12-C14 and C12-C18) preferred saturated fatty alcohol, particularly alkanol (being alkyl alcohol).

At alcohol reactant (ii) is under the situation of alcohol mixture, and this mixture can comprise ethoxylation only a kind of Fatty Alcohol(C12-C14 and C12-C18) extremely in various degree, or ethoxylation is to the fatty alcohol mixture of identical or different degree.When adopting fatty alcohol mixture, its average carbon atom number and preferably is in the above-mentioned preferable range greater than 12 before alkoxylate.No more than 4 of the difference of the carbonatoms of the various alcohol that use in the preferred mixture.

Esterification can be realized by present technique field known technology.

The alkoxylate of Fatty Alcohol(C12-C14 and C12-C18) also can be realized by known technology.

Nucleator also can be only to comprise a crystallizable segment and only not crystallizable segmental segmented copolymer (" double-stranded section " polymkeric substance) and those only comprise not crystallizable segment and have an only crystallizable segmental segmented copolymer (" three segments " polymkeric substance) at its each end.Other three segments-and four segments-multipolymer also be available.(wherein multipolymer derive from divinyl and isoprene obtain) in preferred embodiments, these double-stranded sections and three segmented polymers are referred to as PE-PEP and PE-PEP-PE respectively.

Crystallizable segment mainly is from 1 of divinyl, the unitary hydrogenation product that 4-or end-to-end polymerization obtain, and not crystallizable segment is from 1 of divinyl, the unitary hydrogenation product (PE-PEB) that the 2-polymerization obtains, or alkyl-substituting group divinyl, for example isopentene 1, the unitary hydrogenation product (PE-PEP) that the 4-polymerization draws.

(iv) wax

Wax just comprises and non-normal paraffin hydro carbons.

The preferred C of the scope of normal paraffin hydro carbons ₈H ₁₈To C ₃₅H ₇₂The number-average molecular weight of this paraffinic hydrocarbon preferably is in about scope of 150 to 300.Although can use independent paraffinic, the result normally utilizes the paraffinic of the mixture that comprises hydro carbons to obtain preferably.The scope of this normal paraffin hydro carbons is C ₈To C ₃₀, more preferably C ₁₀To C ₂₅

This paraffinic can be chosen from the waxy stone such as slack wax and slop wax.This paraffinic can utilize in the dewaxing of the routine of about 200 ℃ of various waxy oil refinery streams of ebullient in about 500 ℃ scope and obtain.Specially suitable wax is to be the slack wax that the solvent dewaxing of about 200 ℃ to 400 ℃ oil obtains from boiling spread.

Non-normal paraffin hydro carbons preferably includes in fusing point 10-60 ℃, preferred 20-40 ℃ of scope, and number-average molecular weight is in the amorphous solid material in 150 to 500 scopes.

Suitable amorphous hydro carbons cut can utilize " deoiling " or " hot melt " of wax and obtain in the refining process of wax.Non-nalka chloroflo is also referred to as foots oil and filtrate.

(v) a large amount of branched-alkyl phenolic condensation compounds (APFC)

The alkyl phenolic condenses is disclosed among EP0311452 and the EP0851776.

The alkyl phenolic condenses can prepare by the condensation reaction between the following material:

(i) at least a aldehydes or ketones or their reactive equivalent and

(ii) at least aly comprise one or more at least one formula-XR that contain ¹³Substituting group and at least one other substituting group-R ¹⁴The compound of aromatic group, wherein:

X represents oxygen or sulphur,

R ¹³Expression hydrogen or contain the group of at least one hydrocarbyl group, and

R ¹⁴Represent a large amount of branched hydrocarbyl radical groups, preferably include 4-40 carbon atom, more preferably comprise 8-30 carbon atom, most preferably comprise 8-18 carbon atom.

Suitable a large amount of branched-alkyl phenolic condensation compounds comprise different nonyl phenol aldehyde condensate and Permethyl 99A. base phenolic condensation compound.

(vi) comb shaped polymer

Other comb shaped polymer is to choose from the polymkeric substance of unsaturated ester or multipolymer or alkene copolymer-maleic anhydride.

This comb shaped polymer can be polymkeric substance or the multipolymer that comprises unit of following formula:

Herein, D represents R ¹⁶, COOR ¹⁵, OCOR ¹⁵, R ¹⁶COOR ¹⁵Or OR ¹⁵

E represents H or D;

G represents H or D;

J represents H, R ¹⁶, R ¹⁶COOR ¹⁵, or replacement or unsubstituted aryl or heterocyclic group;

K represents H, COOR ¹⁶, OCOR ¹⁶, OR ¹⁶Or COOH;

L represents H, R ¹⁶, COOR ¹⁶, OCOR ¹⁶Or replacement or unsubstituted aryl;

R ¹⁵Expression has the hydrocarbyl group of 10 or more a plurality of carbon atoms, and

R ¹⁶Expression R ¹⁶COOR ¹⁵Alkylidene group in the group (divalence) and, if not so, alkyl (unit price) group,

And m and n represent mol ratio, itself and be 1, m is a non-zero, maximum can reach for 1 (containing 1), and n be from 0 to less than 1, preferred m is in the scope of 1.0-0.4, n is in the scope of 0-0.6.R ¹⁵With expression have 10-30, preferred 10-24, more preferably the hydrocarbyl group of 10-18 carbon atom is favourable.R ¹⁵Preferably straight chain or the alkyl group of branching slightly, R ¹⁶With expression have 1-30 carbon atom (when its when being monovalent), preferred 6 or more, more preferably 10 or more, preferred maximum 24, more preferably the hydrocarbyl group of maximum 18 carbon atoms is favourable.When its when being monovalent, R ¹⁶Be a straight chain or the alkyl group of branching slightly.Work as R ¹⁶Be divalence the time, its preferred methylene radical or ethylidene." branching slightly " is meant to have only methyl branch.

If wish or needs that comb shaped polymer can comprise the unit that obtains from other monomer derived, example is CO, vinyl-acetic ester and ethylidene.

Comb shaped polymer also can be maleic anhydride acid and other vinyl unsaturated monomer, for example alpha-olefin or unsaturated ester, for example vinyl-acetic ester described in the EP-A-214786.Although 2: 1 to 1: 2 molar ratio range all is suitable, the comonomer of mole numbers such as use is preferably not necessarily.The example that can be used for carrying out the alkene of copolymerization with for example maleic anhydride comprises 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene and vinylbenzene.Other example of comb shaped polymer comprises poly-(methyl) alkyl acrylate.

Multipolymer can also be by any suitable technique esterification treatment, and maleic anhydride or fumaric acid preferred (but not necessary) at least 50% is esterified.The example of operable alcohol comprises positive last of the ten Heavenly stems-1-alcohol, positive 12-1-alcohol, positive 14-1-alcohol, the pure and mild positive 18-1-alcohol of positive 16-1-.This alcohol also every chain can comprise maximum methyl branches, for example the 2-methyl 15-1-alcohol described in the EP-A-213879,2-methyl 13-1-alcohol.This alcohol can be positive and only have the mixture of the alcohol of a methyl branch.The mixture of the preferred alcohol that uses pure alcohol rather than for example can be purchased; If the use mixture is then thought the average carbon atom number of alkyl group in the carbonatoms alcohol mixture in the alkyl group; If use the alcohol have branching on 1 or 2, then the carbonatoms in the alkyl group should be the number in the linear backbone segment of this pure alkyl group.

Multipolymer also can with primary amine and/or secondary amine, for example single-or two-hydrogenated tallow amine reaction.

Comb shaped polymer can be fumarate or itaconic ester polymkeric substance and multipolymer especially, for example european patent application 153176,153177,156577 and 225688 and WO91/16407 described in those.The preferred C of comb-shaped copolymer ₈-C ₁₂Dialkyl fumarate-vinyl acetate copolymer.

The esterified copolymer of polymkeric substance that other suitable comb shaped polymer is an alpha-olefin and multipolymer and vinylbenzene and maleic anhydride and the esterified copolymer of vinylbenzene described in EP-A-282342 and fumaric acid; According to the present invention, the mixture of two or more multipolymers also can use, and as mentioned above, this application may be favourable.

(vii) polar nitrogen compounds

Polar nitrogen compounds is also referred to as the anti-sedimentation additive of wax (WASA).

Polar nitrogen compounds comprises and has one or more, preferred two or more alkyl substituted amido or the substituent oily solubility polar nitrogen compounds of imido grpup, described hydrocarbyl group is monovalent and contains 8-40 carbon atom, and can randomly the serve as reasons form of its positive ion that draws of each substituting group.This oil solubility polar nitrogen compounds can be ionic or non-ionic type, and in fuel oil, can increase properties-correcting agent as wax crystalls.Preferred straight chain of this hydrocarbyl group or straight chain slightly, that is, it can have the alkyl side chain of a short length (1-4 carbon atom).When substituting group was amido, it can have more than an identical or different described hydrocarbyl group.

Term " alkyl " expression has the carbon atom on the other parts that are directly connected to this molecule, and has hydro carbons or mainly be the group of the characteristic of hydro carbons.Example comprises the hydro carbons group, for example the fat group and the alicyclic group of the aromatic group of fat group (for example alkyl or alkenyl), alicyclic group (for example cycloalkyl or cycloalkenyl), aromatic group, alicyclic ring replacement, fragrance replacement.Fat group with saturated be favourable.If what the substituent existence of non-hydrocarbons did not change these groups mainly is the characteristic of hydro carbons, then these groups can comprise the non-hydrocarbons substituting group.For example comprise ketone, halogen, hydroxyl, nitro, cyano group, alkoxyl group and acyl group.If hydrocarbyl group is substituted, preferred substituting group only then.

The example of substituted hydrocarbon radical group comprises 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketone propyl group, ethoxyethyl group, propoxy-propyl group.If not comprise the atom outside the carbon atom on chain that these groups can also be so be made of carbon or the ring.Suitable heteroatoms comprises for example nitrogen, sulphur and preferred oxygen.

More particularly, this amido or imido grpup substituting group are by such as-CO-,-CO ₂ ^(-),-SO ₃ ^(-)-or the middle linking group of alkylene and so on be connected on the group.When this linking group was anionic group, as in the amine salt group, this substituting group was the part of cation group.If this linking group is a carbonyl, then this substituting group partly is imide group or amide group.

When polar nitrogen compounds had more than an amido or imido grpup substituting group, each substituent linking group can be identical or different.

Suitable amido substituting group is the C of long-chain ₁₂-C ₂₄, preferred C ₁₂-C ₁₈Alkyl primary, the second month in a season, uncle or quaternary amine base substituting group.

The preferred two alkyl amine group substituting groups of amido substituting group, it can be the form of its amine salt, form or two kinds of forms of its acid amides as mentioned above.Uncle and quaternary amine can only form amine salt.Described alkyl group can be identical and different.

The amido substituting group preferably includes dodecyl amido, tetradecyl amido, cocoyl amido and hydrogenated tallow amido.The substituent example of secondary amine comprises dioctadecylamine base and methyl docosyl amido.The substituent mixture of amido can be as those that obtain of deriving from spontaneous amine.Preferred amido substituting group is para-hydrogenation Tallow, beef amido or two cocoyl amido substituting group, and its alkyl group is to come from hydrogenated tallow fat, and is typically by weight by about 4% C ₁₄, 31% C ₁₆With 59% C ₁₈Positive alkyl group constitute.

Suitable imines substituting group is long-chain C ₁₂-C ₄₀, preferred C ₁₂-C ₂₄Alkyl substituent.

Described group can be monomer (cyclic or acyclic) or polymkeric substance.When being acyclic, it can be obtained by the cyclic precursor such as acid anhydride or the two lactones of spiral shell.

This cyclic rings system can comprise the homocyclic ring combination, heterocycle combination or condensed ring combination, the system that perhaps two or more such ring combinations (these ring combinations can be identical, also can be different) mutually combine and constitute.When having the combination of two or more such rings, substituting group can be identical or different combination, preferred identical combination.This or each ring combination preferred fragrance ring, more preferably phenyl ring.When individual substituting group preferably was in ortho position or position, this cyclic rings is phenyl ring only most preferably, and this phenyl ring can randomly further be substituted.

The preferred carbon atom of one-tenth annular atoms in the ring combination, but also can comprise for example one or more one-tenth ring N, S or O atom, under this or these situations, this compound is a heterogeneous ring compound.

The examples how ring makes up comprise many cyclophanes perfume base group, by the ring of " end connects " (" end-on ") connection, for example xenyl, heterocycle or alicyclic ring.

The example of polar nitrogen compounds is described as follows:

(i) single-or the amine salt and/or the acid amides of many-carboxylic acid (for example having 1-4 hydroxy-acid group).For example it can replace the acid of amine and one mole or acid anhydrides by the alkyl that for example makes at least one mole and reacts and prepare.

When forming acid amides, linking group is-CO-that when forming amine salt, linking group is-CO ₂ ^(-)

Described group can be a ring-type or acyclic.The example of cyclic group is that acid is hexanaphthene-1,2-dicarboxylic acid, inferior hexanaphthene-1,2-dicarboxylic acid, pentamethylene-1, those of 2-dicarboxylic acid and naphthalene dicarboxylic acids.Usually, these acid have 5-13 carbon atom in this cyclic group.The preferred benzene of ring-type acid two carboxylic acid, for example phthalic acid, m-phthalic acid and terephthalic acids; And benzene tertacarbonic acid, for example pyromellitic acid, especially preferably phthalic acid.US-A-4211534 and EP-A-272889 have described the polar nitrogen compounds that comprises this group.

The example of non-annularity group be when acid be that chain alkyl or alkylidene group replace those of two carboxylic acids (for example succsinic acid), described in for example US-A-4147520.

Other example of non-annularity group is that acid is those of nitrogen acid (for example ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA)).

Further example is to react the group that obtains as two lactones of described pair of alkyl spiral shell of DE-A-392699 and amine.

The (ii) compound or its salt of formula I:

Wherein: B represents aroma system, and A represents hydrocarbyl group, R ¹⁷And R ¹⁸Be identical or different, and each is the aliphatic group group that contains 12-24 carbon atom independently, z is at least 1, and wherein this aroma system has at least one substituting group, and this substituting group is the activating group of loop system or the derivative of activating group.

Term alkyl used in this specification sheets is meant the organic group of being made up of hydrogen and carbon, they are connected on the other parts of this molecule by a carbon atom or a plurality of carbon atom key, unless and offer some clarification in the context, it can be a fat group, comprise alicyclic group, aromatic group or its combination.Also can be replacement or unsubstituted alkyl, aryl or alkaryl, and can choose wantonly and comprise unsaturated group or the heteroatoms such as O, N or S that its condition is the character that is mainly alkyl that heteroatoms is not enough to change this group.Preferred A is the aliphatic group group, and more preferably A is a methylene group.

The term aroma system is meant and comprises fragrant homocyclic ring, heterocycle or condensed ring combination, or two or more such ring combination system of mutually combining and constituting, and these ring combinations can be identical or different.Having combination of two or more rings and z is 2 or when bigger ,-(A-NR ¹⁷R ¹⁸) group may reside in the identical or different combination.Preferably, this aroma system is based on the loop systems of phenyl ring.

The preferred carbon atom of one-tenth annular atoms in the aroma system, but also can in this system, comprise for example one or more such as N, the heteroatoms of S or O and so on, this moment this compound be heterogeneous ring compound.

The example of many ring combinations comprises:

(a) condensed ring benzene structure, for example naphthalene;

(b) condensed ring structure, wherein all rings be not phenyl ring or be not all rings are phenyl ring, indenes for example;

(c) " end connects " ring, for example biphenyl;

(d) heterogeneous ring compound, for example quinoline; With

(e) two aroma systems wherein encircle by one or more divalent groups and couple together, for example dihydroxyphenyl propane.

The term activating group is meant any group except that substituting group fat hydroxyl group, and its activation aroma system is to carry out substitution reaction, for example electrophilic replacement, nucleophilic substitution or Mannich reaction.This activating group can be unsubstituted group, for example for example is in such as the functional group in the aroma system of the heterogeneous ring compound of indoles.This activating group is in by-(A-NR ¹⁷R ¹⁸) at least one ring of the aroma system that replaces of group or on each ring.This activating group preferably is in the group (opposite with the group in this aroma system) on the loop system.Ideally, activating group activates this aroma system and replaces or Mannich reaction to carry out electrophilic, most preferably carries out Mannich reaction.This activating group is preferably at relative himself ortho position or contraposition activation aroma system.Preferred activating group is an oh group.The aroma system that preferably is activated is the hydroxyl aromatic system.The deriveding group of term activating group is meant any group that can be produced by the reaction of activating group.For example, when activating group was oh group, a deriveding group was by oh group and for example acetic anhydride generation-O-C (O)-CH ₃Group.On this aroma system or in this aroma system, can have the deriveding group of one or more activating groups or activating group; They can be in identical or different ring or on the ring.Can exist and be in this aroma system or on this aroma system and be not other substituting group of the deriveding group of activating group or activating group.

Constitute the R among the present invention ¹⁷And R ¹⁸Each aliphatic group group for example can be the single or poly-alkoxy-alkyl group of alkyl or alkylidene group or comprise heteroatomic aliphatic group group such as O, N or S.The preferred straight chained alkyl group of each aliphatic group group.The preferred 12-24 of amount of carbon atom in each aliphatic group group, most preferably 12-18.

For example when z=1, this aroma system also has the substituting group of following general formula I I:

W=0 or 1 wherein; Q represents A; R ¹⁷And R ¹⁸Has aforesaid implication.Preferred w=0, and have only the extra substituting group of an above-mentioned general formula I I.When z is 2 or when bigger, the extra substituting group of this general formula I I also may reside in the aroma system.

The compound of most preferred general formula I is those compounds of being represented by following general formula III:

Wherein X represents the group that hydrogen or hydrocarbyl group or a non-hydrocarbyl group or following general formula I V are represented:

Wherein: Y is a divalent group, and a=1 wherein, 2,3 or 4, b=1,2,3 or 4, c=0,1 or 2, d=0,1,2,3 or 4, e=0,1,2,3 or 4, and R ²¹, R ²², R ²³And R ²⁴Be hydrogen or alkyl, wherein R ¹⁹And R ²⁰Be C independently ₈-C ₃₀The aliphatic group group.D represents the deriveding group of oh group or oh group.When D is the deriveding group of oh group, preferred-O-C (O)-CH ₃Group.C ₁₀-C ₄₀The aliphatic group group can be straight chain or branching.The preferred straight chain of chain.

When X is a group except that the group of formula IV, preferred a=1 or 2, b=1,2,3 or 4, a=1 or 2 most preferably, b=1,2 or 3.

When X is the group of formula IV and c=0, a=1,2 or 3, b=1,2 or 3, d=0,1,2 or 3 and e=0,1,2 or 3, most preferably a=1, b=1, d=1 and e=1.

When X is the group of formula IV and c=1, a=1,2 or 3, b=1,2 or 3, d=0,1,2 or 3, e=0,1,2 or 3, a=1 or 2 most preferably, b=1 or 2, d=0,1 or 2 and e=0,1 or 2.

In general formula III and IV, phenyl ring can be the part of bigger loop systems (for example condensed ring system), or heterocycle or the aromatic nucleus except that phenyl ring.

When c=1, except can being coupled together by divalent group Y, as when the c=0, group III and IV also can directly couple together.During c=2, divalent group Y can be identical or different.

R ²¹, R ²², R ²³And R ²⁴Preferred hydrogen.The aliphatic group radicals R ¹⁹And R ²⁰Can be identical or different, and preferably be C independently ₁₀-C ₄₀Alkyl group.It is desirable to, alkyl group is C independently ₁₂-C ₂₄Alkyl group, most preferably C ₁₂-C ₁₈Alkyl group.When existing more than a R ¹⁹Or R ²⁰During group, they can be identical or different aliphatic group groups.The preferably combination of alkyl group is R wherein ¹⁹/ R ²⁰Be C ₁₆/ C ₁₈, C ₁₂/ C ₁₄, C ₁₈/ C ₁₈Or C ₁₂/ C ₁₂Those.

The aliphatic group group also can comprise the heteroatoms such as O, N or S.Preferably not having heteroatoms and group in this aliphatic group group is straight chain, or those have the group of low-level branching.

Divalent group Y replaces or unsubstituted fat group, for example methylene radical ,-C (CH ₃) ₂-,-CH (Ph)-, the group represented of following formula V or similar group, or such as-C (O)-,-S (O)-,-S (O) ₂-,-O-,-S-,-C (O)-O-and-C (O)-O-R ¹⁵-O-C (O)-and so on group, R wherein ¹⁵It is foregoing hydrocarbyl group.When existing two divalent groups promptly as c=2, they can be identical or different, for example combine (as in fluorescent yellow) of the described group of formula V and-O-.Divalent group Y also can be an aromatic group.Divalent group Y also can comprise active ring, and this activity ring has substituting group-(A-NR in cyclic rings ¹⁷R ¹⁸).

The compound of general formula III also can be replaced by one or more groups of general formula I I.Preferably when X be group except that general formula I V, and when b=1, the group of at least one general formula I I is present in the compound that general formula III represents.The compound that general formula III is represented also can be by such as NO ₂Or the non-hydrocarbyl group of CN group and so on replaces.

In compound by the above formula I that limits, the preferred oh group of activating group.Below the fragrant system of bis (hydroxy-aromatic) is called active compound.This compound is preferably by making formaldehyde or aldehyde and comprise C independently under the Mannich condensation condition ₈-C ₃₀The secondary amine of aliphatic group group produces reaction and prepares.

Each reactant can be to wait mole or to wait molar ratio to use substantially.The mol ratio of active compound and secondary amine can less than etc. the mole, for example 1: 2,1: 3 or 1: 4 or more.The mol ratio of active compound and secondary amine is 1: 2 or is 1: 2 substantially, and has enough formaldehyde, so that reach this mol ratio in the finished product.

This reaction can be in solvent (for example toluene), or does not use solvent but temperature is to carry out in 80 ℃-120 ℃ the scope.

Aldehyde can be any under the Mannich condensation condition with active compound and C ₈-C ₃₀The aitiogenic aldehyde of aliphatic group secondary amine.Preferably use formaldehyde in the method.Formaldehyde can use with any form easily; It can use with the form of the aqueous solution (for example formalin), paraformaldehyde or trioxane.

Suitable hydroxyaromatic compounds for example comprises: fortified phenol, for example 2-, 3-or 4-dihydroxy benaophenonel, 2-, 3-or 4-hydroxy-benzoic acid and 1 or beta naphthal; Dihydroxyl compound, for example Resorcinol, pyrocatechol, Resorcinol, 2,2 '-xenol, 4,4 ' xenol, fluorescent yellow, 2,2-two (p-hydroxybenzene) propane, two dihydroxy benaophenonel, 4, and 4 '-sulfo-xenol or resorcylic acid (for example 2,4-, or 3, the 5-resorcylic acid); Or the benzenetriol compound, for example 1,1,1-three (4-hydroxy phenyl) ethane.Hydroxyaromatic compounds can be replaced by for example one or more following substituting groups: non-hydrocarbyl group, for example-NO ₂Or CN; Or hydrocarbyl group, for example-CHO ,-COOR ,-COR ,-COOR; Or aliphatic group group, for example alkyl group.Substituting group can be the combination of ortho position, contraposition or a position or any of these position with respect to oh group.When hydroxyaromatic compounds was the phenol that replaces, preferred substituents was in ortho position or contraposition.Have been found that the phenol with some para-orientation can be under relatively mild reaction conditions and than using unsubstituted phenol more to be easy to generate from having by C ₈-C ₃₀The secondary amine of the aliphatic group group dialkylamine methyl Mannich reaction products of deriving and getting.In some cases, ortho-substituent also allows more easily reaction under the condition of milder, although some such substituting group is disadvantageous, for example those can produce the substituting group that hydrogen bond is connected with oh group.Suitable ortho-substituent is a cyano group.Be appreciated that concerning the dihydroxyl compound (for example catechol) that in an identical ring, has two or more oh groups any substituting group relatively one of these oh groups can be an adjacent, and position between to another being.

Amine can be any C that comprises straight chain and/or branching ₈-C ₃₀, preferred C ₁₀-C ₂₂, C most preferably ₁₂-C ₁₈The secondary amine of aliphatic group group.Preferred secondary amine is straight chain or has those of low-level branching.

The example of suitable secondary amine comprises simple secondary amine, N for example, N-lauryl amine, N, N-double hexadecyl amine, N, N-dioctadecylamine, N, the two eicosyl amine of N-, N, the two docosyl amine of N-, N, the two hydrogenated tallow amine of N-and two alkyl groups are secondary amine identical or different and that choose from following functional group: dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, hexadecyl, octadecyl, eicosyl, docosyl or hydrogenated tallow or from those of the fatty acid derived of Oleum Cocois.

The extra substituting group of general formula I I can be between the above-mentioned reaction period by the amine that makes active compound with hydroxy-acid group and respective amount react with participate in above-mentioned reaction and in and hydroxy-acid group be formed on the aroma system.In addition, hydroxy-acid group also can be after reaction by the amine that adds requirement neutralize (these amine can be with reaction in the identical or different amine of amine of use) thus in and hydroxy-acid group.

Can convert activating group the derivative of activating group to extra step of reaction, for example convert oh group to acetate fat by reaction with for example diacetyl oxide.

(iii) have the long-chain uncle of the polymkeric substance that contains carboxylic acid or the condenses of secondary amine

Object lesson comprises the polymkeric substance described in GB-A-2121807, FR-A-2592387 and DE-A-3941561; Also comprise the telomer acid described in US-A-4639256 and the ester of alkanolamine; And the reaction product of the amine that comprises the branched carboxylic acids ester described in US-A-4631071, epoxide and monocarboxylic acid polyester.

EP0283292 has described the acid amides that comprises polymkeric substance, and EP0343981 has described the amine salt that comprises polymkeric substance.

Should notice that polar nitrogen compounds can comprise other functional group such as ester functional group.

The jet fuel composition also can comprise at least a following additive: antioxidant, metal deactivator, the static dissipator additive that the specific conductivity of 50-450pS/m is provided, frostproofer, anticorrosive agent, biocide, defoamer, oiliness additive and sanitising agent such as ethylene glycol monomethyl ether (EGEM).

Now, only the present invention is described by way of example with reference to the following stated accompanying drawing.

Fig. 1 is by C to a series of ₈1-alkene and C _xThe result's that (L) CAST test that the multipolymer that 1-alkene forms carries out in the time of-58 ℃ draws graphic representation.

Embodiment

Settling reduces

Prepare two kinds and comprise jet fuel MIL JP8 and C ₆1-alkene and C ₁₂The jet fuel composition of the hydrocarbon comb-shaped polymer of 1-alkene.First kind of jet fuel composition (A) comprise when relative polystyrene standard during by gel permeation chromatography measurement number-average molecular weight be 2500 hydrocarbon comb-shaped polymer, and second kind relatively jet fuel composition (B) comprise when relative polystyrene standard during by gel permeation chromatography measurement number-average molecular weight be 5500 hydrocarbon comb-shaped polymer.

The jet fuel composition is tested by the single burner jet engine that comprises burner.This jet engine with two of idling (the air inlet temperature is 100 ℃) operations 20 minutes during and one 40 minutes during.Therefore total test period is 80 minutes.Air flow quantity is 350g/s and fuel mass flow is 3.4g/s.

Test result is illustrated in the following table 1.

Table 1

Fuel composition	20 minutes	20 minutes	40 minutes	Totally 80 minutes	Settling
Fuel composition	20 minutes	20 minutes	40 minutes	Totally 80 minutes	Settling	(B) relatively	1.05g	?1.12g	?2.08g	?4.25g	?100％
(A)	0.79g	?1.00g	?1.70g	?3.49g	?82％	(B) relatively	1.05g	?1.12g	?2.08g	?4.25g	?100％

The result shows, when jet engine used fuel element (A) operation, the settling quantity that the sedimental quantity that reclaims from this jet engine reclaims during with use high-molecular weight polymer in fuel element (B) had relatively reduced by 18%.

Cold flow properties

Cold flow properties is recorded by (L) CAST cold flow additive sieve test.The purpose of this test is to obtain the low-temperature performance of jet fuel and each fuel dope to these Effect on Performance.

In (L) CAST test, the formulation of fuel and additive is cooled to certain temperature.Make sample pass through the sieve of one 417 μ m (35 order) then, disappear or 60 seconds in the past till the back up to suction.

The detail of testing sequence is as follows:

A) fuel of weighing 250ml is put into vial or nalgene bottle, mixes the test additive of experimental concentration 4.0 grams per liters then.

B) sample is poured into the taper assay flask of known quality and weighing once more.The total mass of underproof fuel and tested additive is recorded as the total mass of sample.After carrying out visual inspection and be sure oing that filter assemblies is original not particulate matter, this filter assemblies is put into fuel.

C) this assay flask and filter assemblies are put into the cooling box that is in test temperature.Then sample is placed and spent the night, and confirm that with hygrosensor the temperature of cooling box and sample all remains the test temperature of choosing.

D) stir (changeing 15 with 1 revolutions per second speed changes) this sample with filter assemblies.

E) write down the outward appearance (for example limpid, muddiness and fluid or be colloidal) of this sample.

F) connecting vacuum pump makes receiving vessel be under the vacuum state of pressure 20kPa with the pipe that is connected.Assay flask is under the vacuum, and fuel is passed through in this filter assemblies suction receiving vessel.Start stopwatch when opening this valve, and when suction disappears, stop stopwatch,, then close this valve, stop at any mobile after this time if fuel continues to flow in the time of 60 seconds.

G) allow this assay flask and filter assemblies be warmed up to envrionment temperature.Remove filter assemblies then, allow adherent fuel droplet return in this assay flask, and this assay flask that will hold residual fuel is weighed again.

H) calculate reservation wax percentage ratio according to following formula:

Keep wax percentage ratio and be commonly referred to be failure greater than 15%.

Fig. 1 represents that (L) CAST that multiple hydrocarbon comb-shaped polymer carries out tests the result who draws in the time of-58 ℃.The polymkeric substance of all tests all is C ₈The multipolymer of the 1-alkene and second alkene, second alkene is C ₁₀, C ₁₁, C ₁₂, C ₁₃, C ₁₄Or C ₁₆1-alkene.Clearly illustrate to have only C among Fig. 1 ₈1-alkene and C ₁₂The multipolymer that 1-alkene forms obtained one " by " (the actual percentage ratio that keeps wax is 10%).(L) CAST test of all other multipolymers has all been failed.These results confirm C ₈/ C ₁₂Multipolymer has beyond thought good cold flow properties energy.

Claims

1, a kind of method that is used for reducing the sedimental amount of jet engine, this method comprises the jet fuel composition is offered jet engine that described jet fuel composition comprises jet fuel and at least a alkyl comb shaped polymer; Wherein when relative polystyrene standard during by gel permeation chromatography measurement, the number-average molecular weight of this at least a alkyl comb shaped polymer is less than 5500, preferably less than 5000.

2, the described method of claim 1, wherein when relative polystyrene standard during by gel permeation chromatography measurement, the number-average molecular weight of described alkyl comb shaped polymer less than 4800, preferably less than 4500, be more preferably less than 4300 in addition be more preferably less than 4000, most preferably less than 3800.

3, claim 1 or 2 described methods, wherein said alkyl comb shaped polymer is C ₃-C ₉1-alkene and C ₁₀-C ₁₄The hydrocarbyl polymers of 1-alkene or multipolymer.

4, the described method of aforementioned arbitrary claim, wherein said alkyl comb shaped polymer is C ₆-C ₈1-alkene and C ₁₂The hydrocarbyl polymers of 1-alkene or multipolymer.

5, the described method of aforementioned arbitrary claim, wherein said alkyl comb shaped polymer is C ₈1-alkene and C ₁₂The hydrocarbyl polymers of 1-alkene or multipolymer.

6, the described method of aforementioned arbitrary claim, wherein said jet fuel composition also comprise at least a in the following material:

(i) multipolymer of ethene and at least a unsaturated ester;

The (ii) multipolymer of ethene and alkene;

(iii) nucleator;

(iv) wax;

(v) a large amount of branched-alkyl phenolic condensation compounds (being referred to as ' APFC ');

(vi) be selected from the polymkeric substance of unsaturated ester or the comb shaped polymer of multipolymer or alkene copolymer-maleic anhydride; With

(vii) polar nitrogen compounds.

7, the described method of aforementioned arbitrary claim, the content range of wherein said at least a alkyl comb shaped polymer in described jet fuel composition are 10-20000ppm, preferred 100-10000ppm, 500-5000ppm (per hundred of additive count w/w very much in the jet fuel) most preferably.

8, the described method of aforementioned arbitrary claim, the pour point of wherein said jet fuel has obtained reduction.

9, the purposes of at least a alkyl comb shaped polymer as the additive of jet fuel, is used for reducing for sedimental amount in the jet engine of this jet fuel; Wherein when relative polystyrene standard during by gel permeation chromatography measurement, the number-average molecular weight of described alkyl comb shaped polymer is less than 5500, preferably less than 5000.

10, a kind of jet fuel composition, it comprises at least a alkyl comb shaped polymer; Wherein said alkyl comb shaped polymer is C ₈1-alkene and C ₁₂The hydrocarbyl polymers of 1-alkene or multipolymer, and when relative polystyrene standard during by gel permeation chromatography measurement, its number-average molecular weight are less than 5500, preferably less than 5000.

11, the described jet fuel composition of claim 10, wherein when relative polystyrene standard during by gel permeation chromatography measurement, the number-average molecular weight of described hydrocarbyl polymers or multipolymer less than 4800, preferably less than 4500, be more preferably less than 4300 in addition be more preferably less than 4000, most preferably less than 3800.

12, claim 10 or 11 described jet fuel compositions, it also comprises at least a following material:

(i) multipolymer of ethene and at least a unsaturated ester;

The (ii) multipolymer of ethene and alkene;

(iii) nucleator;

(iv) wax;

(vii) polar nitrogen compounds.

13, each described jet fuel composition among the claim 10-12, wherein said hydrocarbyl polymers or the multipolymer content range in this jet fuel composition are 10-20000ppm, preferred 100-10000ppm, 500-5000ppm (per hundred of additive count w/w very much in the jet fuel) most preferably.

14, a kind of method that reduces the jet fuel pour point, this method comprises the following steps:

A) provide a kind of jet fuel; With

B) at least a alkyl comb shaped polymer is joined in this jet fuel; Wherein this at least a alkyl comb shaped polymer is C ₈1-alkene and C ₁₂The hydrocarbyl polymers of 1-alkene or multipolymer, and when relative polystyrene standard during by gel permeation chromatography measurement, its number-average molecular weight are less than 5500, preferably less than 5000.

15, the purposes of at least a alkyl comb shaped polymer is used to reduce the low temperature operability of jet fuel; Wherein said at least a alkyl comb shaped polymer is C ₈1-alkene and C ₁₂The hydrocarbyl polymers of 1-alkene or multipolymer, and when relative polystyrene standard during by gel permeation chromatography measurement, its number-average molecular weight are less than 5500, preferably less than 5000.