DE69434213T2 - Use of additives in fuel compositions - Google Patents

Description

These The application is a divisional application of EP-A-94 924 280.4, which is known as EP-0 721 492 A been published is. This invention relates to the use of additives for improvement the cold flow properties of Fuel oil, for example distillate oil fuel such as middle distillate fuel oil, that in the range of 110 ° C up to 500 ° C boils.

If fuel oils may be exposed to low ambient temperatures, may paraffin from the fuel and affect the flow properties of the oil. For example, middle distillate fuels contain paraffin, the at low temperatures fails, around big ones waxy crystals tend to form the small pore openings from clogging fuel filters. This problem is special acute if the fuel is a diesel fuel because the nominal openings in the fuel filter of diesel engines, typically a diameter between about 5 and 50 microns to have. Additives to overcome of the above problem are known in the art and are used as flow improvers designated.

Such Additives can as paraffin crystal modifiers when mixed with paraffinic mineral oil Become the shape (shape) and size of the crystals in it paraffins and modify the adhesion forces between the crystals and reduce between the paraffin and the oil to lower the oil Temperature to remain as flowable in the absence of the additive.

Lots Additives are known in the art for improving cold flow properties of oils described, for example in the form of oil-soluble addition products or condensates which may be polymeric or monomeric and as in U5-A-3 048 479, GB-A-1 263 152, US-A-3 961 961 and EP-A-0 261 957 are described. Some of the above additives are still today commercially as cold flow improver been used.

Of the The prior art describes cold flow improvers as a combination can be used with other additives. For example, this describes GB-A-1 112 808 ethylene / vinyl acetate copolymers in combination with rust inhibitors, Anti-emulsifiers, anti-corrosion agents, antioxidants, Dispersants, dyes, dye stabilizers, haze inhibitors and antistatic additives. DE-A-21 56 425 relates to middle distillate fuel oils which a flow improvement system include, the specific pour point lowering polymers in combination with nitrogen-free, oil-soluble, supportive, flow improving Contains compounds. The second component of the flow-improving Among other things, systems can be an ester.

According to the invention is surprisingly found that the Cold flow properties of cold flow improvers as described above by using co-additives can be improved none of which has heretofore been known in the art to have cold flow improvement properties demonstrate.

Thus, a first aspect of the invention is the use of a co-additive selected from component (A) comprising an oil-soluble lubricity additive comprising an ester of a dicarboxylic acid and a polyhydric alcohol wherein the acid has 2 to 50 carbon atoms, the alcohol one or more Has carbon atoms and is a trihydric alcohol or diol of the formula R ² (OH) _y where R ^{2 is} an unsubstituted polymethylene group of 1 to 10 carbon atoms and y is an integer and the number of hydroxy groups, and in the case of esters only Carbon, hydrogen and oxygen and having one or more free hydroxy groups, the use being in a composition comprising a major proportion of a fuel oil and a minor proportion of a component (B) comprising a cold flow improver additive comprising a copolymeric ethylene oxide; Includes flow improver and is present to the Improve cold flow properties of the composition.

• (i) Komponente (B) wie oben definiert in das Brennstofföl injiziert wird,
• (ii) Komponente (A) wie oben definiert in das Brennstofföl injiziert wird,
• (iii) die Kaltfließeigenschaften des Brennstofföls nach den Injektionen der Stufen (i) und (ii) gemessen werden, und
• (iv) die relative Injektionsrate von Komponente (B) und (A) und dadurch ihre relativen Anteile eingestellt werden, um die Resultate von Stufe (iii) zu berücksichtigen und die gewünschten Kaltfließeigenschaften in dem Brennstofföl zu liefern.

The inventive improvement of the cold flow performance of component (B) by the component (A) can be applied to the mixing of additives in a fuel oil. Thus, a second aspect of the invention is a method for mixing additives with fuel oil, in which

• (i) component (B) is injected into the fuel oil as defined above,
• (ii) component (A) as defined above is injected into the fuel oil,
• (iii) the cold flow properties of the fuel oil are measured after the injections of steps (i) and (ii), and
• (iv) adjusting the relative injection rate of components (B) and (A) and thereby their relative proportions to account for the results of step (iii) and to provide the desired cold flow properties in the fuel oil.

According to the second Aspect of this invention, the fuel oil is preferably in the form of a flowing Current, where stage (i) in a first station and stage (ii) takes place in a second station, although the first and second Station may be adjacent and the injection over a common injector can be done. The procedure can be automated so that one Perform sensor step (iii) can, for. B. by measuring the blockage point of the filter Cold (CFPP), and the information about a control supplied can be to the injection of one or both of the components (B) and (A) to control.

The Invention enables, surprisingly, that less of component (B) is used to achieve a desired cold flow improvement performance to reach.

The inventive features will now be discussed in more detail. Descriptions referenced will be included here.

As used in this specification, the term "hydrocarbon" refers to a group a carbon atom directly attached to the rest of the molecule and hydrocarbon or predominantly hydrocarbon character. Close examples Hydrocarbon groups including aliphatic (eg. Alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic and alicyclic substituted aromatic and aromatic substituted aliphatic and alicyclic groups. Aliphatic groups are advantageously saturated. These groups can Contain non-hydrocarbon substituents, provided that their presence does not change the predominant hydrocarbon character of the group. Examples shut down Keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If the Hydrocarbon group is substituted, is a single (mono) substituent prefers.

Examples for substituted ones Close hydrocarbon groups 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The groups can also or alternatively from Contain carbon atoms different in a chain or a ring, which is otherwise composed of carbon atoms. Include suitable heteroatoms for example, nitrogen, sulfur and preferably oxygen one.

COMPONENT (A)

The Acid, the alcohol and ester that characterize the lubricating additive, will now be discussed in more detail below.

(i) acid

The acid from which the ester is derived may be an aliphatic, saturated or unsaturated, straight or branched chain dicarboxylic acid having 2 to 50 carbon atoms. For example, the acid may be represented by the formula R '(COOH) ₂ in which R 'represents a substituted or unsubstituted polymethylene group having from 2 to 50 carbon atoms, which COOH groups may optionally be substituents on carbon atoms different from each other.

(ii) alcohol

The alcohol from which the ester is derived is a polyhydroxy alcohol which is a diol or a trihydric alcohol of the formula R ² (OH) _y in which y represents an integer and R ^{2 represents} an unsubstituted polymethylene group having 1 to 10 carbon atoms, which OH groups may optionally be substituents on mutually different carbon atoms.

Of the Polyhydric alcohol preferably has 2 to 5 carbon atoms in the Molecule, such as glycerol.

(iii) the esters

The Esters can used alone or as mixtures of one or more esters are and are only made of carbon, hydrogen and oxygen composed and have one or more free hydroxy groups. Preferably, the ester has a molecular weight of 200 or more or has at least 10 carbon atoms or both.

Examples for esters of polyhydric alcohols that can be used those in which all hydroxy groups are esterified, such not all hydroxy groups are esterified, and mixtures thereof. Particular examples are esters derived from trihydric alcohols and one or more of the above saturated or unsaturated dicarboxylic acids are prepared, such as, for example, glycerol diesters, e.g. Dioleate. Such polyvalent esters can produced by esterification as described in the prior art be and / or may be commercially available.

Examples are described in WO-PCT / EP94 / 00148.

Component (B)

Ethylene copolymer flow improvers, z. B. ethylene / unsaturated Ester copolymer flow improvers a polymethylene backbone, which is divided into segments by oxyhydrocarbon side chains is.

In particular, the copolymer may comprise ethylene copolymer which, in addition to units derived from ethylene, has units of the formula -CR ⁵ R ⁶ -CHR ⁷ in which R ^{6 is} hydrogen or a methyl group, R ^{5 is} an -OOCR ⁸ or -COOR ⁸ group, where R ^{8 is} hydrogen or a straight-chain or branched C ₁ to C ₂₈ , preferably C ₁ to C ₉ Alkyl group, provided that R ^{8 is} not hydrogen, when R ^{5 is} -COOR ⁸ , and R ^{7 is} hydrogen or a -COOR ⁸ group.

These can a copolymer of ethylene with an ethylenically unsaturated one Esters or derivatives thereof. An example is a copolymer of ethylene with an ester of an unsaturated carboxylic acid, but the ester is preferably one of an unsaturated alcohol having a saturated Carboxylic acid. An ethylene / vinyl ester copolymer is advantageous, an ethylene / vinyl acetate, Ethylene / vinyl propionate, ethylene / vinyl hexanoate or ethylene / vinyl octanoate copolymer is preferred. Preferably, the copolymers contain 1 to 25, for. B. 1 to 20 mol.% Of the vinyl ester, in particular 3 to 17 mol.% Vinyl ester. You can also in the form of mixtures of two copolymers, such as those described in US-A-3,961,916. Preferably is the number average molecular weight measured by vapor phase osmometry, of the copolymer 1000 to 10,000, in particular 1000 to 5000. If desired can the copolymers of additional Comonomers derived, for. For example, they may be terpolymers or tetrapolymers or higher Polymers, for example, when the additional comonomer isobutylene or diisobutylene.

The Copolymers can be prepared by direct polymerization of comonomers. Such copolymers can also by transesterification or hydrolysis and reesterification of Ethylene / unsaturated Ester copolymer can be made to another ethylene / unsaturated To give ester copolymer. For example, in this way ethylene / vinylhexanoate and ethylene / vinyl octanoate copolymers, e.g. B. off Ethylene / vinyl acetate copolymer.

component (B) can be used with co-components such as one or more of the following be used:

comb polymers

comb polymers are in "Comb-like Polymer. Structure and Properties ", N.A. Platé and V.P. Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974).

In general, comb polymers have one or more long-chain branches, such as hydrocarbon branches, such as oxyhydrocarbon branches having 10 to 30 carbon atoms, laterally from a polymer backbone, which branch or branches bind directly or indirectly to the backbone is or are. Examples of indirect bonding include bonds via intervening atoms or groups, which bond may include covalent and / or electrochemical bonding, such as in a salt.

advantageously, the comb polymer is a homopolymer or a copolymer with at least 25 and preferably at least 40, more preferably at least 50 mol% Units that have side chains that are at least 6, and preferably at least Containing 10 atoms selected from for example carbon, nitrogen and oxygen in one linear chain included.

enthalten, wobei
D = R¹¹, COOR¹¹, OCOR¹¹, R¹²COOR¹¹ oder OR¹¹,
E = H, CH₃, D oder R¹²,
G = H oder D,
J = H, R¹², R¹²COOR¹¹ oder eine Aryl- oder heterocyclische Gruppe,
K = H, COOR¹², OCOR¹², OR¹² oder COOH,
L = H, R¹², COOR¹², OCOR¹² oder Aryl,
R¹¹ eine Kohlenwasserstoffgruppe mit 10 oder mehr Kohlenstoffatomen,
R¹² eine Kohlenwasserstoffgruppe mit 1 oder mehr Kohlenstoffatomen,
und m und n Molverhältnisse bedeuten, deren Summe 1 ist und m endlich ist und bis zu 1 beträgt, 1 eingeschlossen, und n 0 bis kleiner 1 ist, wobei m vorzugsweise im Bereich von 1,0 bis 0,4 ist und n im Bereich von 0 bis 0,6 ist. R¹¹ stellt vorteilhafterweise eine Kohlenwasserstoffgruppe mit 10 bis 30 Kohlenstoffatomen dar und R¹² stellt vorteilhafterweise eine Kohlenwasserstoffgruppe mit 1 bis 30 Kohlenstoffatomen dar.As examples of preferred comb polymers may be mentioned those which are units having the general formula

contain, where
D = R ¹¹ , COOR ¹¹ , OCOR ¹¹ , R ¹² COOR ¹¹ or OR ¹¹ ,
E = H, CH _3, D or R ^12,
G = H or D,
J = H, R ¹² , R ¹² COOR ¹¹ or an aryl or heterocyclic group,
K = H, COOR ¹² , OCOR ¹² , OR ¹² or COOH,
L = H, R ¹² , COOR ¹² , OCOR ¹² or aryl,
R ^{11 is} a hydrocarbon group having 10 or more carbon atoms,
R ^{12 is} a hydrocarbon group having 1 or more carbon atoms,
and m and n denote molar ratios whose sum is 1 and m is finite and is up to 1, 1 inclusive, and n 0 to less than 1, m being preferably in the range of 1.0 to 0.4 and n in the range from 0 to 0.6. R ¹¹ advantageously represents a hydrocarbon group of 10 to 30 carbon atoms, and R ¹² is advantageously a hydrocarbon group of 1 to 30 carbon atoms.

The Comb polymer may contain units other than other monomers are derived, if desired or required. It is within the scope of the invention to include two or more different comb polymers.

These Comb polymers can For example, copolymers of maleic anhydride or fumaric acid and another ethylenically unsaturated Be monomers, e.g. an α-olefin or unsaturated Esters, for example vinyl acetate. It is preferred but not essential that equimolar Amounts of comonomers are used, although molar proportions in the Range of 2 to 1 and 1 to 2 are suitable. Examples of olefins, the e.g. with maleic anhydride can be copolymerized shut down 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.

The copolymer can be esterified by any suitable technique, and although it is preferred, it is not essential that the maleic anhydride or the fumaric acid is at least 50% esterified. Examples of alcohols which can be used include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol and n-octadecan-1-ol , The alcohols may also include up to one methyl branch per chain, for example, 1-methylpentadecan-1-ol, 2-methyltridecan-1-ol. The alcohol may be a mixture of n-alcohols and alcohols with a single methyl branch. It is preferred to use pure alcohols rather than alcohol mixtures, which are commercially available. However, when mixtures are used, R ¹² refers to the average of the carbon atoms in the alkyl group. When alcohols containing a branch in the 1- or 2-positions are used, R ¹² refers to the straight-chain backbone segment of the alcohol.

The Comb polymers can especially fumarate or itaconate polymers and copolymers, such as those described in EP-A-153 176, EP-A-153 177, EP-A-225 688 and WO 91/16407 are described.

Particularly preferred fumarate comb polymers are copolymers of alkyl fumarates and vinyl acetate in which the alkyl groups have 12 to 20 carbon atoms, especially polymers in which the alkyl groups have 14 carbon atoms or in which the alkyl groups are a mixture of C ₁₄ / C ₁₆ alkyl groups prepared, for example, by solution copolymerizing an equimolar mixture of fumaric acid and vinyl acetate and reacting the resulting copolymer with the alcohol or mixture of alcohols, preferably straight-chain alcohols are. When used, the mixture is advantageously a 1: 1 (wt: wt) mixture of nC ₁₄ and C ₁₆ alcohols. In addition, mixtures of C ₁₄ esters with the mixed C ₁₄ / C ₁₆ ester can advantageously be used. In such mixtures, the ratio of C ₁₄ to C ₁₄ / C _{16 is} advantageously in the range of 1: 1 to 4: 1, preferably 2: 1 to 7: 2, and most preferably about 3: 1, by weight. For example, the most preferred fumarate comb polymers may have a number average molecular weight in the range of 1,000 to 100,000, preferably 1,000 to 30,000 as measured by vapor phase osmometry (VPO).

Other suitable comb polymers are the polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride, as well as esterified ones Copolymers of styrene and fumaric acid. mixtures of two or more comb polymers can be used in the present invention and as previously said, this use may be advantageous.

Other examples for Comb polymers are hydrocarbon polymers such as copolymers of ethylene and at least one α-olefin, wherein the α-olefin preferably at most Has 20 carbon atoms, examples are n-decene-1 and n-dodecene-1. Preferably, the number average molecular weight of this copolymer is at least 30,000. The hydrocarbon copolymers can are prepared by methods known in the art, for example, using a Ziegler-type catalyst.

links with a linear group

Such Compounds comprise a compound in which at least one in the Substantially linear alkyl group having 10 to 30 carbon atoms is associated with a non-polymeric organic radical to at least to provide a linear chain of atoms containing the carbon atoms the alkyl groups and one or more non-terminal oxygen atoms includes.

By "substantially linear" is meant that the alkyl group is preferably straight-chain, but that is substantially straight-chain Alkyl groups with a low degree of branching, such as in the form of single methyl group can be used.

Preferably has the compound at least two of these alkyl groups, if the linear chain, the carbon atoms of more than one of the alkyl groups lock in can. When the compound has at least three of the alkyl groups, there may be more than one such linear chain, wherein the chains overlap can. The linear chain or chains may be part of the linking group between any two alkyl groups in the compound.

The Oxygen atom or the oxygen atoms are preferably direct inserted between carbon atoms in the chain and can, for example provided in the binding group in the form of a mono- or polyoxyalkylene group wherein the oxyalkylene group is preferably 2 to 4 carbon atoms Has. Examples are oxyethylene and oxypropylene.

As close the chain or chains contain carbon and oxygen atoms. You can also others Include heteroatoms such as nitrogen atoms.

The Compound may be an ester in which the alkyl groups with the Rest of the compound as -O-CO-n-alkyl or -CO-O-n-alkyl groups connected wherein, in the former case, the alkyl groups are derived from an acid and the rest of the compound is derived from a polyhydric alcohol and in the latter case the alkyl groups are derived from an alcohol and the remainder of the compound is derived from a polycarboxylic acid. The compound may also be an ester in which the alkyl groups as -O-n-alkyl groups are attached to the rest of the molecule. The connection may be both esters and ethers, or may be different Contain ester groups.

Examples include polyoxyalkylene esters, ethers, esters / ethers, and mixtures thereof, especially those containing at least one, preferably at least two, linear C ₁₀ to C ₃₀ alkyl groups and one polyoxyalkylene glycol group having a molecular weight up to 5000, preferably 200 to 5000 in which the alkylene group in the polyoxyalkylene glycol contains 1 to 4 carbon atoms, as in EP-A-61 895 and US-A-4,491,455.

• (a) n-Alkyl-,
• (b) n-Alkyl-CO-,
• (c) n-Alkyl-OCO-(CH₂)_n
• (d) n-Alkyl-OCO-(CH₂)_nCO-

sein können, wobei n beispielsweise 1 bis 34 ist, die Alkylgruppe linear ist und 10 bis 30 Kohlenstoffatome enthält und B das Polyalkylensegment des Glykols wiedergibt, in dem die Alkylengruppe 1 bis 4 Kohlenstoffatome aufweist, beispielsweise ein Polyoxymethylen-, Polyoxyethylen- oder Polyoxytrimethylenanteil, der im wesentlichen linear ist, wobei ein geringer Verzweigungsgrad mit niedrigeren Alkylseitenketten (wie in Polyoxypropylenglykol) toleriert werden kann, jedoch bevorzugt ist, daß das Glykol im wesentlichen linear ist. B kann auch Stickstoff enthalten.The preferred esters, ethers or esters / ethers which may be used may be represented in structure by the formula R ₂₃ OBOR ²⁴ be reproduced in which R ²³ and R ^{24 are the} same or different and

• (a) n-alkyl,
• (b) n-alkyl-CO-,
• (c) n-alkyl-OCO- (CH ₂ ) _n
• (d) n-alkyl-OCO- (CH ₂ ) _n CO-

wherein n is, for example, 1 to 34, the alkyl group is linear and contains 10 to 30 carbon atoms and B represents the polyalkylene segment of the glycol in which the alkylene group has 1 to 4 carbon atoms, for example a polyoxymethylene, polyoxyethylene or polyoxytrimethylene moiety is substantially linear, with a low degree of branching with lower alkyl side chains (as in polyoxypropylene glycol) can be tolerated, but it is preferred that the glycol is substantially linear. B may also contain nitrogen.

Suitable glycols are generally substantially linear polyethylene glycols (PEG) and propylene glycols (PPG) having a molecular weight of about 100 to 5000, preferably about 200 to 2000. Esters are preferred and fatty acids of 10 to 30 carbon atoms are useful for reaction with the glycols Formation of the ester additives, wherein it is preferred to use C ₁₈ to C ₂₄ fatty acid, in particular behenic acid. The esters can also be prepared by esterification of polyethoxylated fatty acids or polyethoxylated alcohols.

Polyoxyalkylene, diethers, ethers / esters and mixtures thereof are as additives suitable, with diesters are preferred when the component petroleum A tight-boiling distillate is when small amounts of mono-alcohols and monoesters (which often during the manufacturing process are formed) may be present. It is for active performance important that one bigger amount the dialkyl compound is present. In particular, stearin or Behendiester of polyethylene glycol, polypropylene glycol or polyethylene / polypropylene glycol mixtures are preferred.

Examples for others Links in this general category are those that are in Japanese Patent Publications Nos. 2-51477 and 3-34790, EP-A-117,108 and EP-A-326,356 are described, and cyclic esterified ethoxylates described in EP-A-356,256 are.

Hydrocarbon polymers

in der
T = H oder R¹
U = H, T oder Aryl
R¹ = C₁- bis C₃₀-Kohlenwasserstoff,
und v und w Molverhältnisse wiedergeben, wobei v im Bereich von 1,0 bis 0,0 liegt und w im Bereich von 0,0 bis 1,0 liegt.Examples are those having the following general formula:

in the
T = H or R ¹
U = H, T or aryl
R ¹ = C ₁ - to C ₃₀ -hydrocarbon,
and v and w represent molar ratios where v is in the range of 1.0 to 0.0 and w is in the range of 0.0 to 1.0.

These Polymers can directly from ethylenically unsaturated Monomers or indirectly by hydrogenating the from monomers such as isoprene and butadiene-produced polymer.

Preferred hydrocarbon polymers are copolymers of ethylene and at least one α-olefin having a number average molecular weight of at least 30,000 α-olefin at most 20 carbon atoms. Examples of such olefins are propylene, 1-butene, isobutene, n-octene-1, isooctene-1, n-decene-1 and n-dodecene-1. The copolymer may also contain small quantities, e.g. B. contain up to 10 wt.% Other copolymerizable monomers, for example, different from α-olefins olefins and non-conjugated dienes. The preferred copolymer is an ethylene / propylene copolymer. It is within the scope of the invention to include two or more different ethylene / alpha-olefin copolymers of this type.

The number average molecular weight of the ethylene / α-olefin copolymer is at least 30,000 as measured above, as measured by gel permeation chromatography (GPC) relative to polystyrene standards, preferably at least 60 000 and preferably at least 80 000. Functionally, there are none upper limit, but mixing problems result from elevated viscosity at molecular weights above about 150,000 and preferred molecular weight ranges are 60,000 and 80,000 to 120,000.

Advantageous the copolymer has a molar ethylene content between 50 and 85 %. Particularly advantageous is the ethylene content in the range of 57 to 80%, and preferably in the range of 58 to 73%, in particular 62 to 71%, and most preferably 65 to 70%.

preferred Ethylene / α-olefin copolymers are ethylene / propylene copolymers with an ethylene molar content from 62 to 71 and a number average molecular weight in the range of 60,000 to 120,000, particularly preferred copolymers are ethylene / propylene copolymers having an ethylene content of 62 to 71% and a molecular weight of 80,000 to 100,000.

The Copolymers can prepared by any of the methods known in the art for example, using a Ziegler-type catalyst. Advantageously, the polymers are substantially amorphous, since highly crystalline Polymers in fuel oil are relatively insoluble at low temperatures.

The Additive composition may also be another ethylene / α-olefin copolymer include, advantageously with an average molecular weight (Number average) of at most 7500, advantageously 1000 to 6000 and preferably 2000 to 5000, measured by vapor phase osmometry. Suitable α-olefins are as indicated above or styrene, with propylene being again preferred is. Advantageously, the ethylene content is 60 to 77 mol.%, Although at Ethylene / propylene copolymers up to 86 mol.% Ethylene advantageous can be used.

Examples for hydrocarbon polymers are in WO-A-9 111 488 described.

Polar compounds

Such compounds include an oil-soluble polar nitrogen compound bearing one or more, preferably two or more substituents of the formula = NR ¹ where R ^{1 is} a hydrocarbon group of 8 to 40 carbon atoms wherein the substituent or one or more of the substituents are optionally in the form of a derived cation. The oil soluble polar nitrogen compound is either ionic or nonionic and is capable of acting as a wax crystal growth modifier in fuels. It comprises, for example, one or more of the compounds (i) to (iii) as follows:
(i) amine salt and / or amide formed by reacting at least one molar hydrocarbon-substituted amine with a molar fraction of hydrocarbylic acid having from 1 to 4 carboxylic acid groups or their anhydride, wherein the substituent (s) having the formula = NR ^{1 is} the formula NR ¹ R ² has, wherein R ^{1 is} as defined above and R ^{2 is} hydrogen or R ¹ , provided that R ¹ and R ^{2 may be the} same or different, wherein the substituents are a part of the amine salt and / or the Provide amide groups of the compound.

Esters / amides having a total of 30 to 300, preferably 50 to 150 carbon atoms can be used. These nitrogen compounds are described in US-A-4,211,534. Suitable amines are usually long chain primary, secondary, tertiary or quaternary C ₁₂ to C ₄₀ amines or mixtures thereof, however, shorter chain amines can be used provided that the resulting nitrogen compound is oil soluble and thus normally contains a total of about 30 to 300 carbon atoms , The nitrogen compound preferably contains at least one straight-chain C ₈ - to C ₄₀ -, preferably C ₁₄ - to C ₂₄ -alkyl segment.

Suitable amines include primary, secondary, tertiary or quaternary, but preferably se kundäre. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecylamine, cocoamine and hydrogenated tallow amine. Examples of secondary amines include dioctadecylamine and methylbehenylamine. Amine mixtures are also suitable, such as those derived from natural materials. A preferred amine is a secondary hydrogenated tallow amine having the formula HNR ¹ R ² , in which R ¹ and R ^{2 are} hydrogenated tallow fat-derived alkyl groups consisting of approximately 4 weight percent C ₁₄ , 31 weight percent C ₁₆ and 59 weight percent. % C ₁₈ are composed.

Examples for suitable carboxylic acids and their anhydrides for producing the nitrogen compounds include cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid and naphthalenedicarboxylic and 1,4-dicarboxylic acids including Dialkyl spiro-bis-lactone. In general, these acids have about 5 to 13 carbon atoms in the cyclic moiety. Preferred useful in this invention acids are benzene dicarboxylic acids like phthalic acid, isophthalic and terephthalic acid. Phthalic acid or their anhydride is particularly preferred. The most preferred Compound is the amide / amine salt obtained by reaction of a molar proportion of phthalic anhydride with 2 molar portions of di (hydrogenated tallow) amine is produced. Another preferred compound is by dehydration This amide / amine salt produced Diamid.

Other Examples are substituted with long chain alkyl or alkylene dicarboxylic acid derivatives such as amine salts of monoamides of substituted succinic acids, wherein Examples of this known in the art and described for example in US-A-4,147,520 are. Suitable amines can be the ones described above.

Other examples are condensates as described in EP-A-327 423.
(ii) A chemical compound comprising or including a cyclic ring system, said compound having at least two substituents represented by the following general formula (I) -A-NR ¹ R ² (I) on the ring system in which A is an aliphatic hydrocarbon group optionally interrupted by one or more heteroatoms and being straight or branched, and R ¹ and R ^{2 are the} same or different and each independently is a hydrocarbon group of 9 to 40 carbon atoms; optionally interrupted by one or more heteroatoms, wherein the substituents are the same or different and the compound is optionally present in the form of its salt.

Preferably A has 1 to 20 carbon atoms and is preferably a methylene or polymethylene group.

Of the Term "hydrocarbon" as in the description used refers to a group with one directly to the rest of the molecule bonded carbon and hydrocarbon or predominantly hydrocarbon character. Close examples Hydrocarbon groups including aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl or cycloalkenyl), aromatic and alicyclic substituted aromatic and aromatic substituted aliphatic and alicyclic groups. aliphatic Groups are preferably saturated. These groups can Contain non-hydrocarbon substituents, provided that their presence does not change the predominant hydrocarbon character of the group. Examples shut down Keto, halogen, hydroxy, nitro, cyano, alkoxy and acyl. If the hydrocarbon group is substituted, is a single (mono) Substituent preferred.

Examples for substituted ones Close hydrocarbon groups 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The groups can also or alternatively from Contain carbon atoms different in a chain or a ring, otherwise composed of carbon atoms. suitable Close heteroatoms for example, nitrogen, sulfur and preferably oxygen one.

The cyclic ring system may include homocyclic, heterocyclic or fused polycyclic structures or a system in which two or more such cyclic structures are linked together and in which the cyclic structures may be the same or different. When two or more such cyclic structures are present, the substituents of the general formula (I) may be on the same or different structures, preferably on the same structure. Preferably, the or each cyclic structure is aromatic, especially a benzene ring. Most preferably, the cyclic ring system is a single benzene ring, it being preferred that the substituents in ortho or meta-positions, where the benzene ring may optionally be further substituted.

The Ring atoms in the cyclic structure or the cyclic structures are preferably carbon atoms but may, for example, be include one or more N, S or O atoms in the ring, wherein the compound in this case or these cases a heterocyclic compound is.

• (a) kondensierte Benzolstrukturen wie Naphthalin, Anthracen, Phenanthren und Pyren,
• (b) kondensierte Ringstrukturen, bei denen keiner oder nicht alle der Ringe Benzol sind, wie Azulen, Inden, Hydroinden, Fluoren und Diphenylenoxide,
• (c) Ende-an-Ende-verbundene Ringe wie Diphenyl,
• (d) heterocyclische Verbindungen wie Chinolin, Indol, 2,3-Dihydroindol, Benzofuran, Cumarin, Isocumarin, Benzothiophen, Carbazol und Thiodiphenylamin,
• (e) nicht-aromatische oder teilweise gesättigte Ringsysteme wie Decalin (d. h. Decahydronaphthalin), α-Pinen, Cardinen und Bornylen, und
• (f) dreidimensionale Strukturen wie Norbornen, Bicycloheptan (d. h. Norbornan), Bicyclooctan und Bicycloocten.

Examples of such polynuclear structures include:

• (a) condensed benzene structures such as naphthalene, anthracene, phenanthrene and pyrene,
• (b) condensed ring structures in which none or all of the rings are benzene, such as azulene, indene, hydroindene, fluorene and diphenylene oxides,
• (c) end-to-end linked rings such as diphenyl,
• (d) heterocyclic compounds such as quinoline, indole, 2,3-dihydroindole, benzofuran, coumarin, isocoumarin, benzothiophene, carbazole and thiodiphenylamine,
• (e) non-aromatic or partially saturated ring systems such as decalin (ie decahydronaphthalene), α-pinene, cardinen and bornylene, and
• (f) three-dimensional structures such as norbornene, bicycloheptane (ie, norbornane), bicyclooctane, and bicyclooctene.

Each hydrocarbon group forming R ¹ and R ² in the invention (formula I) may be, for example, an alkyl or alkylene group or a mono- or polyalkoxyalkyl group. Preferably, each hydrocarbyl group is a straight-chain alkyl group. The number of carbon atoms in each hydrocarbon group is preferably 16 to 40, especially 16 to 24.

It is also preferred that the cyclic system with only two substituents with the general Formula (I) is substituted and that A is a methylene group.

Examples for salts The chemical compounds are the acetate and the hydrochloride.

The compounds can be conveniently prepared by reducing the corresponding amide prepared by reacting a secondary amine with the corresponding acid chloride, and
(iii) long chain primary or secondary amine condensate with carboxylic acid containing polymer.

specific Close examples Polymers as in GB-A-2 121 807, FR-A-2 592 387 and DE-A-3 941 561, and also esters of telomeric acid and alkanolamines as described in US Pat. No. 4,639,256, and US Pat Reaction product of amine, the branched carboxylic acid ester contains Epoxy and monocarboxylic acid polyester, as described in US-A-4,631,071.

sulfur-carboxyl compounds

Examples are those described in EP-A-0 261 957.

fuel oil

The fuel oil is suitably a middle distillate fuel oil. Such Distillate fuel oils generally in the range of about 110 ° C to about 500 ° C, z. B. 150 ° C to about 400 ° C. The fuel oil can atmospheric Distillate or vacuum distillate or cracked gas oil or a Mixture in any proportions from directly distilled and thermal and / or catalytically cracked distillates. The most common Petroleum distillate fuels are kerosene, jet fuel, Diesel fuels, heating oil and heavy fuel oils. The heating oil can be a direct atmospheric Distillate or small amounts, z. B. Up to 35 wt.% Vacuum gas oil or cracked gas oils or both.

The fuel oil can be animal, vegetable or mineral oil and also synthetic be. It may also contain other additives than those mentioned above.

The Concentration of the additive combination in the oil may, for example, in the range from 1 to 5000 ppm by weight of additive (active ingredient) per weight of fuel, such as 10 to 2000 ppm by weight of active ingredient each Weight of the fuel, preferably 25 to 500 ppm, in particular 100 to 200 ppm.

The additive should be moderate in oil to the extent of at least 1000 ppm by weight of the oil Temperature be soluble. However, near the cloud point of the oil, at least a portion of the additive may precipitate out of the solution to modify the paraffin crystals that form.

concentrates are convenient as means for introducing the additive into masses of oil such as distillate fuel, the incorporation by methods known in the art can be done. The concentrates can if necessary, also contain other additives and preferably contain 3 to 75% by weight, especially 3 to 60% by weight, most preferably 10 to 50% by weight of the additives, preferably in solution in oil. Examples of carrier fluids are organic solvents including Hydrocarbon solvents, for example petroleum fractions like naphtha, kerosene and fuel oil, aromatic hydrocarbon-containing aromatic fractions (eg. Solvesso (trade name)) and paraffinic hydrocarbons such as hexane, pentane and isoparaffins, and includes mixtures of the above. The carrier liquid must of course regarding their compatibility be selected with the additive and with the fuel.

The additives according to the invention can according to other methods known in the art in masses of oil be introduced. If other additives are needed, they can simultaneously with the additives of the invention or to a be introduced at another point in time. Examples of others Close additives Antioxidants, anticorrosives, dehumidifiers, metal deactivators, Co-solvent, compatibilizers for additive packages, Odor improvers, antistatic additives (conductivity improvers), biocides, Dyes, smoke reducing agents, agents for increasing the Lifetime of catalysts, power multipliers, fuel economy additives, Demulsifiers and spray modifiers.

Examples

The The following examples illustrate the invention.

additives

The following additives were used and identified by their prefixed reference numbers:
B2: A number average molecular weight ethylene / vinyl acetate copolymer of 5,000 measured by GPC containing about 13.5 weight percent vinyl acetate.
A5: Ester obtained by reacting dilinoleic acid (dimeric C ₃₆ acid) with ethylene glycol and neutralizing the acid groups with methanol as described in US-A-3,287,273.

fuel

Of the The fuel used below is characterized as follows:

LEGEND

• • All Values are in ° C stated
• Distillation characteristics have been measured according to ASTM D-86 (IBP and FBP are initial or final boiling points)
• • CP is the cloud point as per IP 219/82 certainly
• • CFPP is the blockage point of the filter due to cold and SFPP is the simulated Filter clogging point (see "TESTS" for more details)

TESTING

The Additives were dissolved in fuels and the following tests performed on the fuel, the was treated with additives to measure the following to the effectiveness the tested additives as a filterability improver in distillate fuels.

Simulated filter clogging point (SFPP)

Of the Test was carried out in steps, as it essentially in EP-A-0 403 097, and constitutes an amendment of the CFPP test.

The test for determination the blockage point of the filter due to cold (or CFPP test)

Of the Test, which is detailed in the "Journal of the Institute of Petroleum", Volume 52, Number 510, June 1966, pages 173 to 285 is designed to cope with the cold flow behavior of middle distillate to correlate in automobile diesels.

Short That is, a sample of the oil to be examined (40 ml) is cooled in a bath, the kept at about -34 ° C is going to be non-linear cooling at about 1 ° C / minute to surrender. Periodically (with every degree Celsius, starting from above the cloud point) is the cooled oil on his ability examined in a prescribed period by a fine Strainer to flow, using a test device that is a pipette, whose lower end is attached to an inverted funnel, the under surface of the oil to be tested is arranged. about straining the mouth of the funnel is a 350-mesh sieve (mesh number 350) with an area which is given by a diameter of 12 mm. The periodic tests are each initiated by applying a vacuum to the top of the Eyedropper is applied, causing oil through the sieve in the pipette upwards is sucked to a mark indicating 20 ml of oil. After every successful Passage becomes the oil immediately into the CFPP test tube returned. The test is repeated with each degree of temperature drop until the oil is the pipette can not fill in 60 seconds anymore. The temperature, Failure is reported as the CFPP temperature.

Results

LEGEND

• • Set ΔSFPP and ΔCFPP the difference between the SFPP (or the CFPP) of the basic fuel and that of the treated fuel.
• • The Values under the component designations are treatment rates of the active ingredient in ppm based on the weight of the fuel.
• • * indicates results of additive compositions of the invention.
• • One Dash means nothing was read.

The results show that replacing a portion of 'B' component with an 'A' component either improves or does not adversely affect the filterability of the fuel. They also show that a target value of the filterability by combinations according to the invention using less 'B' component can be met, it being noted that the 'A' component itself provides advantageous properties.

The inventive additive combinations can also for to decrease the decrease in the propensity of the paraffin in the fuel be effective (i.e., they can also anti-deposition additives for represent the paraffin), and can even with slow cooling tests activity such as the advanced programmed cool down test (Extended Program Cooling Test, XPCT) Technique is known.

Claims (30)

Use of a co-additive (A) comprising an oil-soluble lubricity additive comprising an ester of a dicarboxylic acid and a polyhydric alcohol wherein the acid has from 2 to 50 carbon atoms, the alcohol has one or more carbon atoms and a trihydric alcohol or a diol Formula R ² (OH) _y is where R ^{2 represents} an unsubstituted polymethylene group having 1 to 10 carbon atoms and y represents an integer and the number of hydroxyl groups, and wherein the ester is composed of only carbon, hydrogen and oxygen and having one or more free hydroxy groups, the use being in a composition comprising a major proportion of a fuel oil and a minor amount of a component (B) comprising a cold flow additive additive comprising and present as a copolymeric ethylene flow improver; to enhance the cold flow properties of the composition. Use according to claim 1, wherein the lubricating additive the ester of an aliphatic, saturated or unsaturated, straight chain or branched chain dicarboxylic acid. Use according to any one of the preceding claims, wherein the lubricating additive is the ester of a dicarboxylic acid of the formula: R '(COOH) ₂ wherein R 'represents a substituted or unsubstituted polymethylene group having from 2 to 50 carbon atoms. Use according to one of the preceding claims, in the lubricant additive comprises the ester of a trihydric alcohol. Use according to claim 4, wherein the trivalent Alcohol is glycerin. Use according to any one of claims 1 to 3, wherein the lubricating additive comprising the ester of a diol. Use according to claim 6, wherein the lubricating additive includes the ester, by the reaction of dilinoleic acid with ethylene glycol and neutralization of the acid groups with methanol becomes. Use according to one of the preceding claims, in the lubricant additive comprises an ester having a molecular weight of 200 or greater. Use according to one of the preceding claims, in the component (B) comprises an ethylene / unsaturated ester copolymer. Use according to claim 9, wherein the unsaturated ester from an unsaturated Alcohol with a saturated carboxylic acid is. Use according to any one of the preceding claims additionally comprising, as a co-additive, an oil-soluble polar nitrogen compound having one or more substituents of the formula -NR ¹ - in which R ^{1 represents} a hydrocarbon-like group containing 8 to 40 carbon atoms, wherein the substituent or one or more of the substituents optionally in the form of a derived cat present. Use according to one of the preceding claims, in the fuel oil a middle distillate fuel oil is. Use of any of the preceding claims, in the total concentration of components (A) and (B) in the fuel oil in the range from 25 to 500 ppm of active ingredient, based on the Weight, per weight of fuel oil. A fuel oil composition comprising a major proportion of a fuel oil and a combination: a component (A) comprising an oil-soluble lubricity additive comprising an ester of a dicarboxylic acid and a polyhydric alcohol wherein the acid has from 2 to 50 carbon atoms, the alcohol one or more carbon atoms and a trihydric alcohol or diol of the formula R ² (OH) _y , wherein R ^{2 represents} an unsubstituted polymethylene group having from 1 to 10 carbon atoms, and y represents an integer and the number of hydroxy groups, and wherein the ester is composed only of carbon, hydrogen and oxygen and has one or more free hydroxyl groups, and a component (B) comprising a cold flow improver additive comprising a copolymeric ethylene cold flow improver and optionally other additives. An additive concentrate comprising: a component (A) comprising an oil-soluble lubricity additive comprising an ester of a dicarboxylic acid and a polyhydric alcohol wherein the acid has 2 to 50 carbon atoms, the alcohol has one or more carbon atoms, and a trihydric alcohol or a diol of the formula R ² (OH) _y , wherein R ^{2 represents} an unsubstituted polymethylene group having 1 to 10 carbon atoms, and y represents an integer and the number of hydroxy groups, and wherein the ester consists of only carbon, hydrogen and Oxygen and having one or more free hydroxyl groups; and a component (B) comprising a cold flow improver additive comprising a copolymeric ethylene cyclic flow improver and optionally other additives. A composition according to claim 14 or 15, wherein the lubricant additive the ester of an aliphatic, saturated or unsaturated, straight chain or branched chain dicarboxylic acid. A composition according to any one of claims 14 to 16, wherein the lubricity additive is the ester of a dicarboxylic acid of formula R '(COOH) ₂ wherein R 'represents a substituted or unsubstituted polymethylene group having from 2 to 50 carbon atoms. A composition according to any one of claims 14 to 17, in which the lubricating additive is the ester of a trivalent alcohol includes. A composition according to claim 18, wherein the trivalent Alcohol is glycerin. A composition according to any one of claims 14 to 17, in which the lubricant additive comprises the ester of a diol. A composition according to claim 20, wherein the lubricating additive includes the ester, by the reaction of dilinoleic acid with ethylene glycol and neutralization of the acid groups with methanol becomes. A composition according to any one of claims 14 to 21, wherein the lubricating additive comprises an ester having a molecular weight of 200 or greater. A composition according to any one of claims 14 to 22, wherein component (B) comprises an ethylene / unsaturated ester copolymer. A composition according to claim 23, wherein the unsaturated ester is an unsaturated alcohol with a saturated carboxylic acid. A composition according to any one of claims 14 to 24 which additionally comprises, as a co-additive, an oil-soluble polar nitrogen compound containing one or more substituents of the formula -NR ¹ wherein R ^{1 represents} a hydrocarbon-type group containing from 8 to 40 carbon atoms, wherein the substituent or one or more of the substituents is optionally in the form of a cation derived therefrom. A composition according to claim 14 or one of claims 16 to 25, if dependent of claim 14, wherein the fuel oil is a middle distillate fuel oil. A composition according to claim 14 or one of claims 16 to 26, if dependent of claim 14, wherein the total concentration of the components (A) and (B) in the fuel oil is in the range of 25 to 500 ppm of active ingredient, per Weight of fuel oil. Method for mixing additives with a fuel oil, which: (I) Injecting component (B) as defined in claim 1 is, in the fuel oil; (Ii) Injecting component (A) as defined in claim 1 is, in the fuel oil; (Iii) Measuring the cold flow properties of fuel oil after injection of steps (i) and (ii) and (iv) Adjust the relative injection rates of components (B) and (A) and thereby from their relative proportions to the results of the step (iii) to take into account and the desired ones Cold flow properties in the fuel oil provide, The method of claim 28, wherein the fuel oil is a flowing Steam of the same covers, step (i) takes place in a first station and step (ii) in a second station takes place. A method according to claim 28 or 29, wherein a Sensor step (iii) performs and information about one control unit supplied is to inject one or both components (B) and (A) to regulate.