PT100984A - Low sulphur content diesel type fuels containing organometallic complexes - Google Patents

Abstract

This invention relates to fuels of the diesel type having a low sulphur content which are useful for use in diesel engines equipped with devices to capture small particles from the exhaust gas system. These fuels contain an effective quantity of an organometallic complex to reduce the ignition temperature of the particles of the exhaust gases collected by the capture device. The sulphur content of these diesel-type fuels is not greater than approximately 0.1% by weight and preferably is no more than approximately 0.05% by weight. The organometallic complex is soluble or stably dispersible in a fuel of the diesel type and is derived from (i) an organic compound containing at least two functional groups connected to a hydrocarbon ligand and (ii) a reagent derived from a metal which is capable of forming a complex with organic compound (i), the metal being any type of metal which is capable of reducing the ignition temperature of the exhaust gas particles. These functional groups include =X, -XR, -NR2, -NO2, =NR, =NXR, =N-R*-XR, <IMAGE>, <IMAGE>, <IMAGE>, -CN, -N=NR and -N=CR2, where the symbol X represents an oxygen or sulphur atom, the symbol R represents an atom of hydrogen or a hydrocarbon group, the symbol R* represents a hydrocarbylene or hydrocarbylidene group and the symbol a represents a number (e.g. between 0 and approximately 10). Useful metals include the metals Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Fe, Co, Cu, Zn, B, Pb and Sb and mixtures of two or more of these metals. This invention also relates to methods for the operation of a diesel engine equipped with a device to capture small particles from the exhaust gas system using the said fuel of the diesel type with a low sulphur content.

Description

THE LUBRIZOL CORPORATION "DIESEL FUELS OF LOW SULFUR CONTENT CONTAINING ORGANOMETRIC COMPLEXES &quot;

Technical Field of the Invention The present invention relates to low sulfur diesel fuels which are useful for diesel engines equipped with separators of the small particles of the exhaust system. These fuels contain an effective amount of an organometallic complex to decrease the ignition temperature of the exhaust particles collected in the separator. The sulfur content of these diesel fuels is not more than about 0.1% by weight and preferably is not greater than about 0.05% by weight. The organometallic complex is soluble or dispersibly stable in the diesel fuel and is derived from (i) an organic compound containing at least two groups

functional bonds coupled to a hydrocarbon linkage and (ii) a reagent of metallic nature capable of complexing with the organic compound (i). Said metal may be any metal capable of reducing the ignition temperature of the exhaust particles by considering the Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Fe, Co, Cu, Zn, B, Pb, Sb, or a mixture of two or more of these metals.

Background of the Invention

Diesel engines have been used as engines for long-haul vehicles due to relatively low fuel costs and better mileage. However, because of their operating characteristics, diesel engines discharge a large amount of particulate coal or very fine condensed particles or their agglomerates into the atmosphere compared to gasoline engines. Such particles or condensates are often referred to as &quot; diesel soot and the emission of such particles or soot causes pollution and is undesirable. In addition, it has been found that diesel soot is rich in condensed polynuclear hydrocarbons and some of these components have been identified as carcinogenic agents. As a consequence, separators or filters were designed for these small particles for use with diesel engines, capable of collecting the coal particles and the

condensed particles.

Conventionally such small particle separators or filters have been made of a heat resistant filter element which is formed of porous ceramic or metallic fibers and an electric heater to heat and burn the small particles of charcoal collected by the filter element. This heater is necessary since the exhaust gas temperatures of diesel engines under normal operating conditions are insufficient to burn accumulated soot that has been collected in the filter or separator. Generally temperatures between 450 and 600øC are required and the heater provides the necessary addition of the exhaust gas temperature to burn the particulates collected in the separator and to regenerate that separator. Otherwise there will be an accumulation of the coal particles and the separator will eventually become clogged causing operational problems due to increased back pressure in the exhaust system. Heated separators of the type described above do not provide a complete solution to this problem since the exhaust gas temperature is lower than the ignition temperature of the small coal particles when the vehicle is operating under normal conditions and the heat generated by the electric heater is dissipated by the exhaust gas flow when the volume of such exhaust gases is

quite large. Alternatively, higher temperatures in the separator can be achieved by periodically enriching the air / fuel mixture burned in the diesel engine thereby providing a higher exhaust gas temperature. However, such higher temperatures may lead to self-regeneration which results in high localized temperatures which could damage the separator.

It has also been suggested that particle accumulation in the separators can be controlled by reducing the ignition temperature of the small particles so that these particles start to be burned to the lowest possible temperature values. A method for reducing the ignition temperature involves adding to said small particles the exhaust system of an improved combustion enhancement agent and the more practical way to effect the addition to the small particles of the exhaust system of an improved combustion agent was to add to the fuel that agent to improve combustion. Copper derivatives have also been suggested as agents for improving the combustion of fuels including diesel fuels. The institution &quot; U.S. Environmental Protection Agency &quot; (EPA) estimates that the average sulfur content in fuels for diesel engines of long 4

This level is reduced to a value of not more than 0,05% by weight as from 1 October 1993. The EPA institution has also determined that this diesel fuel has a minimum cetane number of 40 (or a maximum level of 35% aromatic components). The purpose of this provision is to reduce the emissions of small sulphurous particles and small organic and carbonaceous particles. See &quot; Federal Register, Vol. 55, ns. 162, 21 August 1990, pp. 34120-34151 &quot;. Low sulfur diesel fuels and technology to meet these emission requirements are not yet commercially implemented. One approach to meeting these requirements is to provide an additive for the low sulfur diesel fuel which can be efficiently utilized in a low sulfur diesel type fuel environment in order to reduce the ignition temperatures of the soot is collected in the particulate separators of diesel engines. U.S. Pat. 3 346 493 discloses librifying compositions containing metal complexes made from the reaction products of succinic acid substituted by hydrocarbons (for example succinic anhydride substituted by polyisobutylene) and alkylene amines (for example polyalkylene polyamines), wherein these 5

complexes formed by reacting with said reaction products at least about 0.1 equivalents of a compound derived from a complexing metal. These metals are those having atomic numbers between 24 and 30 (ie Cr, Mn, Fe, Co, Ni, Cu and Zn). U.S. Pat. 4 673 412 discloses fuel compositions (for example, diesel fuels, distillate fuels, heating oils, residual fuels, marine-type fuel oils) which contain a compound derived from a metal and an oxime. This patent indicates that fuels containing this combination are stable during storage and effective in reducing the formation of soot in the exhaust of an internal combustion engine. A preferred compound derived from a metal is a transition metal complex with a Mannich base, said Mannich base being derived from (A) an aromatic phenol, (B) an aldehyde or a ketone and (C) an amine containing hydroxyl groups and / or thiol. The desired metals are selected from Cu, Fe, Zn, Co, Ni and Mn. U.S. Pat. No. 4,816,038 discloses fuel compositions (for example, diesel-type fuels, distillate fuels, heating oils, residual fuels, marine-type fuel oils) containing the reaction product of a transition metal complex of an aromatic Mannich compound containing groups 6

hydroxyl and / or thiol with a Schiff base. This patent indicates that fuels containing this combination are stable during storage and effective in reducing the formation of soot in the exhaust of an internal combustion engine. The Mannich base is derived from (A) an aromatic component containing hydroxyl and / or thiol groups, (B) an aldehyde or a ketone and (C) an amine containing hydroxyl and / or thiol groups. The desired metals are selected from Cu, Fe, Zn and Mn. International Patent Application no. WO 88/02392 discloses a method for exploiting a diesel engine equipped with a particulate separator of the exhaust system in order to reduce accumulation of the exhaust particles collected in the separator. This method consists in operating the diesel engine with a fuel which contains an effective amount of a compound or a complex of titanium or zirconium in order to reduce the ignition temperature of the small exhaust particles collected in the separator.

SUMMARY OF THE INVENTION The present invention relates to low sulfur diesel fuels which are useful in diesel engines equipped with separators of the small particles of the exhaust system. These fuels contain an effective amount of an organometallic complex to lower the ignition temperature of the exhaust particles 7

collected on the tab. The sulfur content of these diesel fuels is not more than about 0.1% by weight and preferably not more than about 0.05% by weight. The organo-organic complex is soluble or dispersibly stable in the diesel-type fuel and is derived from (i) an organic compound containing at least two functional groups coupled to a hydrocarbon bridge and (ii) a reagent derived from a metal capable of forming a complex with the organic compound (i), said metal being any metal capable of reducing the ignition temperature of the exhaust particles. As functional groups, X = -XR, -NR 2, -NO 2, = NR 1 = NXR, = N-R 2 -XR,

-N (R * N) a -R, -P (X) XR, -P (X) XR

III I

RR XR R -CN, -N = NR and -N = CR2; in which X is oxygen or sulfur, R is hydrogen or hydrocarbyl, R is hydrocarbylene or hydrocarbylidene and a is a number (for example, from zero and 10). Useful metals include Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Fe, Co, Cu, Zn, B, Pb, Sb, and mixtures of two or more several of these metals. The present invention also relates to methods of operating a diesel engine equipped with a particulate separator of the exhaust system using low-diesel diesel fuels of 8

sulfur.

Description of Preferred Aspects The term &quot; hydrocarbyl &quot; and related terms such as &quot; hydrocarbylene &quot; &quot; hydrocarbylidene &quot;, &quot; hydrocarbon derivatives &quot;, etc., refer to a chemical group having a carbon atom directly coupled to the remaining part of the molecule and having the characteristics of a hydrocarbon or predominantly of a hydrocarbon within the scope of the present invention. Examples include the following groups: (1) Hydrocarbon groups; aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic and substituted alicyclic-aromatic, aromatic-aliphatic and alicyclic aromatic groups and the like and also the cyclic groups in which the ring is completed through another portion of the molecule (i.e., any two indicated substituents may together form an alicyclic group). Such groups are known to those skilled in the art. Examples include methyl, ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, etc. (2) Substituted hydrocarbon groups; i.e., groups which contain non-hydrocarbon substituents which in the context of the present invention do not alter the predominantly hydrocarbon type characteristics of the group. Those skilled in the art are well aware of suitable substituents. Examples are halo, hydroxy, nitro, cyano, alkoxy, acyl, etc. (3) Heterogroups; i.e. groups which although exhibiting predominantly hydrocarbon type characteristics in the context of the present invention, have atoms other than the carbon atom in a chain or ring which would otherwise only consist of carbon atoms. Suitable heteroatoms are apparent to those skilled in the art and by way of example the nitrogen, oxygen and sulfur atoms.

In general there will be no more than three substituents or heteroatoms and preferably there will be no more than one in ten carbon atoms in the hydrocarbyl group.

Terms such as &quot; alkyl derivatives &quot;, &quot; aryl derivatives &quot; and the like have meanings analogous to those defined above taking into account that they are now alkyl groups, aryl groups and the like. The term &quot; bottom &quot; used herein together with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy and the like is intended to describe groups containing at most 7 carbon atoms.

The aromatic groups referred to herein

and the appended claims associated with the structure of the organometallic complexes of the present invention and in some cases represented by &quot; Ar &quot; in the formulas now provided may be mononuclear type such as the phenyl, pyridyl or thienyl or the polynuclear type groups. The polynuclear type groups may be of the molten type in which an aromatic nucleus is melted at two points with another nucleus as in the naphthyl, anthranyl, azanaphthyl, etc. groups. The polynuclear groups may also be of the coupled type in which at least two nuclei (both mononuclear and polynuclear type) are coupled to each other through bonding bridges. Such bridges may be selected from the group consisting of carbon-carbon type single bonds, ether bridges, keto bridges, sulfide bridges, polysulfide bridges having from 2 to 6 sulfur atoms, sulfinyl bridges, sulfonyl bridges, alkylene bridges, bridges lower alkylene bridges, lower alkylene-bridges, lower alkylene-bridges, lower alkylene-bridges, lower alkylene-polysulfide bridges having from 2 to 6 carbon atoms, amino bridges, polyamino bridges, and mixtures of the bridging linkages divalent In some cases there may be more than one bond bridge between two aromatic nuclei; for example, a fluorene core having two benzene nuclei connected simultaneously by a methylene bridge and a bond 11

covalent. This type of nucleus may eventually be considered to have three nuclei but only two of them are aromatic. However, it is normal for the aromatic group to contain only carbon atoms in the aromatic nuclei per se (plus any alkyl or alkoxy substituent present). The aromatic group may be a single ring aromatic group represented by the general formula ar (Q) m wherein ar is a single ring aromatic nucleus (e.g., benzene) having 4 to 10 carbon atoms, each symbol Q independently represents a lower alkyl group, a lower alkoxy group or a nitro group and ra is an integer from 0 to 4. Examples of cases in which the aromatic group is a single ring aromatic group include the following :

etc., wherein Me represents methyl, Et represents ethyl, Pr represents propyl, and Nit represents nitro.

In case the aromatic group is a ring group 12 /

The polynuclear type moiety can be represented by the general formula wherein Q, m and n are as defined above, m 'is an integer from 1 to 4 and O represents a pair of melt bonds fusing two rings so that two carbon atoms form part of the rings of each of the two adjacent rings. Specific examples of cases in which the aromatic group is a fused ring aromatic group are:

H

In the case where the aromatic group is a linked polynuclear aromatic group it may be represented by the general formula ## STR3 ## wherein w is 1 to 20, the symbol ar the meanings defined above with the proviso that there are at least two unsatisfied (i.e., free) valences in the total of the groups represented by the symbol ar, the symbols Q have the meanings defined above and each symbol Lng represents an individually selected connecting bridge the group consisting of carbon-carbon single bonds, ether bridges (e.g. -0-), keto bridges (e.g.,

O

sulphonyl bridges (e.g. -S-), polysulfide bridges having from 2 to 6 sulfur atoms (e.g., -S-2-6), sulfinyl bridges (e.g., -S (O) -), sulfonyl bridges ( for example, -S (O) 2 -), lower alkylene bridges (for example, -CH2-, -CH2 -CH2-, -CH2 -CH-, R- etc.) / bridges (lower alkyl) -methylene (e.g., C 2₂) /) lower alkylene-ether bridges (e.g., 14β-ch2o-ch2o-ch2-, -ch2ch2-o- / -ch2ch2och2ch2- / -ch2choch2ch- R ° R ° -ch2chochch2-,

(Lower alkylene) -heter bridges (for example, wherein one or more of the lower alkylene-ether bridges is replaced by a -S (O) , lower (lower alkylene) -polysulfide bridges (for example, one or more of which atom (s) -O- is substituted with a -S-2 'group), amino (e.g., -N-, -N- , -CH 2 N-, -CH 2 NCH 2 -, -alk-N, R 2 wherein R 1 is lower alkylene, etc.), polyamino bridges (for example, -N (alk) the unsatisfied free N-valences are taken up with hydrogen atoms or groups R)) and mixtures of such bonding bridges (each R represent representing a lower alkyl group). It is also possible that one or more of the groups represented by the symbol air in the above-mentioned aromatic group is replaced by a molten core such as φ ar φ m '. Specific examples of cases in which the aromatic group is a linked polynuclear aromatic group include:

Mc

(I.e.

1 / ι ~ Τ --Ν · -

(I.e.

For reasons of cost, availability, attributes, etc., the aromatic group is usually a benzene nucleus, a benzene nucleus connected by a lower alkylene bridge, or a naphthalene nucleus.

Qrganometallic Complexes

The organometallic complexes of the present invention are derived from (i) an organic compound containing at least two functional groups coupled to a hydrocarbon bridge, and (ii) a reagent derived from a metal capable of forming a complex with component (i). These complexes are soluble or are stable dispersible in the diesel fuel. The complexes which are soluble in the diesel fuel are such that their solubility corresponds to at least one gram per liter at a temperature of 25 ° C. Complexes which are stable or stablely dispersible in the diesel-type fuel 16

remain dispersed in that diesel fuel for at least 24 hours at 25 ° C.

Component (i); The organic compound (i) may be designated &quot; metal chelating agent &quot; which is an accepted terminology for a well-known class of chemical compounds which have already been described in various texts including Chemistry of the Metal Chelate Compounds, by Martell and Calvin, Prentice-Hall, Inc., N.Y. (1952). Component (i) is an organic compound which contains a hydrocarbon bridge and at least two functional groups. It is possible to use the same or different functional groups in component (i). These functional groups include the groups = X, -XR, -NR2, -NO2, = NR, = NXR, = NR * -XR, -N- (R * N) a R, -P (X) XR, -P X) XR, -N = CR2, -CN and -N = NR,

III I

RR R XR wherein X is oxygen or sulfur, R is hydrogen or hydrocarbyl, R is hydrocarbylene or hydrocarbylidene, and a is preferably a number between zero and about 10.

Preferred functional groups are the groups = X, -OH, -NR2, -NO2, = NR1, = NH2, -N- (R * N), and -CN.

R 17

According to one embodiment the functional groups are different carbon atoms of the hydrocarbon bridge. According to a variant the functional groups are adjacent or are in beta position relative to one another.

In one embodiment, the component (I) is a compound represented by the general formula (I):

(R) d (i) in which: b is from 0 to about 10, preferably from zero to about 6, more preferably from zero to about 4, and even more preferably from zero and about 2; c is from 1 to about 1000 or from 1 to about 500 or from 1 to about 250 or preferably from 1 to about 100 or from 1 to 50; d is zero or 1; 18

in the case where c is greater than 1, d is 1; each R is independently hydrogen or hydrocarbyl group; R 1 is hydrocarbyl or G; R and R are each independently hydrogen, hydrocarbyl groups or together may form a C1 to C2 double bond; R 2 is hydrogen, hydrocarbyl, or G; R, R, R and R may together form a triple bond between C and C; 13 12

R and R may together with C and C form an alicyclic, aromatic, heterocyclic, alicyclic-heterocyclic, alicyclic-aromatic, heterocyclic-aromatic, heterocyclic-alicyclic, aromatic-alicyclic or aromatic-heterocyclic alicyclic group; or a substituted hydrocarbyl-alicyclic, substituted hydrocarbyl-aromatic, substituted hydrocarbyl-heterocyclic, substituted-hydrocarbyl-alicyclic-substituted-heterocyclic, substituted-hydrocarbyl-alicyclic-aromatic, substituted-hydrocarbyl-heterocyclic-aromatic, substituted-hydrocarbyl-heterocyclic-alicyclic , substituted hydrocarbyl aromatic-alicyclic or substituted hydrocarbyl aromatic heterocyclic; 19

R6 and R7 are each independently hydrogen, hydrocarbyl or C1-6 alkyl; R is hydrocarbylene or hydrocarbylidene; each of the substituents represented by

Q is independently = X, -XR, -NR2, -NO2, -RXR, -R8 NR2, -R8 N02, -C (R) = X, -R8 C (R) = X, -C (R) = NR (R) = NXR, -C (R) = N-R 9 -XR, -R 8 -C (R) = N-R 9 -XR, -N- (R 9 N (X) XR, -R8-N (R9 N) eR, -P (X) XR, -P (X)

II III I I

(X) XR, -N-CR 2, -R N-CR 2,

XR if d is zero, T is = X, -XR, -NR2, -NO2, -C (R) = X, -C (R) = NR, -C (R) = NXR, -C (R) = N-R9-XR, -N- (R9 N) eR, -P (X) XR,

I I I

RR R -P (X) XR, -N = CR2, = NXR, -n (R10) -Q, -CN, -N = NR or -N (R9 N) e-Q;

XR RR

if d is one, T is -X-, -NR-, -C-, -c-, -CR, -c-, N (R 9 N) e R, -N (R 9 N) e,

II II 9 II 9 II II

(X) XR, -P (X) X-, -P (X) X- or -P (X) XR;

III I R XR X- 1 2

G and T together form C and C 20

will form a group of general formula

N II N

N

X is oxygen or sulfur; e are each independently from 0 to about 10, preferably from 1 to about 6, more preferably from 1 to 4; Each R is a hydrocarbylene or hydrocarbylidene group, a substituted hydroxyhydrocarbylene or hydrocarbylidene group, or a substituted amino-hydrocarbylene or hydrocarbylidene group; Each R is a hydrocarbylene or hydrocarbylidene group; R 2 is hydrogen atom or a hydrocarbyl group or a substituted hydroxyhydrocarbyl group; Q represents a group R11 R13 G-C4-C5-R12 R14 R15 L15 -R16 g 21 is a number from zero to about 10, preferably from zero to about 6 , more preferably from zero to about 4, and even more preferably from zero to about 2; R 2 is hydrocarbyl or G; R 1 and R 2 independently represent a hydrogen atom or hydrocarbyl groups or together may form a double bond between and; R 2 represents a hydrogen atom, a hydrocarbyl group or G; R 1, R 2, R 3 and R 4 may together form a triple bond between C and C; R and R may together with C and 22 C form an alicyclic, aromatic, heterocyclic, alicyclic-heterocyclic, alicyclic-aromatic, heterocyclic-aromatic, heterocyclic-alicyclic, aromatic-alicyclic or aromatic- heterocyclic; or a substituted hydrocarbyl alkyclic, substituted hydrocarbyl heterocyclic, substituted hydrocarbyl heterocyclic, substituted hydrocarbyl alicyclic heterocyclic, substituted hydrocarbyl alicyclic aromatic, substituted hydrocarbyl heterocyclic aromatic, substituted hydrocarbyl heterocyclic alicyclic, aromatic-alicyclic or substituted hydrocarbyl-aromatic-heterocyclic; Each of Rx and Rx is independently hydrogen, hydrocarbyl or C1-6 alkyl. R13 and R13 are independently hydrocarbyl groups preferably having up to about of 250 carbon atoms, more preferably up to about 200 carbon atoms, more preferably up to about 150 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about of 30 carbon atoms. Each R, R 13 and R may also represent the hydrogen atom. Any of R1 and R3 'or both may represent G. t. i η2 n4 π5 πβ "12 14 _15" 16

R, R, R, R, R, R, R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 20 carbon atoms, more preferably up to about 12 carbon atoms, and most preferably up to about of 6 carbon atoms. 7 8 9

R, R and R are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups, more preferably alkylene groups preferably have

S up to about 40 carbon atoms, more preferably up to about 30 carbon atoms, more preferably up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably 2 to 6 carbon atoms and more preferably between 2 and 4 carbon atoms. R 2 is hydrogen, hydrocarbyl or substituted hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms , more preferably up to about 30 carbon atoms, and most preferably up to about 10 carbon atoms. G is preferably a group = X, -XR, -NR2, -NO2, -C (R) = X, -C (R) = NR, C (R) = NXR, -N = CR2 or -r8n = cr2.

In the case where d is zero, T is preferably X, -XR, -NR2, -NO2, -C (R) = X,

(R) = NR, -C (R) = NXR, -N = CR2, -N (RXU) -Q or -N (R N) eR.

R R

In the case where d is one, T is preferably -X-, -NR-, -C-, 1-c-, -CR, II. (R 9 N) e R or -N (R 9 N) e.

R RR 24 κ ο

In one embodiment R is a group other than ethylene when G is -OH. In one embodiment, G and T represent different groups of the group -NO 2. In one embodiment, component (i) is other than an N, δ'-di- (3-alkenylsalicylidene) diamino alkane. In one embodiment, component (i) is different from Ν, Ν'-di-salicylidene-1,2-ethane-diamine.

In one embodiment, the component (i) is a compound represented by the general formula II

In general formula (II), i is from 0 to about 10, preferably from 1 to about 8. R is hydrogen or a hydrocarbyl group preferably having up to about 200 atoms of carbon, preferably up to about 150 carbon atoms, more preferably up to about 100 carbon atoms, more preferably between about 10 and 60:22 carbon atoms. R and R are independently hydrogen or hydrocarbyl groups having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, and

preferably up to about 10 carbon atoms. T is -XR, -NR 2, -NO 2, -CN, -C (R) = X / -C (R) = NR, -C (R) = NXR, -N = CR 2, -N (R 10) -Q or -N (R 9 N) eR.

R R 9 10

R, X, Q, R, R and e are as previously defined for the general formula (I). Component (i) may be selected from a wide variety of organic compounds containing two or more of the functional groups referred to above. Examples include aromatic Mannich compounds, hydroxyaromatic oximes, Schiff's bases, calixarenes, β-substituted phenols, α-substituted phenols, carboxylic acid esters, acylated amines, hydroxiazylenes, benzotriazoles, amino acids, β-diketones, hydroxamic acids, bound phenolic compounds, aromatic difunctional compounds, dithiocarbamates, xanthates, formazils, pyridines, acylated boronated amines, phosphorus containing acylated amines, pyrrole derivatives, porphyrins, sulfonic acids and EDTA derivatives. (1) Mannich Aromatic Compounds According to a variant, component (i) is an aromatic Mannich compound derived from an aromatic hydroxyl and / or thiol containing compound, an aldehyde or a ketone, and an amine. These aromatic Mannich compounds are preferably the reaction product of 26

(A-1) an aromatic hydroxy- and / or thiol-containing aromatic compound having the general formula

- (X H) m (A-1) wherein Ar is an aromatic group; m is 1, 2 or 3; n is 1

number between 1 and about 4; R 2 is independently a hydrogen atom or a hydrocarbyl group having approximately 1 to 100 carbon atoms; R 2 is hydrogen, amino or carboxyl; and X represents an oxygen or sulfur atom or both in the case where m represents the integer 2 or represents an upper integer; (A-2) an aldehyde or a ketone having the general formula

Or a precursor thereof, wherein R 1 and R 2 independently represent a hydrogen atom or saturated hydrocarbyl groups having 1 to about 18 carbon atoms and (A-2) R may also represent a hydrocarbyl group containing a carbonyl radical and having 27 /

from 1 to about 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amino group.

In the general formula (A-1) Ar may represent a benzene nucleus or a naphthene nucleus. Ar may represent a coupled aromatic compound, the coupling agent preferably being O, S, CH 2, a lower alkylene group having from 1 to about 6 carbon atoms, NH and the like, the group 1 being represented by R 1 and R 2, XH groups usually pendant from each of the aromatic nuclei. Examples of specific coupled aromatic compounds include diphenylamine, diphenylmethylene and the like. M is usually an integer from 1 to 3 and desirably represents the integer 1 or 2, with the integer 1 being preferred. N is usually an integer from 1 to 4 and desirably represents the integer 1.

preferably 1 to 2, with the integer 1 being preferred. X represents the oxygen and / or sulfur atom and the oxygen atom is preferred. Where m is 2, the two X may represent the oxygen atom, may represent the sulfur atom or one of them may represent the oxygen atom and the other may represent the sulfur atom. The symbol R represents a hydrocarbyl group preferably having up to about 28 250 carbon atoms, more preferably up to about 150 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, and more preferably to about 30 carbon atoms. R may represent an alkyl group having up to about 100 carbon atoms, more preferably 4 to 20 carbon atoms and more preferably 7 to 12 carbon atoms. R 2 may represent a mixture of alkyl groups, each of which alkyl groups have from 1 to about 70 carbon atoms and more preferably 1

between 4 and 20 carbon atoms. R may represent an alkenyl group having preferably between 2 and about 30 carbon atoms and more preferably between 8 and 20 carbon atoms. R 2 may represent a cycloalkyl group having from 4 to about 10 carbon atoms, an aromatic group having from about 6 to about 30 carbon atoms, an alkyl group substituted by aromatic radicals or an aromatic group substituted by alkyl radicals having from about 7 and 30 carbon atoms and preferably having from 7 to 12 carbon atoms. Preferably R is preferably an alkyl group having from 4 to 20 carbon atoms and preferably from 7 to 1229 carbon atoms. Examples of aromatic compounds of formula (Al) containing hydrocarbyl groups substituted by hydrocarbyl groups include the various naphthol derivatives and more preferably the various alkyl group substituted catechol, resorcinol and hydroquinone derivatives, the various xylenol derivatives, the various cresol derivatives, aminophenol and the like. Specific examples are heptyl phenol, octyl phenol, nonyl phenol, decyl phenol, dodecyl phenol, propylene-phenol tetramer, icosyl-phenol and the like. Preferred are the dodecyl phenol compounds, propylene-phenol tetramer and heptyl-phenol. Examples of aromatic compounds containing thiol groups substituted by suitable hydrocarbyl groups include heptyl thiophenol, octylthiophenol, nonylthiophenol, dodecylthiophenol, propylenethiophenol tetramer and the like. Examples of suitable thiol and hydroxyl group-containing aromatic compounds include the dodecyl-monothio-resorcinol compound. 3 4

In the general formula (A-2) R 1 and R 2 are independently hydrogen, hydrocarbyl groups preferably up to about 18 carbon atoms, more preferably up to about 6 carbon atoms and more preferably 1 or 2 carbon atoms. carbon. R3 and R4 may independently represent groups

phenyl or phenyl groups substituted by alkyl radicals preferably having up to about 18 carbon atoms and most preferably up to about 12 carbon atoms. Examples of suitable aldehydes and ketones of formula (A-2) include the compounds formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, benzaldehyde and the like, and the compounds acetone, methyl ethyl ketone, ethyl propyl ketone , butyl methyl ketone, glyoxal, glyoxylic acid, and the like. It is also possible to use precursors of such compounds which react as aldehydes under the reaction conditions of the present invention including the paraformaldehyde, formalin, trioxane and the like compounds. Formaldehyde and its polymers, for example, paraformaldehyde, are preferred. Mixtures of the various reactants of formula (A-2) may also be used. The third reagent used for the preparation of the aromatic Mannich compounds is an amine of formula (A-3) which contains at least one primary or secondary group. Thus the amine is characterized by the presence of at least one &gt; N-H group. The remaining valences of the above-indicated nitrogen atom are preferably met by hydrogen, amino, or organic groups attached to said nitrogen through direct carbon-nitrogen bridges. The amine of formula 31

(A-3) may be represented by the general formula (A-3-1)

R5 -N-H

Rc 5

In general formula (A-3-1) R represents a hydrocarbyl group or represents an amino-substituted hydrocarbyl group, hydroxy-substituted hydrocarbyl or alkoxy-substituted hydrocarbyl g. R 5 is a hydrogen atom or R 5. Thus, the compounds from which the group containing the nitrogen atom may optionally derive include primarily ammonia, aliphatic amines, aliphatic hydroxyl or thioamines, aromatic amines, heterocyclic amines or carboxylic amines . The amines in question may be primary or secondary amines and may also be polyamines such as alkylene amines, arylene amines, cyclic polyamines and derivatives of such polyamines substituted by hydroxy groups. Examples are methyl amine, N-methyl ethyl amine, N-methyl octyl amine, N-cyclohexyl aniline, dibutyl amine, cyclohexyl amine, aniline, di (p-methyl) amine, dodecylamine, acrylamine, o-phenylene diamine, N, N'-di-n-butyl-p-phenylene diamine, morpholine, piperazine, tetrahydro-pyrazine, indole, hexahydro -1,3,5-triazine, 1-H, 2,4-triazole, melamine, bis (p-aminophenyl) methane, phenyl methylene imine, methane diamine,

cyclohexamine, pyrrolidine, 3-amino-5,6-diphenyl-1,2,4-triazine, ethanolamine, diethanolamine, quinone dihydrin, 1,3-indane dihydrin, 2-octadecyl- imidazoline, 2-phenyl-4-methyl-imidazolidine, oxazolidine and 2-heptyl-oxazolidine. The reactant of formula (A-3) may be an amine containing hydroxyl radicals represented by the general formula R 9 R 7 NH- (R 8 N) n R 10 (A-3-2)

In the general formula (A-3-2) R, R and R are each independently hydrogen, hydrocarbyl, hydroxy-hydrocarbyl, amino-hydrocarbyl or hydroxy-amino-hydrocarbyl groups provided that at least one of the g R 2 represents a hydroxy-hydrocarbyl or

The hydroxy-amino-hydrocarbyl. R is preferably an alkylene group, more preferably an ethylene or propylene group, and still more preferably the ethylene group. Examples are compounds ethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, di- (3-hydroxy- 3-hydroxybutylamine, 4-hydroxybutylamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-1-propanol, 3-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-3-

-2-ethyl-1,3-propanediol, diethanolamine, di- (2-hydroxypropyl) amine, N- (hydroxypropyl) propylamine, N- (2-hydroxyethyl) -cyclohexyl amine, 3-hydroxy-cyclopentyl amine, N-hydroxyethyl-piperazine and the like. The amine of formula (A-3) may be a polyamine represented by the general formula H-N (alkylene-N) nH (A-3-3)

In the general formula (A-3-3) n is from 0 to about 10 and most preferably from 2 to 7. R 12 and R 12 are independently hydrogen or hydrocarbyl groups having up to about 30 carbon atoms. The &quot; alkylene &quot; preferably has up to about 10 carbon atoms, with methylene, ethylene and propylene groups being preferred. Examples of alkylene amines include the group of the methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, hexene amines, octylene amines, other polymethylene amines , and also the higher cyclic and homologous compounds of such amines such as the piperazine group and the piperazine and alkylpiperazine substituted amino groups. Specifically, the following compounds are mentioned: ethylene diamine, triethyleneethylene

tetramine, propylene diamine, decamethylene diamine, octamethylene diaryan, di (heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di (trimethylene) triamine, 2-heptyl-3 - (2-aminopropyl) imidazoline, 4-methylimidazoline, 1,3-bis (2-aminoethyl) imidazoline, pyrimidine, 1- (2-aminopropyl) piperazine, 1,4-bis (2-aminoethyl) piperazine and 2 methyl-1- (2-aminobutyl) piperazine. The higher homologues are obtained by condensation of the two or more previously mentioned alkylene amines and are also useful.

The hydroxyalkyl-substituted alkylene amines, i.e. the alkylene amines having one or more hydroxy-alkyl substituents on the nitrogen atoms are also usable as reactants of formula (A-3). The alkylene amines substituted by hydroxyalkyl radicals are preferably those in which the alkyl group is a lower alkyl group, i.e., has less than 6 carbon atoms. Examples of such amines are N- (2-hydroxyethyl) ethylene diamine, N, Ν'-bis (2-hydroxyethyl) ethylene diamine, 1- (2-hydroxyethyl) piperazine , mono-hydroxy-propyl (substituted diethylene) -triamine, 1,4-bis (2-hydroxypropyl) piperazine, dihydroxy-propyl- (substituted tetraethylene) -pentamine, N- (3- -propyl) tetramethylene diamine and 2-heptadecyl-1- (2-hydroxy-ethyl) -imidazoline. 35

are of the

Higher homologues such as those obtained by condensation of the alkylene amines or alkylene amines substituted by hydroxyalkyl radicals as depicted above via amino groups or via hydroxy groups are also useful as reagents of general formula (A-3 ). It will be appreciated that condensation through amino groups gives a higher amine together with removal of the ammonia and condensation through hydroxy groups gives products containing ether bridges together with the removal of water. The preparation of the aromatic Mannich compounds may be carried out according to a number of methods known in the art. One such method involves the addition of the aromatic compound of formula (A1) which contains hydroxyl and / or thiol radicals, aldehyde or ketone of general formula (A-2) or amine of formula (A-3) in a container and heating to carry out the reaction. It is possible to use reaction temperatures of from about room temperature to the decomposition temperature of any component or the Mannich compound. During the reaction the water is eventually removed by the forced action of a gas. Desirably the reaction is carried out in a solvent such as an aromatic type oil. The amount of the various reactants used is desirably based on one mole per mole of (A-1) and (A-2) for each group 36

(A-3) or two moles of (A-1) and (A-2) for each primary amino group (A-3) although larger or smaller amounts may be used.

According to another method for the preparation of aromatic Mannich compounds the aromatic compound of formula (A1) containing hydroxyl and / or thiol radicals and the amine derivative of formula (A-3) are introduced into the reaction vessel, . The aldehyde or ketone of formula (A-2) is generally added rapidly and the exothermic reaction is carried out which is generated by moderately heating to a reaction temperature of about 60 ° C to 90 ° C. Desirably, the addition temperature is inferred from the boiling point of the water otherwise bubbles would form in the water which would give rise to processing problems. After the reaction is substantially complete the by-product of the water is removed by any conventional process such as evaporation which can be achieved under vacuum by the forced action of a gas, by heating or by the like, the nitrogen as the removal agent at a temperature in the range of about 100 ° C to 120 ° C. It is also possible to work at lower temperatures. In one embodiment the reaction is carried out between the components (A-1), (A-2) and (A-3) at a temperature below about 120Â ° C. 37

According to a variant, the aromatic Mannich compound which is useful as component (i) is a product prepared from the reaction of an aldehyde, a ketone or an aromatic compound containing hydroxyl radicals and an amine, said amine containing at least a primary or secondary amino group and being characterized by the absence of hydroxyl and / or thiol groups.

In one embodiment the aromatic Mannich compound is different from a high temperature product being prepared from a phenol, an aldehyde and a polyamine at a temperature slightly above 130 ° C.

In one embodiment, component (i) is an aromatic Mannich compound represented by the general formula

XR ° (R Ar) R Ar, R N-, R N-, R N-, R 1, R 1, R 1,

In the general formula (III) Ar and Ar represent aromatic groups, preferably benzene nuclei or naphthalene nuclei and more preferably represent 1 2 4 6 8 9

nuclei of benzene. R, R, R, R, R, and R are independently hydrogen or aliphatic hydrocarbyl groups preferably having up to about 250 carbon atoms, more preferably up to about 38

200 carbon atoms, more preferably up to about 150 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, and most preferably up to about 30 carbon atoms. R 4 may represent an aliphatic hydrocarbyl group substituted by hydroxy radicals. R 3, R 4 and R 5 independently represent hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups and more preferably alkylene groups preferably having up to about 40 carbon atoms, more preferably up to about 30 carbon atoms, more preferably to about 20 carbon atoms, more preferably to about 10 carbon atoms, more preferably to about 6 carbon atoms, and most preferably to about 4 carbon atoms. X represents the oxygen or sulfur atom and preferably represents the oxygen atom.  € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ i is preferably from 0 to about 10 and more preferably from 0 to about 6. According to a variant, i represents the integer 5 or a number greater preferably of 5 to about 10 , In the case where Ar and Ar are benzene cores, the groups XR and XR are the OH radical and R is the ethylene group. 39

In one embodiment, component (i) is an aromatic Mannich compound represented by the general formula

OH

OH

(TV) 1 3

In general formula (IV) R and R are independently hydrogen or aliphatic hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms , more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms. The symbol R represents a hydrocarbyl group or a hydrocarbyl group substituted by hydroxy radicals preferably having up to about 40 carbon atoms, more preferably up to about 30 carbon atoms, more preferably up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, and most preferably up to about 4 carbon atoms. In a variant R1 and R2 are in the para position relative to the OH groups and individually represent alkyl groups having from about 6 to 18 carbon atoms or more

preferably between 10 and 14 carbon atoms, and most preferably about 12 carbon atoms, and R is ethanol or butyl.

According to a variant of component (i) is an aromatic Mannich compound represented by the general formula OR 11 OR 10 (o) -R 2 -NR 6 -NR 8 - (O) ® 1 3 5 7 9 10

In the general formula (V) R 1, R 2, R 3, R 4, R 5 and R 11 are independently hydrogen or aliphatic hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms. carbon, more preferably up to about 50 carbon atoms and most preferably, to about 30 carbon atoms. R, R, R and

R² are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups and more preferably alkylene groups having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms and more 41

preferably up to about 4 carbon atoms. According to a variant of either or both R and R are alkylene groups having approximately 3 to 20 carbon atoms and preferably any of them represents the propylene group. According to a variant the 2 8 4

R and R are methylene; R 65 and R represent the propylene group; R 3 is methyl; R, R, R and R are hydrogen; and R 1 and R 2 independently represent aliphatic hydrocarbyl groups, preferably alkyl groups having up to about 30 carbon atoms, preferably between 2 and 18 carbon atoms, and more preferably between 4 and 12 carbon atoms, more preferably between 6 and 8 carbon atoms, and most preferably about 7 carbon atoms.

In one embodiment, component (i) is an aromatic Mannich compound represented by the general formula

42

In general formula (VI) R1 and R2 are independently hydrogen or aliphatic hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, and most preferably 34 to about 30 carbon atoms. R 1, R 2, R 3 and R 4 are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups and more preferably alkylene groups having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, and most preferably up to about 4 carbon atoms. According to one of the variants R 1, R 2, R 3 and R 4 are methylene; R 2 represents the ethylene group or the propylene group, preferably represents the ethylene group; R, R, R and R are hydrogen; and R 1, R 2, R 3 and R 4 are independently aliphatic hydrocarbyl groups, preferably alkyl groups having up to about 30 carbon atoms, preferably from 2 to 18 carbon atoms, and most preferably from 4 to 12 carbon atoms , more preferably from 6 to 8 carbon atoms, and more preferably from

about 7 carbon atoms.

In one embodiment, component (i) is an aromatic Mannich compound represented by the general formula OR1 I-O & OO OJ &quot; R 3 -N (R 5 N) f R 7 Tâ (VII) Y or R 2 R 4 R 6 '

In general formula (VII) R 1, R 2, R 4, R 6, R 8 and R 9 are independently hydrogen or aliphatic hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, plus preferably up to about 50 carbon atoms and more preferably - 357

to about 30 carbon atoms. R, R and R are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups and more preferably alkylene groups having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, and most preferably up to about 4 carbon atoms.  € ƒâ € ƒâ € ƒâ € ƒâ € ƒI is a number from 0 to about 10, more preferably 1 to 6, more preferably 2 to 6,

3 approximately. In one embodiment R5 and R5 represent the methylene group; R 2 represents the ethylene or propylene group and preferably the ethylene group; R 24 is hydrogen or the methyl group; R, R and R are hydrogen; R and R are aliphatic hydrocarbyl groups, preferably alkyl groups having from about 2 to about 30 carbon atoms, more preferably from 6 to about 12 carbon atoms; and â € ƒâ € ƒâ € ƒis 1 to about 6. According to a variant 29 the symbols R and R are the heptyl group and i represents the integer 4. In a variant R and R represents the propylene tetramer and i represents the integer 1. In a variant, the symbol i represents the integer 5 or a higher number, preferably from 5 to about 10 in the case of the symbols R and R represent the hydrogen atom and R represents the ethylene group.

According to a variant, component (i) is an aromatic Mannich compound represented by the general formula (VIII): wherein R 1, R 2, R 3, R 4,

In the general formula (VIII), R 1, R 2, R 3, R 4, R 5 and R 6 independently represent a hydrogen atom or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably to about 50 carbon atoms and most preferably to about 30 78 carbon atoms. R and R are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups and more preferably alkylene groups having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms more preferably up to about 3 carbon atoms, and most preferably up to about 2 carbon atoms. In one embodiment, R1 is an alkyl group preferably having from 3 to 12 carbon atoms, more preferably from 6 to 8 carbon atoms, and most preferably about 7 carbon atoms; R, R and R are hydrogen; R 1 and R 2 are methyl; and R7 and R7 individually represent the ethylene group.

In one embodiment, component (i) is an aromatic Mannich compound represented by the general formula

(IX) independently represent a hydrocarbyl hydrogen atom having preferably up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, and more preferably to about 30 carbon atoms. R 1, R 2, R 3 and R 4 are independently alkylene or alkylidene groups having from 1 to about 10 carbon atoms, more preferably from 1 to about 4 carbon atoms and more preferably from 1 to about 2 carbon atoms. carbon atoms. The symbols i and j independently stand for numbers ranging from 1 to about 6, more preferably from 1 to about 4, and most preferably about 2. In a variant, R is an alkyl group having from 4 to 12 carbon atoms, more preferably from 6 to 8 carbon atoms, and most preferably about 7 carbon atoms; R 2 is hydrogen; the 3 6 4

R 2 and R 2 are methylene; the symbols R 47-5 tf. and R 2 represent the ethylene group and i and j individually represent the integer 2.

In one embodiment, component (i) is an aromatic Mannich compound represented by the general formula

(X)

In the general formula (X) Ar represents an aromatic group, preferably a benzene nucleus or a naphthalene nucleus and more preferably a benzene nucleus. 1 3

R 1 and R 2 are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups, more preferably alkylene groups preferably having up to about 20 carbon atoms, more preferably up to about 12 carbon atoms, and most preferably up to about 6 carbon atoms. carbon. R 2 is hydrogen or a lower hydrocarbyl group (preferably a 45 alkyl group). R and R are independently hydrogen, aliphatic hydrocarbyl groups, aliphatic hydrocarbyl groups substituted by hydroxy radicals, aliphatic hydrocarbyl groups substituted by amine radicals or aliphatic hydrocarbyl groups substituted by alkoxy radicals. R 1 and R 2 are

independently, preferably contain up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, more preferably up to about 20 carbon atoms. carbon, and most preferably up to about 6.. carbon atoms. R 2 is hydrogen or an aliphatic hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms and more preferably between 6 and 30 carbon atoms. In one embodiment the compound represented by the general formula (X) has the following structure: (X-1) ???????? R 6 ???????? R?

In general formula (X-1) R 1, R 2, R 3 and R 4 have the same meanings as defined in general formula (X). According to a variant, component (i) has structure 3

represented by the general formula (X-1) in which R191 is the propylene group, R3 is the atom

R 5 is an alkyl or alkenyl group containing from about 16 to 18 carbon atoms and R 2 is heptyl. According to a variant, component (i) has the structure indicated in formula (X-1) wherein R is propylene, R4 and R4 are methyl and R3 is heptyl. According to a variant, component (i) has the structure indicated in formula (XI) wherein R is methylene, R is propylene, R4 and R4 are and R represents an alkyl or alkenyl group having from about 12 to 24 carbon atoms, more preferably from 16 to 20 carbon atoms and more preferably about 18 carbon atoms.

According to a variant, component (i) is an aromatic Mannich compound represented by the general formula (XI)

In the general formula (XI) Ar represents an aromatic group, preferably a benzene nucleus or a naphthalene nucleus and more preferably a benzene nucleus. R 2 is hydrogen atom or an aliphatic hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, and most preferably to about 30 2 3 4 carbon atoms. R, R and R are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups and more preferably alkylene groups having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, and most preferably up to about 4 carbon atoms. In one embodiment, Ar 2 represents a benzene nucleus; R 2 is methylene, R 2 and R 2 are independently ethylene or propylene groups and preferably ethylene group; and R is an aliphatic hydrocarbyl group, preferably an alkyl group preferably having up to about 30 carbon atoms, more preferably between 6 and 18 carbon atoms, more preferably between 10 and 14 carbon atoms, and most preferably about of 12 carbon atoms and advantageously R represents the propylene tetramer. (2) Hydroxyaromatic Qximes According to a variant, component (i)

represents a hydroxy aromatic oxime. These oximes encompass the compounds represented by the general formula OH NOH or L II. R-Ar-C-R1 (ΧΠ) R2

In the general formula (XII) Ar is an aromatic group which is preferably a benzene nucleus or a naphthalene nucleus and more preferably a benzene nucleus. R, R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, and most preferably up to about 50 carbon atoms. R 2 may represent a group 2 containing up to about 20 carbon atoms. R3 and R5 independently represent groups containing from 6 to 30 carbon atoms. R 2 and R 2 independently represent the groups CH 2 N (R) 2 or 4, wherein R 2 is hydrogen or an aliphatic hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about of 100 carbon atoms, more preferably up to about 50 carbon atoms and more 52

preferably from 6 to 30 carbon atoms. According to a variant the compound represented by the general formula (XII) represents a kethoxime having the structural formula

12 3

In general formula (XII-1) R 1, R 2 and R 2 have the same meanings as defined in general formula (XII). According to a variant, component (i) is a compound 1

represented by the general formula (XII-1) wherein R 2 is methyl, R 3 is propylene tetramer and R 2 is hydrogen.

In one embodiment, component (i) is a hydroxy aromatic oxime represented by the general formula

1 2

In the general formula (XIII) R and R are independently hydrogen or

hydrocarbyl moiety having preferably up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms and more preferably between 6 and 30 carbon atoms. R 3 and R 23 are independently CH 2 N (R 2) or COOR 3 wherein R 2 is hydrogen atom or aliphatic hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms and more preferably between 6 and 30 carbon atoms. The symbol i represents a number from 0 to 4 and preferably from 0 to 2 and more preferably represents the integer 1. j is a number from 0 to 5, preferably from 0 to 2 and more preferably represents whole 1.

Examples of useful hydroxyaromatic oximes include dodecyl-salicylaldexime, 4,6-di-tert-butyl-salicylaldehyde, raethyl dodecyl-salicyl-kethoxime, 2-hydroxy-3-methyl-5 5-nonyl-benzophenone oxime, 5-heptyl-salicylaldexime, 5-nonyl-salicylaldoxine, 2-hydroxy-3,5-dinonyl-benzophenone oxime, 2-hydroxy-5-nonyl-benzophenone oxime and polyisobutenyl-salicylaldehyde. (3) Schiff Bases

In one embodiment, component (i) is a

base of Schiff which is a compound having at least one group represented by the general formula &gt; C = NR. These compounds are well known in the art and are typically prepared by a condensation reaction of an aldehyde or a ketone with a primary amine. The Schiff base-type compounds which are useful as component (i) encompass the compounds represented by the general formula:

In general formula (XIV) Ar represents an aromatic group which is preferably a benzene nucleus or a naphthalene nucleus and more preferably is a benzene nucleus. R, R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, and most preferably up to about of 30 carbon atoms. R 2 is

has up to about 20 carbon atoms. R 2 is a group which may have from about 6 to about 30 carbon atoms. R 5 is a group of the general formula 55

-R 4 -N = C-Ar 1 -R 1 2 (XV) 4

In general formula (XV) R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group and more preferably an alkylene group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, more preferably about 2 to 6 carbon atoms, and most preferably about 2 to 4 carbon atoms. R 2 and R 3 independently represent hydrogen, hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about about 30 carbon atoms. R represents a group which may contain up to about 20 carbon atoms. R2 may represent a group containing approximately 6 to 30 carbon atoms. Ar is an aromatic group, preferably a benzene nucleus or a naphthalene nucleus and more preferably represents a benzene nucleus. According to a variant the compound represented by the general formula (XIV) has the following structural formula

NR2 11 i C-R1 (XIV-1) 12 3

In general formula (XIV-1) R 1, R 2 and R 2 are as defined in general formula (IX). R 2 may also be a group of formula

4 5 6

In general formula (XV-1) R, R and R have the same meanings as defined in general formula (XV).

In one embodiment, the Schiff bases which are useful as component (i) are represented by the general formula R1 -Ar-CH = N-R2-N = CH-Ar1 -R3 (XVI)

In the general formula (XVI) Ar and Ar independently represent aromatic groups, preferably benzene or naphthalene nuclei and most preferably the benzene nucleus. R and R are independently hydrogen or hydrocarbyl groups containing

preferably up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, ratios preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms. R 2 represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms and more preferably up to about 3 carbon atoms. In one embodiment, Ar and Ar are 1-3 benzene nuclei; R 2 and R 2 are hydrogen atom 2; and R is ethylene or propylene, and preferably ethylene.

According to a variant, component (i) is a hydroxy-aromatic Schiff base represented by the general formula

OH (ΧΥΠ) R1a-N3 CH-Ar1

In the general formula (XVII) are Ar and Ar independently aromatic groups of 58

preferably benzene or naphthalene nuclei and more preferably benzene nuclei. R represents a hydrocarbyl group preferably having up to about 200 carbon atoms, and most preferably up to about 100 carbon atoms. According to a variant the compound represented by the general formula (XVII) has the structural formula:

(XVII-1) 1

In general formula (XVII-1) R is as defined in formula (XVII). According to a variant, component (i) has the structure 1 represented by the general formula (XVII-1) and R represents an alkyl or alkenyl group, preferably a polybutenyl or polyisobutenyl group having a mean molecular weight comprised preferably between 600 and 1200, more preferably between 800 and 1100, more preferably between 900 and 1000 and more preferably between 940 and 950.

In one embodiment, component (i) is a hydroxy-aromatic Schiff base containing nitro groups represented by the general formula:

(XVΙΠ)

HO-Ar-CH = Ν-Αγ1-Ν02 ι / L R2 R1 1

In general formula (XVIII) Ar and Ar independently represent aromatic groups which are preferably benzene nuclei or naphthalene nuclei and most preferably are benzene nuclei. R 1 and R 2 are independently hydrogen or hydrocarbyl groups preferably containing up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about of 30 carbon atoms and more preferably up to about 20 carbon atoms. According to a variant the compound represented by the general formula (XVIII) is a compound having the structural formula:

(R) -cyclohexanecarboxylic acid (2-hydroxyethyl)

In general formula (XVIII-1) R 1 and R 2 have the same meanings as defined for the general formula (XVIII). Examples include the compounds salicylal- (3-nitro-4-sec-butyl) aniline, salicylal- (3-nitro-4-octyl) aniline,

salicylal- (p-t-amyl) aniline, salicylaldehyde n-dodecylamine and N, N'-disalicylidene-1,2-diaminopropane.

According to a variant, component (i) is an aromatic Schiff base containing nitro groups represented by the general formula: (XIX)

R 1

In general formula (XIX) Ar and Ar independently represent aromatic groups, preferably benzene or naphthalene nuclei, and more preferably benzene nuclei. R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms. R 2 represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group and more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms and 61

more preferably up to about 3 carbon atoms. 2

Advantageously R is methylene, ethylene or propylene. According to a variant the compound represented by the general formula (XIX) has the following structural formula: R1 NO,

N = CHR 2 CH = Ni NO, (XIX-1)

RJ 12 3

In general formula (XIX-1) R 1, R 2 and R 2 have the same meanings as defined for the general formula (XVIII). Examples are the malonal-di- (3-nitro-4-t-butyl) aniline, malonal-di- (en-amyl) -aniline and 4-methyl-imino-2-butanone compounds, the latter derivative of formyl-acetone and methylamine.

According to a variant, component (i) is a hydroxy-aromatic Schiff base represented by the general formula:

(XX)

In the general formula (XX) R is 62

hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, more preferably carbon atoms 10 carbon atoms, more preferably to about 6 carbon atoms and most preferably to about 3 carbon atoms. R, R, R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms.

According to a variant, component (i) represents a Schiff base containing carbonyl groups represented by the general formula:

(XXI)

In general formula (XXI) R 1, R 2, R 3, R 4, R 5, R 5, R 7

O and R are independently hydrogen or

hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably to about 20 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, and most preferably up to about 3 carbon atoms.

According to a variant, component (i) is a hydroxy-aromatic Schiff base represented by the general formula

In general formula (XXII) the symbols RJ

R

R 64

represent independently hydrogen atom or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about of 20 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, more preferably up to about 12 carbon atoms more preferably up to about 6 carbon atoms, and most preferably about 2 to 6 carbon atoms. The symbol i represents a number from 1 to about 1000 or from 1 to about 800 or from 1 to about 600 or from 1 to about 400 or from 1 to about 200 or from 1 to about 100 or from 1 and about 50 or between 1 and about 20 or between 1 and about 10 or between 1 and about 6 or between 1 and about 4 or between 2 and about 4.

According to a variant, component (i) is a Schiff base containing carbonyl groups represented by the general formula R1 -N = CH-COOR2 (XXIII)

1 2

In general formula (XXIII) R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms and more preferably up to about 30 carbon atoms. The total number of carbon atoms in the groups represented by R 1 and R 2 must be sufficient to cause the resulting organometallic complex formed with this component to be soluble or stably dispersible in the diesel fuel. Preferably the total number of carbon atoms in the groups 12 represented by the symbols R and R and of at least about 6 carbon atoms and more preferably is at least about 10 carbon atoms. R may be an alkyl or alkenyl group having from about 10 to 20 carbon atoms and preferably from 12 to 18 carbon atoms.

carbon atoms. In one embodiment R 2 is a mixture of alkyl or alkenyl groups containing from about 12 to 18 carbon atoms and R 2 is hydrogen.

According to a variant, component (i) is a Schiff base containing oxime groups, represented by the general formula R1-N = CHCH = N-OH (XXIV)

1

In general formula (XXIV) R represents a hydrocarbyl group preferably having from 6 to 200 carbon atoms, more preferably 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and more preferably from 6 to 100 carbon atoms, more preferably from 6 to 100 carbon atoms, more preferably from 6 to 100 carbon atoms, 30 carbon atoms. R may represent an alkyl or alkenyl group having from about 10 to 20 carbon atoms and preferably from 12 to 18 carbon atoms. In one embodiment R is a mixture of alkyl or alkenyl groups having from about 12 to 18 carbon atoms.

According to a variant, component (i) is a hydroxy-aromatic Schiff base, represented by the general formula

(R 5) rC-N-N = C-R 4 R 1 R 2 R 2 R 2 R 2

R '

In general formula (XXV), R1, R2, R3, R4, R4 and R4 are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms more preferably up to about 50 carbon atoms, more preferably up to about 30

L carbon atoms and most preferably up to about 20 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, more preferably up to about 10 carbon atoms more preferably up to about 6 carbon atoms, and most preferably up to about 3 carbon atoms. The symbol i represents the integer 0 or 1.

According to a variant, component (i) is a hydroxy-aromatic Schiff base represented by the general formula: wherein R 1, R 2, R 3, R 4,

In the general formula (XXVI) Ar represents an aromatic group, preferably a benzene nucleus or a nucleus

of the naphthalene and most preferably a benzene nucleus. R 2 represents the hydrogen atom or a hydrocarbyl group, preferably an alkyl group having up to about 10 carbon atoms and more preferably up to about 6 carbon atoms, preferably a methyl, ethyl or propyl group and more preferably a methyl group. The symbol R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group and more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 12 carbon atoms, more preferably to about 6 carbon atoms, and most preferably up to about 3 carbon atoms. The R 3 and R 4 are independently hydrogen, aliphatic hydrocarbyl groups, aliphatic hydrocarbyl groups substituted by hydroxy radicals, aliphatic hydrocarbyl groups substituted by amine radicals or aliphatic hydrocarbyl groups substituted by alkoxy radicals. R 1 and R 2 are independently selected from the group consisting of halogen atoms, halogen atoms, halogen atoms, halogen atoms, halogen atoms, halogen atoms, halogen atoms, halogen atoms, more preferably up to about 20 carbon atoms, and most preferably up to about 6 carbon atoms. R 2 is hydrogen or an aliphatic hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, and most preferably up to about 30 carbon atoms, carbon atoms. 69

The compound represented by the general formula (XXVI) has the following structural formula: R3 (XXVI-1) (o)

In general formula (XXVI) R1, R2, R3, R4 and R5 have the same meanings as defined for the general formula (XXVI). According to a variant, component (i) has the structure represented by the general formula (XXVI-1) wherein the symbol R is hydrogen or methyl, R is propylene,

R 2 is hydrogen, R 2 is alkyl or alkenyl having 5 to 5 carbon atoms;

about 8 to 24 carbon atoms and R is hydrogen.

Examples of useful Schiff bases are the 1 dodecyl-β, β-disalicylidene-1,2-propane diamine compounds; 11 dodecyl-Î ±, β-disyllicylidene-1,2-ethane diamine; N, N -dissalicylidene-1,2-propane diamine; N-salicylidene aniline; 1 N, N -dissalicylidene-ethylene diamine; salicylal-beta-N-aminoethylpiperazine; and N-salicylidene-N-dodecylaraine. (4) Calixarenos

According to a variant the component (i) is a calixarene. Typically these compounds have a geometry 70

ί &lt; similar to that of a basket or a cone or a geometry partially similar to that of a basket or a cone and have been described by C. David Gutsche in Calixarenes &quot; Royal Society of Chemistry, 1989. According to a variant component (i) is a calixyl] arene compound which may be represented by structural formula

In general formula (XXVII) R 1, R 2, R 2 and R 2 (XXVII) independently represent hydrogen atom or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 atoms more preferably up to about 50 carbon atoms, more preferably between 6 and 30 carbon atoms, and more preferably between 6 and 18 carbon atoms. According to a variant 124, R 1, R 2, R 3 and R 4 are each individually alkyl groups having from about 10 to 14 carbon atoms and more preferably about 12 carbon atoms, and more preferably each represents

propylene tetramer.

In one embodiment, component (i) is a calix [5] arene compound which may be represented by formula

(XXVIII) independently represent the hydrogen atom or hydrocarbyl groups preferably having up to about 200 carbon atoms, preferably up to about 100 carbon atoms, more preferably 50 carbon atoms, more preferably between 6 and 30 carbon atoms, and more preferably between 6 and 18 carbon atoms. In one embodiment each of R 1, R 2, R 3, R 4 and R 5 represents an alkyl group having from about 10 to 14 carbon atoms and more preferably about 12 carbon atoms, and more preferably represents the propylene tetramer.

In one embodiment, component (i) is a 72

compound calix [6] arene which may be represented by the general formula

R (XXIX)

In general formula (XXIX) R1, R2, R3, R4, R5 and R6 are independently hydrogen, hydrocarbyl groups having up to about 200 carbon atoms, preferably up to about 100 carbon atoms, more preferably up to about of carbon atoms, more preferably between 6 and 30 carbon atoms, and most preferably between 6 and 18 carbon atoms. According to a variant each of R 1, R 2, R 3, R 4, R 5 and R 8 represents an alkyl group having from about 10 to 14 carbon atoms and more preferably about 12 carbon atoms and more preferably represents the propylene tetramer. 73

(5) β-Substituted phenols According to a variant the β-substituted phenol component represented by any of

CH3-NHR1 (i) is a (XXX-1) (XXX-2) (XXX-3)

OH

In the general formula (XXX-1), (XXX-2) and (XXX-3) each R1 is hydrogen, hydrocarbyl, preferably about 200, more preferably up to about 100 atoms more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms. The derivatives of the above-mentioned compounds in which one or more of the ring carbon atoms are substituted with hydrocarbyl groups, preferably with lower alkyl groups, are useful. In one embodiment, R1 is an alkyl group having about 74

preferably between 10 and 14 carbon atoms and preferably having about 12 carbon atoms. R may also be represented by the general formula wherein R 1 and R 2 are independently hydrogen, hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group and more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, and most preferably to about 6 carbon atoms. In accordance with a variant R is alkyl having from 10 to 20 carbon atoms and preferably from 12 to 18 carbon atoms; or 4 3

R is methylene; and R is hydrogen. (6) G-substituted phenols

According to a variant, component (i) is an unsubstituted phenol represented by structural formula 75

1

In the general formula (XXXI), T is a NR, SR or NO2 group wherein R is hydrogen atom or a hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms. The derivatives of the above-mentioned compounds in which one or more of the ring carbon atoms are substituted with hydrocarbyl groups, preferably with lower alkyl groups, are useful. (7) Carboxylic Acid Esters According to a variant the component (i) is an ester of a carboxylic acid. These compounds are characterized by the presence of at least one carboxylic acid ester group -C00R and at least one additional functional group, each group being different from a hydrocarbon bridge. The other functional group may be a carboxylic acid ester group.

According to a variant, component (i) is an ester of a carboxylic acid represented by the general formula R 1 -CH-CO (OR 3) 4 OR 4 (XXXII) CH 2 -CONOR 76, 51 -

In general formula (XXXII) R 1, R 2 and R 2 are independently hydrogen, hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms of carbon and most preferably between 6 and 30 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms and more preferably from 2 to 4 carbon atoms. I is 1 to 10, more preferably 1 to 6, more preferably 1 to 4, and more preferably 1 or 2. represents an alkyl group having approximately 6 to 20 carbon atoms, more preferably 10 to 14 carbon atoms and more preferably about 12 carbon atoms; R 1 and R 2 are hydrogen; R 2 represents an ethylene or propylene group and preferably the ethylene group; and i is from 1 to about 4 and from 77

preferably about 2.

According to a variant, component (i) is an ester of a carboxylic acid represented by the general formula (XXXIII)

In general formula (XXXIII) R 1 is hydrogen or a hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms and more preferably from about 6 to about 30 carbon atoms. R2 and R3 are independently hydrogen, hydrocarbyl groups preferably having up to about 40 carbon atoms, and most preferably up to about 20 carbon atoms. R 4 represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms. more preferably up to about 4 carbon atoms, more preferably up to about 2 carbon atoms, more preferably up to about 4 carbon atoms, more preferably up to about 2 carbon atoms.

Carbon. In a variant R and R are alkyl groups having from about 6 to 18 carbon atoms and more preferably about 12 carbon atoms,

Preferably the dodecyl group is represented by the symbol 23

R is preferably the dodecyl group; R4 is hydrogen; and R is methyl ethylene. (8) Acylated amines

In one embodiment the component (i) is an acylated amine. These compounds are characterized by the presence of at least one RCO- acyl group and at least one amino group -NR2 at different carbon atoms of the hydrocarbon bridge. These acylated amines may also contain other functional groups of the type discussed above.

In one embodiment the component (i) is a carbonyl amine represented by the formula OR 4

(XXXIV)

In the general formula (XXXIV) the symbols R1, R2, and R4 are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms.

carbon, more preferably up to about 50 carbon atoms, and most preferably up to about 30 carbon atoms. R 2 is a group containing from 6 to 30 carbon atoms, more preferably from 6 to 18 carbon atoms and more preferably from 10 to 14 carbon atoms. R and R are preferably hydrogen or lower alkyl. According to a variant R represents an alkyl group having from about 10 to 14 carbon atoms and preferably about 12 carbon atoms; and R1, R2 and R3 are hydrogen.

According to a variant the component (i) is an acylated amine represented by the general formula B-CH (C) -O-NH (R) -NH-R 2 NR 3 R 4 (XXXV)

In general formula (XXXV) R1, R2, R3 and R4 are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, plus preferably up to about 50 carbon atoms, and most preferably up to about 30 carbon atoms. R 2 represents a hydrocarbylene group or

hydrocarbylidene, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms and more preferably between 2 and about 4 carbon atoms. R is preferably a hydrocarbyl group, more preferably an alkyl group having from about 6 to 20 carbon atoms, more preferably from 10 to 14 carbon atoms and more preferably about 12 carbon atoms. In one embodiment R 2 represents an alkyl group having from about 10 to 14 carbon atoms and preferably 2 to 12 carbon atoms, R 2 is ethylene or propylene group and preferably ethylene group and R, R and R are hydrogen.

According to a variant, component (i) is an acylated araine represented by the general formula

O O

r4o-c-ch2 II 0 81 (XXXVI)

In the general formula (XXXVI) R1, R2, R3 and R1 are independently hydrogen, hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms and more preferably up to about 30 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 and more preferably from 2 to 4 carbon atoms. R and R are preferably hydrocarbyl groups and more preferably alkyl groups having from about 6 to 20 carbon atoms, more preferably from 10 to 14 carbon atoms, and most preferably about 12 carbon atoms. In a variant R 2 and R 2 are alkyl groups having from 10 to about 14 carbon atoms and preferably about 12 carbon atoms, R 2 is ethylene or 3-propylene group and preferably the group ethylene and R and 82 are the hydrogen atom.

According to a variant, component (i) is an acylated amine represented by the general formula (XXXVII) R 2 -NR 7 -NR 7 -N

In general formula (XXXVII) R1, R2, R3, R4, R3 and R3 are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms and more preferably between 6 and 30 carbon atoms approximately. Re R 2 are independently hydrocarbylene or hydrocarbylidene groups, preferably alkylene or alkylidene groups, more preferably alkylene groups preferably having up to about 20 carbon atoms, more preferably up to about 6 carbon atoms and more preferably 2 to 4 atoms approximately. In one embodiment, R 1 and R 2 are independently alkyl or alkenyl groups having from about 6 to 30 carbon atoms, more preferably from 12 to 24

carbon atoms, and more preferably 2 3 4 5

about 18 carbon atoms; R, R, R and R 'are hydrogen; and R 1 and R 2 are independently alkylene groups having from 1 to about 4 carbon atoms, preferably the ethylene or propylene group and more preferably the propylene group. (9) Hydroxyazylenes

In one embodiment the component (i) is a hydroxiazylene compound. These compounds are characterized by the presence of at least one hydroxiazylene group &gt; NOH and at least one other functional group of the type discussed above. The other functional group may also be a hydroxiazylene group.

According to a variant, component (i) is a hydroxiazylene compound represented by the general formula

R1 R2 O

R6 R5 R4 (XXXVIII)

In the general formula (XXXVIII) R1, R2, R3, R4, R5 and g are independently hydrogen or

hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms of carbon.

According to a variant the component (i) is a hydroxiazylene compound represented by the general formula R 1, HON-N-C = N-NR 1 (XXXIX) 1 2

In general formula (XXXIX) R 1 and R 2 independently represent hydrogen atom or hydrocarbyl groups preferably having up to about 40 carbon atoms, more preferably between 6 and 30 carbon atoms, and more preferably between 12 and 20 carbon atoms. carbon dioxide. 0 total number of 1

carbon atoms in the groups represented by R 851 and R should be sufficient to cause the resulting organometallic complex formed with this component to be soluble or stably dispersible in the diesel fuel. Preferably the total number of 12 carbon atoms in the groups R and R is at least about 6 carbon atoms and more preferably is at least about 10 carbon atoms.

(10) Benzotriazoles

In one embodiment, the component (i) is a benzotriazole compound which may optionally be substituted or unsubstituted. Suitable examples are benzotriazole, benzotriazole substituted by alkyl groups (for example, tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.) / benzotriazole substituted by aryl groups (for example, phenyl benzotriazole, etc.), benzotriazole substituted by alkaryl- or arylalk- groups and further substituted benzotriazoles in which the substituents may for example be hydroxy, alkoxy, nitro, carboxy or carbaloxy groups or halogen atoms, especially chloro.

In one embodiment, component (i) is a benzotriazole compound represented by the general formula

1 2

In general formula (XL) R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms.

Preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms. In a variant R is an alkyl group having from 6 to 18 carbon atoms, more preferably from 10 to 14 carbon atoms and more preferably 2 to 12 carbon atoms and R is hydrogen. An example of a useful compound is the dodecyl benzotriazole compound. (11) Amino acids

In one embodiment, the component (i) is an amino acid represented by the general formula

R 3 R 4 R 1 R 2 NCH- (CH) zCOOH (XLI) 1

In the general formula (XLI) R 2 is hydrogen or a hydrocarbyl group; R 2 have the same meaning as R 2 or R 3 is acyl; R 1 and R 2 are independently and independently hydrogen, lower alkyl; and z is 0 or 1. The hydrocarbyl groups represented by R 1 and R 2 may optionally be any of the hydrocarbyl groups 87

1 2

previously defined. Preferably R 1 and R 2 are independently alkyl, cycloalkyl, phenyl, phenyl substituted by alkyl, benzyl or benzyl groups substituted by alkyl groups. According to a variant R and R are individually and independently alkyl groups having from 1 to about 18 carbon atoms; cyclohexyl groups; phenyl; phenyl having alkyl substituents containing from 1 to about 12 carbon atoms at the 4-position of the phenyl ring; benzyl groups; or benzyl groups having an alkyl group containing from 1 to about 12 carbon atoms at the 4-position of the phenyl ring. Generally R 2 in general formula (XLI) represents a lower alkyl group such as the methyl group and R represents an alkyl group having from about 4 to 18 carbon atoms. 1

In one embodiment R is as defined above and R is acyl. Although a wide variety of acyl groups represented by the symbol 2 R may optionally be used, such acyl groups may be generically represented by the general formula R 5 C (O) - 5 wherein R is an aliphatic group containing up to about 30 atoms carbon. More generally, R5 represents a group containing approximately 12 to 24 carbon atoms. Such acyl radicals substituted aminocarboxylic acids are obtained by reacting an aminocarboxylic acid with a carboxylic acid or with a carboxylic halide. For example, a fatty acid can be reacted with an aminocarboxylic acid to provide the desired acyl radical substituted aminocarboxylic acid. It is possible to react acids such as dodecanoic acid, oleic acid, stearic acid, linoleic acid etc. with aminocarboxylic acids 2

represented by the general formula (XLI) wherein R is hydrogen. 3 4

R 1 and R 2 of the general formula (XLI) are independently and independently hydrogen or lower alkyl. Generally, the symbols R3 and R4 are independently hydrogen or methyl groups and more often R4 and R4 represent hydrogen.

In general formula (XLI) z may possibly be 0 or 1. Where z is 0, the amino acid compound is glycine, alpha-alanine and glycine and alpha-alanine derivatives. Where z is 1, the aminocarboxylic acid represented by the general formula (XLI) is beta-alanine or beta-alanine derivatives. 89

Amino acid compounds of general formula (XLI) which are useful as component (i) may be prepared by methods described in the prior art and some such amino acids are commercially available. By way of example, the amino acids glycine, alpha-alanine, beta-alanine, valine, arginine and 2-methyl-alanine are mentioned. The preparation of the amino acid compounds represented by the general formula (XLI) in which z represents the integer 1 is described, for example, in U.S. Pat. For example, it is possible to prepare the amino acids by reacting an amine of Formula 1

RRNH 90

dimethyl amine, dodecyl amine, octadecyl amine, N-n-octylamine, aminopentane, sec-butylamine, propylamine, etc.

The amino acid compounds of formula (XLI) wherein R is methyl or acyl may be prepared by reacting a primary amine of the formula R 1 NH 2 wherein R is as defined for formula (XLI) with a compound of the general formula R 3 CH = C (R 4) -COOR 6 3 6 wherein R 1, R 2 and R 3 are as defined above. This intermediate is then converted to the methyl derivative by N-methylation and ester hydrolysis followed by acidification. The corresponding acyl derivative is formed by reacting the intermediate with an acid or an acid halide such as stearic acid, oleic acid, etc. Specific amino acids of the type represented by the general formula (XLI) are shown in Table Next. 91

TABLE I

R 1 -CH 2 CH 3 CH 3 CH 3 CH 3 CH 3 isoamyl H 1 H CH 3 octadecyl H 1 H CH 3 octadecyl H 1 CH 3 CH 3 -butyl C2 H5 1 H n-octyl n-octyl n-propyl 1 ch3 cyclohexyl cyclohexyl H 1 H 3 n-octadecyl ch 3 1 H ch 3 isopropyl H 1 H ch 3 oleyl H 1 H ch 3 ch 3 H 0 - HH ch 3 0 - ch 3 (12) Beta-diketones The component (i) may be a compound of formula (I) or a compound of formula (I) beta-diketone. In general beta-diketone compounds are represented by the general formula 1-O (O) -012-O (O) -112 (XLII)

In the general formula (XLII) R and R are individually and independently hydrocarbyl groups. Such hydrocarbyl groups may optionally be aliphatic or aromatic hydrocarbyl groups of the above-defined type. Among the aliphatic hydrocarbyl groups, lower hydrocarbyl groups containing up to about 7 carbon atoms are preferred. As specific examples 1 2 of groups R 1 and R 2 are methyl, ethyl, phenyl, benzyl, etc., and specific examples of beta-diketone compounds include acetylacetone and benzoylacetone . (13) Hydroxamic Acids

According to a variant, component (i) is a hydroxamic acid compound represented by the general formula R 1 -C (O) -NHOH (XLIII) i

In the general formula (XLIII) R represents a hydrocarbyl group having approximately 6 to 200 carbon atoms, more preferably 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, and more preferably 93

between about 6 and about 30 carbon atoms. According to a variant R is an alkyl or alkenyl group having from about 12 to 24 carbon atoms, more preferably from 16 to 20 carbon atoms, and most preferably about 18 carbon atoms. Advantageously, R 2 represents the oleyl group. (14) Linked Phenolic Compounds The component (i) may optionally be a phenolic compound represented by the structural formula

OH

OH R3 - [Aj (XLIV) R2 1 2

In the general formula (XLIV) R and R are 3

independently hydrocarbyl groups. R is CH 2, S or CH 2 OCH 2. In one embodiment, R 1 and R 2 are independently aliphatic groups generally having from 4 to 20 carbon atoms. Typical examples of groups 1 and 2 represented by the groups R 1 and R 2 include butyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl etc. Phenolic compounds represented by the general formula XLIV) can be prepared by reacting the appropriate substituted phenol with formaldehyde or with a sulfur derivative such as sulfur dichloride. In the case where a mole of formaldehyde is reacted with two moles of the substituted phenol, the 3 R bonding group is the group (¾). In case the molar ratio of formaldehyde to substituted phenol is 1: 1, bis-phenolic compounds bridged by the group CH2OCH2.

If two moles of a substituted phenol are reacted with one mole of sulfur dichloride a bis-phenolic compound is formed which is bridged by a

sulfur. In a variant R and R 3 are the propylene tetramer and R is sulfur. (15) Aromatic Difunctional Compounds The component (i) may optionally be an aromatic difunctional compound represented by the general formula (R ') i

(XLV)

In general formula (XLV) R1 is a hydrocarbyl group containing from 1 to about 100 atoms of

carbon. I is 0 to 4, preferably 0 to 2, and more preferably 0 or 1. The symbol T is in the ortho or 11-position or meta to G. G and T are independently OH, NH 2, NR 2, COOR, SH or C (O) H groups, wherein R 2 is hydrogen or hydrocarbyl. In one embodiment this compound is an aminophenol. Reference is made to the aminophenol compound which may contain other substituent groups such as hydrocarbyl groups. According to a variant this compound is a nitrophenol. Preferably such nitrophenol is an ortho-nitrophenol compound which may optionally contain further substituent groups such as hydrocarbyl groups. According to a variant the compound represented by the general formula (XLV) is a nitrophenol in which R1 is the dodecyl group, ii is the integer 1, G is OH, T is group NO 2 being this NO 2 group was ortho position relative to the OH group, this compound being dodecyl nitrophenol.

In one embodiment, G in the general formula (XLV) represents the OH group, T is NO2 and is ortho to the OH group, i is the integer 1 and R is represented by the general formula 96 2 3 4 5 6

R 1, R 2, R 3, R 4, R 5, R 5, R 5, R 5, R 7, R 9, R 9,

about 40 carbon atoms and R and R are independently alkylene or alkylidene groups having from 1 to about 6 carbon atoms. Accordingly in a variant R is an alkyl or alkenyl group having from about 16 to 20 carbon atoms and more preferably about 18 carbon atoms, the symbols R and R are hydrogen, R represents an ethylene or propylene group and preferably the propylene group and R 6 represents a methylene or ethylene group and preferably the methylene group. (16) Dithiocarbamates Component (i) may be a 1,2-dithiocarbamate compound containing the group R 1 NC (= S) S- wherein R 1 and R 2 independently represent hydrogen atom or hydrocarbyl groups. These dithiocarbamate compounds should contain at least one other functional group of the type discussed above. The other functional group may be a dithiocarbamate group. In one embodiment, component (i) is a dithiocarbamate compound represented by the general formula

(XLVI): I, 971 (R)

In general formula (XLVI) R and R are independently hydrogen or hydrocarbyl groups having up to about 40 carbon atoms, more preferably between 6 and 20 carbon atoms, and more preferably between 10 and 20 atoms of carbon dioxide. R 1 and R 2 are alkylene groups having up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, and most preferably up to about 2 or 3 carbon atoms. 1 1

G and T are independently selected from

OH and CN. In one embodiment R 1 and R 3 are individually the butyl group; R4 and R4 are ethylene or propylene groups and preferably any of them represents the ethylene group; and G and 1 T are CN. According to a variant the 1 5 6 7 5

R 1 represents the group R 1 RNRR- wherein R 2 and R 2 are independently hydrogen, lower alkyl, preferably hydrogen, R 2 is ethylene or propylene, preferably propylene, R is an alkyl or alkenyl group having from about 16 to 18 carbon atoms and preferably about 18 carbon atoms, R 1 and R 2 are each independently of the ethylene group and the symbols 11 G and T the CN or OH group. According to a 98

In another preferred embodiment of the present invention, R 1 represents the group R 2 R 2 R 2 R 2 wherein R 2 represents an alkyl or alkenyl group having from about 16 to 20 carbon atoms and more g

preferably about 18 carbon atoms, R 7 is hydrogen, R 2 is ethylene or propylene and preferably 2 is propylene, R 2 is hydrogen, R 3 is R represents individually the ethylene group 11 and G and T represent the CN or OH groups. (17) Xanthates The component (i) may be a xanthate compound which contains the group R 0 C (= S) S- wherein R is hydrocarbyl. These xanthate compounds should contain at least one other functional group of the type discussed above. The other functional group may be a xanthate group. In one embodiment, component (i) is a xanthate compound represented by the general formula

S (XLVII) R10-C-S-R2-R3-T '.

In the general formula (XLVII) R represents a hydrocarbyl group having up to about 40 carbon atoms, more preferably between 6 and 30 carbon atoms, and more preferably between 10 and 20 carbon atoms

of approximately carbon. R 2 is preferably an aliphatic group and more preferably 23 is an alkyl group. R 1 and R 2 are alkylene groups having up to about 10 carbon atoms, more preferably up to about 6 carbon atoms and more preferably about 2 or 3 carbon atoms. The 1 1

G and T are independently OH or CN groups. In one embodiment R is alkyl having from 1 to about 10 carbon atoms; R and R are ethylene or propylene groups and preferably any of them represents ethylene group; G and T are CN. In one embodiment R 2 represents the group R 5 R 6 NR 7 - wherein R 5 and R 6 are independently hydrogen,

lower alkyl, preferably the hydrogen atom, R is ethylene or propylene group, preferably the propylene group, R 1 and R 2 are each individually ethylene or propylene group and R 1 and T are the groups CN or OH. According to one embodiment R 2 represents the group R 2 is an alkyl or alkenyl group having 6 to 5 carbon atoms;

about 16 to 20 carbon atoms, R 7 is hydrogen, R 2 is

ethylene or propylene group, any of R and R 100 is ethylene or propylene group and G and 1 T represent the CN or OH groups. (18) Formazilos

According to a variant the component (I) is a paraformaldehyde compound represented by the general formula (XLVIII): ## STR3 ##

In the general formula (XLVIII) Ar and Ar independently represent aromatic groups which are preferably benzene nuclei or naphthalene nuclei, preferably benzene nuclei. R, R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about of 30 carbon atoms and more preferably up to about 20 carbon atoms. In one embodiment the symbols Ar 1 and Ar individually represent benzene nuclei; R 1 is a straight-chain or branched alkyl group having from about 4 to 12 carbon atoms, more preferably from 6 to 10 carbon atoms, and is preferably from about 8 carbon atoms.

2 carbon atoms; R 2 is hydrogen or lower alkyl; and R is an alkyl group having from about 6 to 18 carbon atoms, more preferably from 10 to 14 carbon atoms, and most preferably about 12 carbon atoms. In one embodiment the two symbols Ar and Ar represent benzene nuclei, the

R 2 is 1-ethyl-pentyl, R 3 is dodecyl and R 2 is hydrogen. (19) Pyridines The component (i) may be a pyridine derivative. In one embodiment, component (i) is a 2,2'-bipyridine compound represented by the general formula (XLIX)

In the general formula (XLIX) one or more of the ring carbon atoms may be substituted by a hydrocarbyl group, preferably a lower alkyl group. According to one embodiment the component (i) is a substituted pyridine represented by the general formula

N

102

1

In the general formula (L) R is hydrogen atom or hydrocarbyl groups preferably up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably to about 30 carbon atoms, and most preferably to about 20 carbon atoms. R 2 is preferably hydrogen or lower alkyl. In the general formula (L) one or more of the ring carbon atoms may be substituted by a hydrocarbyl group, preferably a lower alkyl group. (20) Boronated Acylated Blends Component (i) may be a borated acylated amine. These compounds can be prepared by first reacting a hydrocarbyl-substituted succinic acid-producing compound (hereinafter referred to as &quot; succinic acylating agent &quot;) with at least about one-half equivalent, per equivalent of the acid producing compound, of an amine which contains at least one hydrogen atom coupled to a nitrogen atom. The nitrogen-containing compositions obtained by this process are usually complex mixtures. These nitrogen-containing compositions are often referred to as &quot; acylated amines &quot;. The nitrogen containing composition is then boronated by reaction with a boron derivative compound selected from the group consisting of boron trioxide, boron halides, boron boron acids and boron acid esters.

Acylated alkynes are described in many U.S. patents including: 3 172 892 3 215 707 3 272 746 3 316 177 3 341 542 3 346 493 3 444 170 3 454 607 3 541 012 3 630 904 3 632 511 3 787 374 4 234 435

The above-referenced U.S. patents are hereby expressly incorporated herein by reference with respect to their teachings for the preparation of acylated arains which are useful for the present invention.

In general, a convenient route for the preparation of the acylated amines is to react a hydrocarbyl-substituted succinic acid-producing compound (&quot; carboxylic acid acylating agent &quot;) with an amine containing at least one hydrogen atom coupled to a nitrogen atom (i.e., HN =). The hydrocarbon substituted succinic acid producing compounds encompass the acids, anhydrides, halides and succinic esters. The number of carbon atoms in the hydrocarbon substituent in the succinic acid producing compound may vary over a wide range provided that the resulting organometallic complex is soluble or stable dispersible in the

diesel type. Such a hydrocarbon substituent will generally contain an average of at least about 10 aliphatic carbon atoms, preferably at least about 30 aliphatic carbon atoms and more preferably at least about 50 aliphatic carbon atoms.

The sources of the hydrocarbon substituent in question mainly comprise the substantially saturated and high molecular weight petroleum fractions and the practically saturated olefin polymers, particularly the monoolefin polymers having from 2 to 30 carbon atoms. Especially useful polymers are polymers of 1-mono-olefins such as ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1 -butene and 2-methyl-5-propyl-1-hexene. Also useful are the medium olefin polymers, i.e., olefins in which the olefinic bridge is not in the terminal position, examples are 2-butene, 3-pentene and 4-octene as examples.

Also useful are the interpolymers of olefins, such as those shown above, with other interpolymerizable olefinic substances such as aromatic olefins, cyclic olefins and polyolefins. Such interpolymers include, for example, those which are prepared by polymerization of isobutene with styrene; isobutene with butadiene; propene with isoprene; Ethylene with piperylene; isobutene with chloroprene; isobutene with p-methylstyrene; 1-hexene with 1,3-hexadiene; 1-octene with 1-hexene; 1-heptene with 1-pentene; 3-methyl-1-butene with 1-octene; 3,3-dimethyl-1-pentene with 1-hexene; isobutene with styrene and piperylene; etc..

The relative proportions between the raffinolines and the other monomers in the interpolymers influence the stability and the oil solubility of the final products derived from these interpolymers. Thus, for reasons of oil solubility and stability the interpolymers contemplated for use in the present invention should be practically aliphatic and practically saturated, i.e., should contain at least about 80%, and preferably at least about 95%, taking as based on the weight of units derived from aliphatic mono-olefins and not more than 5% of olefinic bridges based on the total number of carbon-carbon type covalent bridges. In many cases the percentage of olefin bridges should be less than about 2% of the total number of carbon-to-carbon covalent bridges.

Specific examples of such interpolymers include the copolymer of 95% (by weight) isobutene with 5% styrene; the terpolymer of 98% isobutene with 1% piperylene and 1% chloroprene; the terpolymer of 95% isobutene with 2% 1-butene and 3% 1-hexene; the terpolymer of 80% isobutene with 20% 1-pentene and 20% 1-octene; or 106

copolymer of 80% of 1-hexene and 20% of 1-heptene; the terpolymer of 90% isobutene with 2% cyclohexene and 8% propene; and the copolymer of 80% ethylene and 20% propene.

Another acceptable source of hydrocarbon groups is saturated aliphatic hydrocarbons such as highly refined white high molecular oils or synthetic alkanes such as those obtained by hydrogenation of the aforementioned high molecular weight olefin polymers or from olefinic substances of high molecular weight.

The use of olefinic polymers having average molecular weights (Mn) of approximately 700 to 10,000 is considered to be preferred. In one embodiment the substituent is derived from a polyolefin characterized by an Mn value of from about 700 to 10,000 and one Mp / Mn value comprised between 1.0 and 4.0.

For the preparation of the substituted succinic acylating agents one or more of the above polyalkenes are reacted with one or more acidic reagents selected from the group consisting of maleic or fumaric reagents such as acids or anhydrides. Typically such maleic or fumaric reagents will be maleic acid, fumaric acid, maleic anhydride 107

or a mixture of two or more of these compounds. In general, maleic reactants are preferred over the fumaric reactants since it is easier to obtain the former and further generally to react more readily with the polyalkenes (or derivatives thereof) for the preparation of the succinic acid producing compounds substituted derivatives useful in the present invention. Especially preferred reagents are maleic acid, maleic anhydride and mixtures thereof. For ease of production and ease of reaction, maleic anhydride is usually used.

For the sake of convenience and brevity the term &quot; maleic reagent &quot; will be used hereinafter. Where this term is used, it is to be understood that it is a generic term for acidic reagents selected from maleic and fumaric reagents including any mixture of such reagents. The term &quot; succinic acylating agents &quot; is also used herein. to represent the substituted succinic acid producing compounds.

There is a process for the preparation of substituted succinic acylating agents of the present invention which is partially illustrated in U.S. Pat. 3,219,666 which is hereby expressly incorporated by reference with respect to 108

to their teachings for the preparation of succinic acylating agents. Conveniently this procedure is called &quot; two-step procedure &quot;. This procedure involves the first accomplishment of the chlorination of the polyalkene and subsequent reaction of the chlorinated polyalkene with the maleic reagent.

A further procedure for the preparation of these acylating agents of substituted succinic acids utilizes the process described in U.S. Pat. 3 912 764 and in the British Patent η 2. 1 440 219, both of which are expressly incorporated by reference with reference to their teachings on this process. In accordance with this process the polyalkene and the maleic reagent are first reacted by heating them together according to a &quot; direct alkylation &quot; procedure. Upon completion of the direct alkylation step chlorine is introduced into the reaction mixture to provide the reaction of the remaining unreacted maleic reagents.

Another process for the preparation of substituted succinic acylating agents according to the present invention is the so-called &quot; one step &quot; process. This process is described in U.S. Pat. Nos. 3215707 and 3231587. These two patents are expressly incorporated herein by reference with respect to their teachings on the process. This one-step process involves the preparation of a mixture of the polyalkene and the maleic reagent containing the required amounts of both compounds to provide the desired substituted succinic acylating agents of the present invention. This means that there must be at least one mole of maleic reactant per mole of polyalkene so that there is at least one succinic group per equivalent equivalent in weight of substituent groups. Chlorine is then introduced into the mixture, usually by passing chlorine in the gaseous state through the mixture, with stirring.

The amines which react with the succinic acid producing compounds to provide the acylated amines may optionally be any of the amines of formula (A-3) described above for the preparation of the aromatic Mannich compounds of the present invention. A preferred class of such amines is the alkylene polyamines represented by the above formula (A-3-3).

The acylated amines obtained by reacting the succinic acid producing compounds and amines described above may optionally be amine, amide, imide, imidazoline salts and also mixtures thereof. For the preparation of the acylated amines one or more of the succinic acid producing compounds and one or more of these amines are heated, optionally in the presence of a

solvent / diluent usually in the liquid state, at an elevated temperature generally comprised between the temperature of 80 ° C and the temperature corresponding to the point of decomposition of the mixture or the product. Temperatures in the range of approximately 100 ° C to 300 ° C are generally used provided that the temperature of 300 ° C does not exceed the point of decomposition.

The succinic acid-producing compound and the amine are reacted in amounts sufficient to provide at least about equivalent equivalent, equivalent of the acid producing compound, of the amine. In general, the maximum amount of the amine present will be about two moles of amine per equivalent of the succinic acid producing compound. For the purposes of the present invention, one equivalent of the amine is the amount of such amine corresponding to the total weight of the amine divided by the total number of the nitrogen atoms present. Thus, the octylamine has an equivalent weight equal to its molecular weight; the ethylene diamine has an equivalent weight equal to one half of its molecular weight; and the amino ethyl piperazine has an equivalent weight equal to one third of its molecular weight. The number of equivalents of the succinic acid producing compound depends on the number of carboxylic functions present in the hydrocarbon substituted succinic acid producing compound. Thus, the number of lll

equivalents of the hydrocarbon substituted succinic acid producing compound will vary with the number of succinic groups therein and there will generally be two equivalents of acylating reagent per each succinic group present in the acylating reagents. It may be possible to use conventional techniques to determine the number of carboxyl functions (for example, acid number, saponification number) and consequently the number of equivalents of acylating reagent available to react with the amine. It is mentioned that other details and examples of the procedures for the preparation of such acylated amines can be found, for example, in U.S. Pat. 3,172,892; 3,219,666; 3,272,746; and 4 234 435 the contents of which are hereby incorporated by reference.

The acylated amine is then reacted with at least one boron acid selected from the class consisting of boron trioxides, boron halides, boronic acids, boron amides and boron acid esters. The amount of the compound which reacts with the acylated amine intermediate is generally sufficient to provide an atomic ratio for boron from about 0.1 per mole of the acylated amine to an atomic ratio for boron of about 10 to any atomic ratio to the nitrogen of said acylated amine. More generally, the amount of boron compound 112 present is sufficient to provide an atomic ratio for boron from about 0.5 per mole of the acylated amine to an atomic ratio for boron of about 2 to any atomic ratio of the nitrogen used .

Useful boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acids such as boronic acid (i.e. (i.e. H 2 BO 3), tetraboric acid (i.e., H2 B 4 O 7), metaboric acid (i.e., HBO 2), alkylb (OH) 2 or aryl-B (OH) 2), boric acid boron anhydrides, boron amides and various esters of such boron acids. The use of boron trihalide complexes with ethers, organic acids, inorganic acids or hydrocarbons is a convenient means of introducing the boron-derived reagent into the reaction mixture. Such complexes are known and examples are boron trifluoride triethyl ester, boron trifluoride phosphoric acid, boron trichloride chloroacetic acid, boron tribromide dioxane and boron trifluoride ether- ethyl-methyl ester.

Specific examples of boronic acids include methyl boronic acid, phenyl boronic acid, cyclohexyl boronic acid, p-heptyl phenyl boronic acid and dodecyl boronic acid.

Esters of boron acids especially include the organic mono-, di- and tri-esters of boric acid with alcohols or with phenols such as for example methanol, ethanol, isopropanol, cyclohexanol, cyclopentanol, 1-octanol , 2-octanol, dodecanol, benzyl alcohol, stearyl alcohol, benzyl alcohol, 2-butyl cyclohexanol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,4-hexanediol, 1 , 2-cyclohexanediol, 1,3-octanediol, glycerol, pentaerythiol, diethylene glycol, carbitol, &quot; Cellosolve &quot;, triethylene glycol, tripropylene glycol, phenol, neftol, p-butylphenol, di-heptylphenol, n-cyclohexylphenol, 2,2-bis- (p-hydroxyphenyl) propane, polyisobutene (1500 molecular weight) -phenol substituted, ethylene-chlorohydrin, o-chlorophenol, m-nitrophenol , 6-bromo-octanol and 7-keto-dodecanol. Lower alcohols, 1,2-glycols and 1,3-glycols, i.e., those having less than 8 carbon atoms are especially useful for the preparation of boric acid esters for the purposes of the present invention.

Methods for the preparation of boron acid esters are known and are described in the literature of the art (such as &quot; Chemical Reviews &quot;, pp. 959-1064, Vol. 56). Thereby, a method involving the reaction of boron trichloride with 3 moles of an alcohol or a phenol is provided to provide a triorganic borate. Another method involving the reaction of boric oxide with an alcohol or a phenol is mentioned. Still another method involves the direct esterification of the tetraboric acid with 3 moles of an alcohol or a phenol. There is yet another method which involves the direct esterification of a boric acid with a glycol to provide, for example, a cyclic alkylene borate. The reaction of the acylated amine with the boron compounds can be effected by simply mixing the reactants at a desired temperature. The use of an inert solvent is optional although it is often desirable, especially where a solid or highly viscous reagent exists in the reaction mixture. The inert solvent may optionally be a hydrocarbon such as benzene, toluene, naphtha, cyclohexane, n-hexane or a mineral oil. The reaction temperature may optionally vary within wide limits. Generally it is preferably in the range of from about 50 ° C to about 250 ° C. In some cases it may be of the order of 25 ° C or possibly lower. The upper temperature limit is the point of decomposition of the particular product and / or reaction mixture. The reaction is usually complete after a short time possibly between 0.5 and 6 hours. After the reaction is complete, it is possible to eventually dissolve the product in the solvent by purifying the resulting solution by centrifugation or by filtration if

present with an obscured appearance or contain insoluble substances. Normally the product is sufficiently pure so that no further purification is necessary or to make it optional. The reaction of the acylated amine with the boron compounds provides a boron-containing product and substantially all the nitrogen originally present in the acylated amine reactant. The reaction is believed to result in the formation of a complex between boron and nitrogen. Such a complex may in some cases imply an atomic ratio for boron greater than unity with an atomic proportion to the nitrogen corresponding to the unit and in some cases an atomic proportion to the nitrogen above the unit with a corresponding atomic proportion to the boron the unity. The nature of the complex is not clearly understood.

Insofar as the exact stoichiometry of complex formation is not known, the relative proportions of the reactants usable in the process are based primarily on utility considerations of the products, for the purposes of the present invention. In this regard, it is understood that useful products are obtained from reaction mixtures in which the reactants are present in relative proportions to provide atomic proportions for boron from about 0.1 per mole of acylated amine to atomic ratios for the boron of about 10 to any atomic ratio of the nitrogen 116 -3

of said acylated amine being used. Useful amounts of the reactants are such as to provide an atomic ratio for boron from about 0.5 to each mole of the acylated amine to about 2 atomic proportions for boron per mole of the acylated amine. By way of illustration, it is meant that the amount of a boron compound having one boron atom per molecule used with one mole of an acylated amine having 5 nitrogen atoms per molecule ranges approximately in the range of 0.1 mol to 50 moles and preferably between 0.5 moles and 10 moles.

In one embodiment, these boronated acylated amines are. useful as component (i) in the formation of the organometallic complexes of the present invention. In another embodiment, such borated acylated amines are useful as organometallic complexes of the present invention. (21) Phosphorus-containing acylated amines The component (i) may be an acylated amine containing phosphorus. These compounds are prepared by the reaction of (Pl) at least one carboxylic acid acylating agent, (P-2) at least one amine characterized by the presence within its structure of at least one HN = e (P-3) at least one phosphorus-containing acid of formula 117

{R '(x3) m- x2 Ρ-Χ'Η (P-3-1) 12 3 4

In the general formula (P-3-1) each of X, X, X and X is independently an oxygen or sulfur atom, each m is zero or one and each R2 is independently a hydrocarbyl. The carboxylic acylating agent (P-1) and the amine (P-2) have been previously described with respect to the preparation of borated acylated amines. Examples of acids which contain phosphorus (P-3) include the following: Dihydrocarbyl phosphino dithioic acids corresponding to general formula

S R! 2. S-hydrocarbyl-hydrocarbyl-phosphono-trithioic acids corresponding to the general formula

S R1

JP-SH R2 118 3.-Dithioic acids corresponding to the general formula O-hydrocarbyl-hydrocarbyl-phosphono-

S, P-SH

S, S-dihydrocarbyl-phosphono-tetrathioic acids corresponding to the general formula

s

R1-S

'P-SH

R2-S5. O, S-dihydrocarbylphosphono-trithioic acids corresponding to the general formula

s

119

6. Ο, Ο-Dihydrocarbyl phosphono dithioic acids corresponding to the general formula

S P-SH R1 -O.

R2 -O

Useful acids of general formula

S P-SH R1-0

R2-O are readily obtained by the reaction of phosphorus pentasulphide (P2S5) and of an alcohol or a phenol. This reaction involves mixing at a temperature of about 20 ° C to 200 ° C, 4 moles of an alcohol or a phenol with one mole of phosphorus pentasulfide. In this reaction hydrogen sulfide is liberated. Analogs of these oxygen-containing acids are conveniently prepared by treating the dithioic acid with water or with 120

water vapor which actually replaces one or both sulfur atoms.

Useful phosphorus-containing acids are acids containing phosphorus and sulfur. Among these acids are those in which at least one of the symbols X or X represents the sulfur atom and more preferably those in which the two symbols X and X represent sulfur atoms, at least one of the X and X are oxygen or sulfur, more preferably X and X are oxygen and m is 1. It is possible to use mixtures of these acids. 1 2

Each R 1 and R 2 independently represents a hydrocarbyl derivative group which is preferably free of acetylenic groups and is also normally free of any ethylenic unsaturation and having approximately 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms and more preferably between 3 and 18 carbon atoms. In a variant each of R 1 and R 2 represents the same or different groups having approximately 4 to 8 carbon atoms. 1 2

Each of R 1 and R 2 may be for example isopropyl, isobutyl, 4-methyl-2-pentyl, 2-ethyl-1-hexy, isooctyl, and the like. Any of R 1 and R 2 may represent groups identical to each other although 121

may be different and either or both may be mixtures. Any of R 2 and R 2 preferably represents an alkyl group and more desirably represents a branched chain alkyl group. The reaction for the formation of the phosphorus-containing acylated amines can be carried out by mixing the (P-1), (P-2) and (P-3) components in any order. The three reactants may optionally be mixed at room temperature and heated to a temperature in excess of 80øC to effect acylation. In a similar manner, it is also possible to carry out the reaction by first reacting the (P-2) and (P-3) components and then acylating the intermediate with the component (Pl) or by acylating the ) with the component (P-1) and then reacting the acylated amine with the (P-3) component. The preferred temperature for carrying out the acylation reaction is from about 100 ° C to 300 ° C and preferably from about 150 ° C to about 250 ° C. The acylation reaction is accompanied by the formation of water. Removal of such formed water may be effected by heating the reaction mixture to a temperature of 100 ° C or higher. Removal may possibly be facilitated by aerating the reaction mixture with an inert gas such as nitrogen during the heating process. Removal 122

may also be facilitated by using in the reaction mixture an inert solvent which forms with the water a co-distilled azeotropic mixture. Examples of such solvents are benzene, n-hexane, toluene, xylene, and the like. The use of such solvents enables the water to be removed at a much lower temperature, for example at the temperature of 80 ° C.

The relative proportions of the reactants used in the process are based on the stoichiometry of the reaction involved in the process and the usefulness of the products obtained therefrom for the purposes of the present invention. The minimum amounts of the components (P-1) and (P-3) used are about 0.5 equivalents of each of these components (P-1) and (P-3) per mole of the (P-2) component. The maximum amounts of the components (P-1) and (P-3) used are based on the total number of equivalents of the (P-2) component used.

In order to prepare these phosphorus-containing acylated amines, the number of equivalents of an amine (P-2) is based on the number of groups HN < existing in this amine. A weight equivalent of an amine is the total weight of the amine divided by the total number of groups HN < existing. Thus, the ethylene diamine has a weight equivalent of one-half of its molecular weight; and the tetraethylene pentamine has a weight equivalent of one fifth of its molecular weight. By way of example, it is also noted that the weight equivalent of a commercially available amine mixture can be determined by dividing the atomic weight of the nitrogen (14) by the percentage value by weight of the nitrogen contained in the amine. Accordingly, a mixture of amines having 34% N will have a weight equivalent of 41.2. The number of equivalents of an amine can be determined by dividing its total weight by its equivalent weight. The number of equivalents of the acylating agent (P-1) depends on the number of carboxylic functions (for example, carboxylic acid groups or their functional derivatives) on the acylating agent. In this way the number of equivalents of acylating agents will vary with the number of carboxy groups present therein. For the determination of the number of equivalents of acylating agents carboxyl functions which are not capable of reacting with the carboxylic acid acylating agent are excluded. However, in general there is one equivalent of the acylating agent for each carboxy group in the acylating agents. For example, there will be two carboxy groups on the acylating agents derived from the reaction of one mole of olefinic polymer and one mole of maleic anhydride. Conventional techniques are readily applicable for the determination of the number of carboxyl functions (e.g., acid number, saponification number) and consequently for the determination of the number of equivalents of available acylating agent to react with the amine. The equivalent weight of the component (P-3) may be 124

determined by dividing the molecular weight of the (P-3) component by the number of -PXXH groups. These values are usually determined from the structural formula of the (P-3) component or empirically by well-known titration procedures. The number of equivalents of the component (P-3) can be determined by dividing the weight of the component (P-3) by its equivalent weight. The maximum number of combined equivalents of the components (P-1) and (P-3) reactable with one mole of the (P-2) component is equal to the number of groups HN <. In case an excess of components (P-1) and (P-3) is used, such excess will not take part in the reaction. On the other hand, if the total amount of components (P-1) and (P-3) is less than the maximum amount, the products will contain nitrogen atoms of unreacted free amino groups. Useful products are those which are obtained by using the components (P1) and (P3) in relative amounts contained within the range of from about 0.5: 4.5 to 4.5: 0.5 . A specific example illustrating the limits of the relative proportions of the reactants is given below: a mole of tetraalkylene is reacted with an amount of from about 0.5 to 4.5 equivalents of a succinic anhydride substituted by a polyisobutene and an amount of from about 0.5 to 4.5 equivalents of a phosphorodithioic acid. 125

(22) Pyrrole derivatives The component (i) may be a pyrrole derivative represented by the general formula

N 'H (L1)

In the general formula (II), T is OH, NH 2, NR 2, COOR, SH or C (O) H, wherein R is hydrogen, hydrocarbyl, preferably lower alkyl. Any of the ring carbon atoms may be substituted with hydrocarbyl groups, preferably with lower alkyl groups. (23) Porphyrin The component (i) may be one or more porphyrins.

Porphyrins are a class of heterocyclic compounds containing 4 pyrrol rings joined by methylene groups. These compounds may be represented by the general formula

R5 R9 (LU) 126 / ί

In the general formula (LII) R 1, R 2, R 3, R 4, R 5,

Q and R are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, more preferably up to about 30 carbon atoms. carbon, most preferably up to about 10 carbon atoms. In a variant each of R 1, R 2, R 3, R 4, R 5, R 5, R 5 and R 5 independently represents hydrogen, lower alkyl, lower alkenyl, hydroxy substituted lower alkyl, or -COOH-substituted lower alkyl. Examples are: pyrroporphyrin, dicarporphyrin, filoporphyrin, phylloeritrin, dueteroporphyrin, etioporphyrin III, protoporphyrin, hematoporphyrin, mesoporphyrin IX, coproporphyrin, uroporphyrin and bilirubin. (24) Sulphonic acids The component (i) may be a sulfonic acid represented by the general formula R1S03H (LIII) 127 1

In the formula (LIII) R represents a hydrocarbyl group preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to 60 carbon atoms, more preferably between 10 and 60 carbon atoms.

carbon. Sulfonic acids are characterized by the presence of the sulfo group -SO 3 H (or -SO 2 OH) and may be considered sulfuric acid derivatives in which one of the hydroxyl groups has been replaced by an organic radical. Type-detecting compounds are generally obtained by treatment of petroleum fractions (petroleum sulfonates). Due to the variable nature of the branches of the oil and in particular due to the particular fraction of oil being used, the sulfonates generally constitute a complex mixture. Useful sulfonates include those having an alkaryl group, that is, an alkylated benzene group or an alkylated naphthalene group. Exemplary sulfonic acids include dioctyl benzenesulfonic acid, dodecyl benzenesulfonic acid, didodecyl benzenesulfonic acid, dinonyl naphthalenesulfonic acid, dilauryl benzenesulfonic acid, lauryl-cetyl-benzenesulfonic acid, benzene sulfonic acid alkylated with a polyolefin such as polybutylene and polypropylene, etc. Further details on sulfonic acids written by Kirk-Othmer can be found in &quot; Encyclopedia of Chemical Technology &quot;, Second Edition, 1969, Vol. 311 to 319 and in &quot; Petroleum

Sulphonates &quot; by R. Leslie in Manuracturing Chemist, October 1950 (XXI, 10), pp. 417-422.

(25) EDTA Derivatives Component (i) may be an ethylene diamine tetraacetic acid (EDTA) derivative represented by the general formula ## STR3 ## -CH? CH? N? 11? -Oc? Ch2-coor3

In the general formula (LIV) R1, R2, R3 and R4 are independently hydrogen or hydrocarbyl groups preferably having up to about 200 carbon atoms, more preferably up to about 100 carbon atoms, more preferably up to about about 50 carbon atoms, more preferably up to about 30 carbon atoms, more preferably up to about 20 carbon atoms. In one embodiment, R 1, R 2, R 3 and R 4 are independently hydrogen or lower aliphatic hydrocarbyl groups, preferably hydrogen or lower alkyl groups.

Component (ii): The metal used in said organometallic complex is any metal that reduces the ignition temperature of the exhaust particles collected in separator 129

of the small particles of the exhaust system of a diesel engine and which form a complex with component (i). According to a variant such metal is Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Mn, Fe, Co, Cu, Zn, B, Pb, Sb or a mixture of two or several of these metals. According to a particularly preferred aspect this metal is copper. The metal may be comprised of Cu in combination with one or more metals selected from Fe, V or Mn. The metal may be selected from the group consisting of one or more metals Cu, Ti, Mn, Fe, B, Zn, Mg, Ca, Na, K, Sr, Ba and Zr. This metal may be Cu in combination with one or more metals selected from Ti, Mn, Fe, B, Zn, Mg, Ca, Na, K, Sr, Ba and Zr.

According to a variant the metal is different from Ti or Zr. According to another variant the metal is different from a rare earth metal group. According to another embodiment the metal is different from Ce, Mn or a mixture of Ce and Mn. The reagent derived from the metal (ii) may be a nitrate, nitrite, halide, carboxylate, phosphate, phosphite, sulfate, sulfite, carbonate, borate, hydroxide or oxide. Examples are the cobaltous nitrate compounds, cobaltous oxide, cobalt oxide, cobalt nitrite, cobaltous phosphate, cobaltous chloride, cobaltous chloride, chromous acetate, chromic acetate, chromium bromide, chromium chloride, chromium fluoride, chromium oxide, chromium sulfite, hepta-130

chromium phosphate, chromium phosphate, manganous acetate, manganous benzoate, manganese carbonate, manganese dichloride, manganese trichloride, manganous trichloride, manganous citrate, manganous form, manganous nitrate, manganous oxalate, Manganous Phosphate, Manganese Pyrophosphate, Manganese Rapatephosphate, Manganous Valerate, Ferrous Acetate, Ferric Benzoate, Ferrous Bromide, Ferric Carbonate, Ferric Lactate, Ferrous Lactate, Ferric Oxide, Ferric Oxide, Ferric Hypophosphite, Ferric Sulphate, Ferric Hydrosulfite, Copper Propionate , cupric acetate, cupric metaborate, cupric benzoate, cupric format, cupric laurate, cupric nitrite, cupric oxychloride, cupric palmitate, cupric salicylate, cuprous oxide, copper carbonate, copper naphthenate, zinc benzoate, zinc borate, zinc bromide , zinc iodide, zinc lactate zinc oxide, zinc stearate, sul zinc acetate, sodium acetate, sodium benzoate, sodium bicarbonate, sodium bisulfate, sodium bisulfite, sodium bromide, sodium carbonate, sodium chloride, sodium citrate, sodium hydroxide, sodium hypophosphite, sodium iodide sodium, sodium metabisulfite, sodium naphthenate, sodium nitrite, sodium phosphate, sodium sulfite, potassium acetate, potassium benzoate, potassium bicarbonate, potassium bisulfate, potassium bisulfite, potassium bromide, potassium carbonate, potassium chloride, citrate 131

potassium hydroxide, potassium hydroxide, potassium hypophosphite, potassium iodide, potassium metabisulphite, potassium naphthenate, potassium nitrite, potassium pentaborate, potassium phosphate, potassium sulphite, titanium dichloride, titanium dioxide, titanium monoxide , titanium oxalate, titanium sulfate, titanium tetrachloride, zirconium acetate, zirconium oxide, zirconium carbonate, zirconium chloride, zirconium fluoride, zirconium hydroxide, zirconium lactate, zirconium naphthenate, zirconium nitrate, orthophosphate zirconium phosphate, zirconium sulfate, zirconium tetrachloride, zirconium tetrafluoride, boron oxide, boron tribride, boron trichloride, boron trifluoride, calcium acetate, calcium bisulfite, calcium bromide, calcium carbonate , calcium chloride, calcium fluoride, calcium hydroxide, calcium iodide, calcium laurate, calcium naphthenate, calcium nitrite calcium carbonate, calcium phosphate, calcium phosphate, calcium stearate, calcium sulfate, calcium sulfite, magnesium acetate, magnesium bisulfite, magnesium bromide, magnesium carbonate, magnesium chloride, magnesium fluoride, Magnesium hydroxide, Magnesium iodide, Magnesium laurate, Magnesium naphthenate, Magnesium nitrite, Magnesium oxalate, Magnesium phosphate, Magnesium phosphite, Magnesium stearate, Magnesium sulfate, Magnesium sulphite, Strontium acetate, strontium bromide, carbonate of 132

strontium chloride, strontium chloride, strontium fluoride, strontium hydroxide, strontium iodide, strontium laurate, strontium naphthenate, strontium nitrite, strontium oxalate, strontium phosphate, strontium phosphite, strontium stearate, strontium sulfate, sulphite of strontium, acetate of strontium, barium bisulphite, barium bisulphite, barium bromide, barium carbonate, barium chloride, barium fluoride, barium hydroxide, barium iodide, barium laurate, barium naphthenate, barium nitrite, barium oxalate, barium phosphate, barium phosphite, barium stearate, barium sulfate and barium sulfite. Hydrates of the foregoing compounds are useful.

Formation reaction of the organometallic complex The reaction according to which the organometallic complexes of the present invention are formed from components (i) and (ii) may optionally be carried out by simply mixing the reactants at the desired temperature. The reaction may be carried out at a temperature of at least about 80 ° C. In some cases the reaction temperature may be at room temperature, for example at 20 ° C. The upper limit of the reaction temperature is the decomposition point of the reaction mixture although it is rarely necessary to use a temperature above 250 ° C. The reaction is preferably carried out in the presence of a diluent or a solvent in which the reactants are soluble or the product is soluble. The solvent may be any fluid inert solvent such as benzene, xylene, toluene, kerosene, a mineral oil, chlorobenzene, dioxane or the like.

The relative amounts of components (i) and (ii) vary within wide limits. Typically at least about 0.1 equivalents of component (ii) is used for each equivalent of component (ii). The amount of component (ii) may preferably range from about 0.05 to about 1, more preferably from 0.1 to 0.4 equivalents of component (ii) per equivalent of component (i). The equivalent weight of component (i) is based on the number of functional groups in component (i) which are capable of forming a complex with the metal in component (ii). Thus, the weight of one equivalent of the propylene-nitrophenol tetramer is equal to half of its molecular weight. The equivalent weight of component (ii) is based on the number of metal atoms in the molecule. Thus, the weight of one equivalent of cuprous oxide is one half of its molecular weight and the weight of one equivalent of cupric hydroxide is equal to its molecular weight. Likewise, the relative amount of component (ii) is somehow based on the coordination number of the metal in the component (ii) reactant. For example, it is possible for the maximum of six equivalents of component (i) to combine with one equivalent of a metal reagent in which the coordinate number of the metal is six. The product obtained by the reaction of component 134 (i) with component (ii) is an &quot; organometallic complex &quot;. This means that it results from the combination of the functional groups in component (i) with the metal in component (ii) by means of the secondary valence of the metal. The exact nature of the organometallic complex is not known. For the purposes of the present invention it is only necessary that such complexes are sufficiently stable in the diesel fuel to allow their use in the diesel engine equipped with a separator of the small particles of the exhaust system in order to decrease the ignition temperature of the particles collected by said separator.

According to a variant the organometallic complex is different from a complex consisting of a transition metal of an aromatic Mannich compound in combination with a Schiff base, said Mannich compound being derived from an aromatic phenol, aldehyde or ketone and a amine containing hydroxyl and / or thiol groups.

According to a variant the organometallic complex is different from a complex consisting of a transition metal of an aromatic Mannich compound in combination with an oxime, said Mannich compound being derived from an aromatic phenol, aldehyde or ketone and an amine which contains hydroxyl and / or thiol groups.

According to a variant the organometallic complex is different from a copper complex of an aromatic Mannich compound in combination with dodecyl-salicylaldexime, said Mannich compound being derived from dodecylphenol, ethanolamine and paraformaldehyde.

The following examples illustrate the preparation of the organometallic complexes which are used in accordance with the present invention. Unless otherwise specified / in the following examples and also throughout the specification and the appended claims, all parts and percentages are calculated by weight, all pressure values correspond to atmospheric pressure and all temperature values are in degrees Celsius.

Example 1

An amount of 204 grams of 2-hydroxyacetophenone, 385.5 grams of tridecyloxypropylamine, 400 ml of xylene and 0.5 grams of para-toluenesulfonic acid were mixed in a flask equipped with a water condenser. The mixture was heated under a nitrogen atmosphere to its reflux temperature and kept under reflux conditions for 6 hours. A quantity of 26 grams of water was collected in the water condenser. An amount of 103.6 grams of copper carbonate was added. The mixture was warmed to its reflux temperature and kept under reflux conditions for 7 hours. A quantity of 20.5 grams of water was collected in the water condenser. The mixture was allowed to cool to room temperature. The mixture was filtered and then removed by heating to a temperature of 136 ° C.

hours at 130øC and at an absolute pressure of 20 mbar for 2 hours. The mixture was filtered on diatomaceous earth at 125 to 130øC to provide an amount of 596 grams of product having a copper content of 5, 72% by weight.

Example 2

Part A: A mixture of 530 grams of propylene-phenol tetramer, 66 grams of paraformaldehyde, 60 grams of ethylenediamine and 500 ml of toluene was prepared in a flask equipped with a water condenser. The mixture was warmed to its reflux temperature and kept under reflux conditions for 2 hours.

An amount of 45 grams of water was collected in the condenser. The solvent was removed from the mixture by vacuum filtration to provide 555 grams of product as an oil.

Part B: An amount of 307 grams of the product obtained in Part A was heated at 60-70 ° C in a flask equipped with a water condenser. 55 grams of copper carbonate was added under stirring. A quantity of 58 grams of aqueous ammonium hydroxide solution was added dropwise over a period of 10 minutes. The mixture was warmed to 100 ° C and maintained at that temperature for 2 hours with nitrogen aeration at the rate of 0.1 cubic feet (0.1133 m) per hour. An amount of 50 grams of water was collected in the water condenser. 137

The mixture was warmed to 150 to 160 ° C and kept at this temperature for 0.5 hours. A quantity of 10 grams of water was collected in the condenser. The mixture was filtered on diatomaceous earth to afford 460 grams of product as a dark green oil having a copper content of 4.89% by weight.

Example 3

Part A: An amount of 290 grams of 8-hydroxy-quinoline, 66 grams of paraformaldehyde, 556 grams of &quot; Armeen OL &quot; (an Armak product identified as being a mixture of fatty amines having a primary amine content of the order of 95% by weight, the remainder being secondary and tertiary amines and further having a chain whose length ranges from C12 to C18 (about 79% by weight corresponding to 0.5 g) and 80 ml of toluene was heated to reflux temperature and kept under reflux conditions for a period of 2 to 3 hours in a flask equipped with a condenser Water.

An amount of 45 grams of water was collected in the condenser. The solvent was removed from the mixture in vacuo. The mixture was filtered over diatomaceous earth to afford an amount of 848 grams of product as an oil.

Part B: An amount of 212 grams of the product of Part A, 28 grams of copper carbonate and 250

ml of toluene in a flask equipped with a water condenser. The mixture was heated to reflux temperature and kept under reflux conditions for 2 hours. The solvent was removed and the residue was filtered over diatomaceous earth to provide an amount of 255 grams of product as an oil and whose copper content was 5.3% by weight.

Example 4

An amount of 78 grams of &quot; Aloxime 200 &quot; (a product of Henkel identified as 7-dodecyl-8-hydroxy-quinoline), 14 grams of copper carbonate, 55 grams of a 100 N mineral oil and 100 ml of toluene in a flask equipped with a water condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 4 grams of water was collected in the condenser. The solvent was removed in vacuo to provide an amount of 120 grams of product as a green oil whose copper content is 4.3% by weight.

Example 5

Part A: An amount of 203 grams of p-heptyl-phenol, 350 grams of "Duomeen T" was mixed. (an Armak product identified as N-tallow-1,3-diaminopropane), 33 grams of paraformaldehyde and 250 ml of toluene in a flask equipped with a water condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. A quantity of 23 139

grams of water in the water condenser. The solvent was removed from the mixture in vacuo to an amount of 500 grams of the product as a brown oil.

Part B: An amount of 141 grams of the product of Part A was mixed, 157 grams of copper naphthenate having a copper content of 8% by weight and 200 ml of toluene in a flask equipped with a water condenser. The mixture was warmed to 60 ° C and held at that temperature for 2 hours. The mixture was then heated to reflux temperature and kept under reflux conditions for 2 hours. The solvent was removed from the mixture by heating the mixture to 150 ° C under vacuum at an absolute pressure of 20 mm Hg. The mixture was filtered to provide 260 grams of product as a brownish green oil whose copper content is 4.6% by weight.

Example 6

Part A: A quantity of 530 grams of propylene-phenol tetramer and 400 grams of acetic acid were mixed in a flask equipped with a water condenser and immersed in a cooling bath. An amount of 140 ml of 70% nitric acid solution was added to the mixture while maintaining the temperature of the mixture below 15øC. The mixture was warmed to room temperature and kept at that temperature under stirring over a period of 2 to 3 hours. The mixture was then heated to 140C.

temperature of 100 ° C. Acetic acid and water were removed from the mixture by heating to 130 to 140 ° C and absolute pressure of 20 mm Hg. The mixture was filtered over diatomaceous earth to give an amount of 600 grams of product as an orange-brown oil.

Part B: An amount of 200 grams of the product of Part A was mixed, 225 grams of copper naphthenate having a copper content of 8% by weight and 250 ml of toluene under a nitrogen atmosphere in a flask equipped with a condenser of water. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. The solvent was removed from the mixture in vacuo. The mixture was filtered on diatomaceous earth to provide 390 grams of product as a green oil and the copper content is 4.8% by weight.

Example 7

Part A: An amount of 530 grams of propylene-phenol tetramer, 61 grams of ethanol-amine and 68 grams of solvent was blended. &Quot; SC-100 &quot; (an Ohio Solvents product identified as an aromatic hydrocarbon solvent) in a flask equipped with a water condenser. The mixture was heated to 60 ° C. Then 66 grams of paraformaldehyde was added, the mixture was warmed to the reflux temperature and kept under reflux conditions for 3 hours with nitrogen aeration at the rate of 0.085 m 3 (3 cubic feet) per hour. An amount of 37 grams of water was collected in the condenser. A quantity of 20 ml of volatiles was removed from the mixture. The mixture was filtered over diatomaceous earth to afford an amount of 630 grams of product.

Part B: An amount of 74.6 grams of the product of Part A of Example 5 was blended, 26.1 grams of the product of Part A of this Example 7, 23.2 grams of &quot; 30% Cu Cem All &quot; (a product of Mooney Chemicals identified as a copper carboxylate salt having a copper content of 30% by weight) and 76 grams of solvent &quot; SC-100 &quot;, at a temperature of 60 ° C to provide an amount of 320 grams of product.

Example 8

Part A: An amount of 203 grams of p-heptyl phenol, 66 grams of paraformaldehyde, 206 grams of tetraethylene-pentamine and 250 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 40 grams of water was collected in the condenser. 150 grams of a 100 N mineral oil was added. The mixture was filtered over diatomaceous earth to provide an amount of 560 grams of product as an oil.

Part B: An amount of 242 grams of the product of Part A and 393 grams of copper naphthenate having a copper content of 8% by weight was blended and heated to temperature 142 of 100-120 ° C, and stirred at this temperature for 2 hours under stirring. A quantity of 25 grams of volatiles was removed from the mixture by evaporation in vacuo. The mixture was filtered on diatomaceous earth at a temperature of 120 ° F to provide an amount of 563 grams of product as a blue-green oil whose copper content is 3.84% by weight.

Example 9

Part A: 406 grams of p-heptyl phenol, 66 grams of paraformaldehyde, 31 grams of ethylenediamine and 250 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 40 grams of water was collected in the condenser. The solvent was evaporated in vacuo to provide an amount of 470 grams of product.

Part B: An amount of 270 grams of the product of Part A and 459 grams of copper naphthenate having a copper content of 8% by weight was blended, heated to a temperature comprised between 100 and 120 ° C and maintained The mixture was filtered on diatomaceous earth to provide an amount of 653 grams of product as a colorless oil and having a copper content corresponding to 5.06% by weight.

An amount of 203 grams of p-heptyl phenol, 66 grams of paraformaldehyde, 150 grams of N-methyl ethanolamine and 250 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 50 grams of water was collected in the condenser. The solvent was removed from the mixture in vacuo. The mixture was filtered over diatomaceous earth to give an amount of 295 grams of product as an oil.

Part B: 150 grams of the product of Part A and 157 grams of copper naphthenate having a copper content of 8% were blended and heated to 100 ° C and maintained at that temperature for 2 hours under shaking. The mixture was filtered on diatomaceous earth to provide an amount of 295 grams of product as a green oil having a copper content corresponding to 4.7% by weight.

Example 11

Part A: An amount of 406 grams of p-heptyl phenol, 204 dimethyl-propylene diaraine, 66 grams of paraformaldehyde and 250 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 2-3 hours. An amount of 37 144

water in the condenser. The solvent was removed and the mixture was filtered to provide 580 grams of product as an oil.

Part B; An amount of 178 grams of the product of Part A and 196 grams of copper naphthenate having a copper content of 8% was blended, heated to between 90-100 ° C and held at that temperature for 2 hours under stirring. The mixture was filtered on diatomaceous earth to afford an amount of 360 grams of product as a green oil having a copper content corresponding to 4.4% by weight.

Example 12

Part A: An amount of 406 grams of p-heptylphenol, 145 grams of 3,3'-diamino-N-methyl-dipropylamine, 66 grams of paraformaldehyde and 200 ml of toluene were mixed in a flask equipped with a condenser of water, warmed to reflux temperature and kept under reflux conditions for a period of 2-3 hours. An amount of 35 grams of water was collected in the condenser. The solvent was removed in vacuo. The mixture was filtered over diatomaceous earth to provide an amount of 510 grams of product as an oil.

Part B: An amount of 290 grams of the product of Part A and 393 grams of copper naphthenate having an 8% copper content was mixed and heated to a temperature comprised between 90-100 ° C and maintained at this temperature for 2 hours under stirring. The mixture was filtered on diatomaceous earth to give an amount of 628 grams of product as an oil having a copper content corresponding to 4.9% by weight.

Example 13

Part A: An amount of 406 grams of p-heptyl phenol, 206 grams of tetraethylene pentamine, 66 grams of paraformaldehyde and 500 ml of toluene were mixed in a flask equipped with a water condenser, warmed to the temperature of was refluxed and kept under reflux conditions for a period of 2-3 hours. An amount of 39 grams of water was collected in the condenser. The solvent was removed in vacuo. The mixture was filtered over diatomaceous earth to provide an amount of 595 grams of product as an oil.

Part B: An amount of 330 grams of the product of Part A and 393 grams of copper naphthenate having a copper content of 8% was blended, heated to 100-120 ° C and held therein. temperature for a period of time comprised between 2 and 3 hours. The mixture was filtered on diatomaceous earth to provide 613 grams of product as an oil and having a copper content corresponding to 3.77% by weight.

Example 14

Part A: An amount of 262 grams

266 grams of a t-dodecyl mercaptan hydroxide thioether and propylene oxide having a sulfur content corresponding to 12% by weight, 5 grams of p-toluenesulfonic acid and 200 ml of dodecyl succinic anhydride toluene, heated to reflux temperature and kept under reflux conditions for a period of time ranging from 8 to 10 hours. The solvent was removed and the mixture was filtered over diatomaceous earth to provide an amount of 520 grams of product as a light yellow oil.

Part B: An amount of 396 grams of the product of Part A, 41 grams of copper carbonate, 200 grams of a 100 N mineral oil and 250 ml of toluene were mixed in a flask equipped with a water condenser and heated to at a temperature in the range of 50-60 ° C. An amount of 50 grams of aqueous ammonium hydroxide solution was added to the mixture. The mixture was warmed to 90-110 ° C with nitrogen aeration. An amount of 50 grams of water was collected in the condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. The solvent was removed in vacuo. The mixture was filtered on diatomaceous earth to afford 590 grams of product as a green oil and having a copper content corresponding to 3.64% by weight. 147

% ·

Example 15

An amount of 410 grams of the sulfur dichloride reaction product was mixed with the propylene-phenol tetramer, 55 grams of copper carbonate and 250 ml of toluene in a flask equipped with a water condenser and heated to the temperature of 50 ° C. An amount of 58 grams of an aqueous ammonium hydroxide solution having an ammonia content corresponding to 28.9% by weight was added to the mixture under stirring. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 40 grams of water was collected in the condenser. The solvent was removed by evaporation. The mixture was filtered on diatomaceous earth to provide 390 grams of product as a dark brown oil and having a copper content corresponding to 7.14% by weight.

Example 16

An amount of 262 grams of dodecyl succinic anhydride, 2 grams of p-toluenesulfonic acid and 150 ml of toluene were mixed in a flask equipped with a water condenser. An amount of 106 grams of diethylene glycol was added to the mixture under stirring. The mixture was warmed to 70 to 80 ° C and held at that temperature for 1 hour. The temperature of the mixture was reduced to 50 ° C and 55 grams of copper carbonate was added thereto under stirring. 148

To the mixture was added 58 grams of an aqueous ammonium hydroxide solution. The mixture was warmed to 90 ° C and maintained at this temperature for 2 hours. A quantity of 42 grams of water was collected in the condenser. The solvent was removed from the mixture by heating the mixture to a temperature of 120 ° C and an absolute pressure of 20 mm Hg. The solvent was added to the mixture &quot; SC-100 &quot; to reduce viscosity. The mixture was filtered on diatomaceous earth to provide an amount of 515 grams of product as a blue-green oil and having a copper content corresponding to 3.7% by weight.

Example 17

Part A; An amount of 609 grams of p-heptyl phenol, 282 grams of paraformaldehyde and 150 grams of a 100 N mineral oil in a flask equipped with a water condenser was mixed. 5.4 grams of a 36 wt% aqueous sodium hydroxide solution was added to the mixture. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours with nitrogen aeration. A quantity of 23 grams of water was collected in the condenser. The mixture was diluted with toluene and 5% aqueous hydrochloric acid was added thereto to adjust the pH value of the mixture to 7. The water was removed from the mixture. The mixture was warmed to reflux temperature and kept under reflux conditions until removal of the remaining water. The solvent was removed in vacuo to provide 149

an amount of 815 grams of product.

Part B: An amount of 268 grams of the product of Part A and 275 grams of copper naphthenate having an 8% copper content was mixed and heated to 100 ° C and held at that temperature for 2 hours under stirring. The mixture was filtered on diatomaceous earth to give an amount of 415 grams of product as a green oil and having a copper content corresponding to 4.39% by weight.

Example 18

An amount of 46 grams of glyoxylic acid and 250 ml of toluene was mixed in a flask equipped with a water condenser. 140 grams of &quot; Armeen OL &quot; under stirring. An exothermic reaction has been observed which raises the temperature from room temperature to 50 ° C. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 16 grams of water was collected in the condenser. The mixture was cooled to 50 ° C. 28 grams of copper carbonate was added under stirring. An amount of 28 ml of an aqueous ammonium hydroxide solution having an ammonia content corresponding to 29% by weight was added to the mixture. The mixture was warmed to 80-90 ° C and held at that temperature for 2 hours. A quantity of 21 grams of water was collected in the condenser. 150

the solvent in vacuo. 100 grams of solvent &quot; SC-100 &quot; was added to the blend. The mixture was filtered on diatomaceous earth to provide an amount of 150 grams of product as a green oil and having a copper content corresponding to 4.15% by weight.

Example 19

Part A: An amount of 74 grams of glycidol, 95 grams of carbon disulfide and 200 ml of toluene were mixed in a flask equipped with a condenser. The flask was kept in an ice bath at a temperature below 20 ° C. A drop of 390 grams of &quot; Armeen 2C &quot; (a product of Armak identified as being a mixture of secondary fatty amines) for a period of from 1 to 1.5 hours. The mixture was stirred at ambient temperature for 2 to 3 hours. The solvent was removed in vacuo. The mixture was filtered over diatomaceous earth to give an amount of 519 grams of product as a light yellow oil.

Part B: An amount of 137 grams of Part A product and 196 grams of copper naphthenate having a copper content corresponding to 8% by weight in a flask was added, warmed to 80 to 90 ° The solution was stirred at this temperature for 2 hours under stirring. The mixture was filtered on diatomaceous earth to afford 325 grams of product of 151

f *! &gt; the aspect of a brownish oil and having a copper content corresponding to 4.68% by weight.

Example 20

An amount of 131 grams of dodecyl succinic anhydride, 69 grams of anthranilic acid and 250 ml of toluene was mixed in a flask equipped with a water condenser, heated to reflux temperature and kept under reflux conditions for a period between 2 and 3 hours. The solvent was evaporated from the mixture. An amount of 394 grams of copper naphthenate having a copper content corresponding to 8% by weight was added to the mixture. It was warmed to 80 ° C and maintained at that temperature for 2 hours under stirring. The mixture was filtered on diatomaceous earth to afford an amount of 500 grams of product as a green oil and having a copper content corresponding to 4.23% by weight.

Example 21

Part A: A quantity of 318 grams of 2-methylene-glutaronitrile, 342 grams of carbon disulfide and 250 ml of toluene were mixed in a flask equipped with a water condenser. Over a period of 2 hours an amount of 387 grams of dibutylamine was added dropwise maintaining the temperature of the mixture comprised between 10 and 15 ° C. The mixture was kept at room temperature under stirring for 2 hours. The mixture was warmed to 152 ° C.

temperature of 50 ° C and held at that temperature for 1 hour. The solvent was evaporated off from the mixture. The mixture was filtered over diatomaceous earth to afford 855 grams of product as an oil.

Part B; An amount of 80 grams of the product of Part A and 99 grams of copper naphthenate having a copper content corresponding to 8% by weight was blended in a flask and heated to 80 ° C and held therein temperature for 2 hours under stirring. The mixture was filtered to provide 155 grams of product as a green oil and having a copper content corresponding to 4.34% by weight.

Example 22

Part A; An amount of 145 grams of an aqueous solution of glyoxal having a glyoxal content corresponding to 40% by weight and 69 grams of NH 2 OH.HCl was mixed together with 200 ml of water and cooled to a temperature below 15 ° C using dry ice. An amount of 84 grams of sodium bicarbonate was added to the mixture over a period of 1.5 hours. The mixture was allowed to warm to room temperature and kept at that temperature for 10 hours under stirring. 278 grams of &quot; Armeen OL &quot; and 500 ml of toluene and added to the mixture. The mixture was heated to reflux temperature and kept under reflux conditions until distillation of water. 153

The solvent was removed from the mixture. The mixture was filtered over diatomaceous earth to afford 285 grams of product as an oil.

Part B: An amount of 167 grams of the product of Part A and 196 grams of copper naphthenate having a copper content corresponding to 8% by weight was mixed and heated to a temperature in the range of 70-80 ° C and was maintained at that temperature for 2 hours under stirring. The mixture was filtered on diatomaceous earth to give an amount of 350 grams of product as a brownish oil and having a copper content corresponding to 3.1% by weight.

Example 23

Part A; An amount of 530 grams of propylene-phenol tetramer, 66 grams of paraformaldehyde, 60 grams of ethylene diamine and 500 ml of toluene were mixed in a flask equipped with a water condenser. It was warmed to reflux temperature and kept under reflux conditions for 24 hours. An amount of 43 grams of water was collected in the condenser. The solvent was removed in vacuo. The mixture was filtered over diatomaceous earth to afford an amount of 580 grams of product as an oil.

Part B: An amount of 307 grams of the product of Part A, 100 grams of 100 N mineral oil and 100 ml of toluene were mixed in a flask equipped with a water condenser. 154

The mixture was warmed to 60-70 ° C and added with 28 grams of copper carbonate. An exothermic reaction occurred which allowed the temperature to rise to 90øC. The mixture was warmed to reflux temperature and kept under reflux conditions for 1 hour. An amount of 4.3 grams of water was collected in the condenser. The mixture was maintained at 140 ° C for 0.5 hours. The solvent was removed in vacuo. The mixture was filtered through diatomaceous earth to provide an amount of 330 grams of product as a green oil and having a copper content corresponding to 3.9% by weight.

Example 24

An amount of 205 grams of the product of part A of Example 7 was mixed with 200 ml of toluene in a flask equipped with a water condenser and heated to a temperature between 60 and 70 ° C. Eleven grams of copper carbonate was added under stirring. Then 11 ml of ammonium hydroxide was added. The mixture was warmed to reflux temperature and kept under reflux conditions for 1 hour. A quantity of 10 grams of water was collected in the condenser. The solvent was removed in vacuo. The mixture was filtered through diatomaceous earth to give an amount of 130 grams of product as a viscous oil and having a copper content corresponding to 3.9% by weight. 155

Example 25

An amount of 287 grams of dodecyl benzotriazole and 236 grams of copper naphthenate having a copper content corresponding to 8% by weight was mixed, heated to 90 ° C and maintained at that temperature for 2 hours. hours under agitation. The mixture was filtered through diatomaceous earth to give an amount of 495 grams of product as a green oil and having a copper content corresponding to 3.41% by weight.

Example 26

Part A: An amount of 106 grams of benzaldehyde was mixed with 200 ml of toluene in a flask equipped with a water condenser. An amount of 3 grams of ethylene diamine was mixed with 100 ml of toluene. The ethylene diamine / toluene mixture was added to the benzaldehyde / toluene mixture dropwise and at ambient temperature over a period of 1 hour. An exothermic reaction was observed in the mixture which raised the temperature to between 30 and 40Â ° C. The mixture was then heated to reflux temperature and kept under reflux conditions for 0.5 hours. An amount of 18 grams of water was collected in the condenser. The solvent was removed in vacuo to provide an amount of 118 grams of product as an orange oil.

Part B: An amount of 607 grams

of the product of Part A, 157 grams of copper naphthenate having a copper content corresponding to 8% by weight, 18 grams of the reaction product of polyisobutenyl succinic anhydride (having an average molecular weight of 950) with a polyamine commercially available and which is the residual product of distillation, and 100 grams of solvent &quot; SC-100 &quot; and heated to between 50 and 60 ° C and maintained at that temperature under a nitrogen atmosphere for 1 hour under stirring. The mixture was filtered on diatomaceous earth to afford an amount of 305 grams of product as a green oil and having a copper content corresponding to 3.1% by weight.

Example 27

Part A: An amount of 265 grams of propylene-phenol tetramer, 123 grams of NH (CH 2 CH 2 CN) 2, 33 grams of paraformaldehyde and 250 ml of toluene were mixed in a flask equipped with a water condenser. It was warmed to reflux temperature and kept under reflux conditions for 3 hours. A quantity of 20 grams of water was collected in the condenser. The mixture was warmed to reflux temperature and held at that temperature. The solvent was evaporated in vacuo. The mixture was filtered over diatomaceous earth to afford 370 grams of product as an oil.

Part B: An amount of 200 grams of product of Part A was mixed, 158 grams of copper naphthenate 157

having a copper content corresponding to 8% by weight and 35 grams of the reaction product of polyisobutenyl succinic anhydride (950 average molecular weight) with a commercially available polyamine and which is a residual distillation product, was heated to a temperature of 80 ° C and maintained at that temperature for 1 hour under stirring. The mixture was piloted to provide 370 grams of product as a dark green oil and having a copper content corresponding to 2.24% by weight.

Example 28

An amount of 254 grams of p-polyisobutenyl (940) -o-amino-phenol, 10.6 grams of benzaldehyde and 250 ml of toluene was mixed in a flask equipped with a water condenser . The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. A quantity of 1.8 grams of water was collected in the condenser. The mixture was allowed to cool to room temperature. An amount of 4.2 grams of copper carbonate and 5 ml of a 30% aqueous solution of ammonium hydroxide was added to the mixture. The mixture was warmed to reflux temperature and kept under reflux conditions for 1 hour. An amount of 5 grams of water was collected in the condenser. The solvent was removed in vacuo. The mixture was filtered through diatomaceous earth to afford 260 grams of product as a brown oil and having a copper content of 0.22% by weight.

Example 29

Part A: An amount of 69 grams of NH 2 OH.HCl was mixed with 300 ml of methanol. An amount of 80 grams of sodium hydroxide was mixed with 300 ml of methanol. The sodium hydroxide / methanol solution was added to the NH2 OH.HCl / methanol solution dropwise over a period of 2 hours with the mixture maintained below 15 ° C. 269 grams of methyl bromide was added dropwise over a period of 0.5 hours to the mixture maintaining the temperature below 15Â ° C. The mixture was allowed to warm to room temperature and maintained at that temperature for 3 to 5 hours under stirring. The mixture was filtered to provide an amount of 210 grams of product.

Part B: An amount of 81 grams of Part A product was blended, 79 grams of copper naphthenate having a copper content corresponding to 8% by weight and 40 grams of solvent &quot; SC-100 &quot; was heated to at a temperature in the range of 80-90Â ° C and maintained at that temperature for 21 hours under stirring to provide 175 grams of product as a dark green gel and having a copper content of 1, 93% by weight. 159 &lt; *

THE

Example 30

Part A; An amount of 795 grams of propylene-phenol tetramer and 99 grams of paraformaldehyde was mixed with toluene in a flask equipped with a water condenser. An amount of 109 grams of butylamine was added to the mixture. It was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 60 grams of water was collected in the condenser. The solvent was removed in vacuo. The mixture was filtered on diatomaceous earth to provide an amount of 938 grams of product as an oil.

Part B: 188 grams of product of Part A, 11 grams of copper carbonate and 150 ml of toluene were blended and heated to 50 ° C in a flask equipped with a water condenser. To the mixture was added 10 ml of 30% aqueous ammonium hydroxide solution. The mixture was warmed to reflux temperature and kept under reflux conditions for 2 hours. An amount of 12 grams of water was collected in the condenser. The solvent was removed from the mixture in vacuo. The mixture was filtered through diatomaceous earth to afford 155 grams of product as a viscous brownish green oil and having a copper content corresponding to 3.98% by weight.

Example 31

Part A: An amount of 1143 grams

of propylene-phenol tetramer and 482 grams of acetic anhydride was heated to 120 ° C and held at that temperature for 5 hours. The mixture was evaporated in vacuo and at 120 ° C at an absolute pressure of 10mm Hg for 1.5 to provide an amount of 1319 grams of the product in the liquid state and brown

Part B: 44.7 grams of AICI3 and 200 grams of mineral essences were mixed at room temperature under a nitrogen atmosphere. An amount of 154 grams of the product of Part A was added over a period of 0.5 hours. An exothermic reaction was added to the mixture which raised the temperature to 37øC. The mixture was then heated to 142 ° C and kept at that temperature for 25 hours. The mixture was cooled to 80 ° C and 50 grams of water was added. The mixture was warmed to 110-115 ° C and maintained at that temperature for 1.25 hours and then allowed to cool to room temperature. The mixture was washed with water, mineral oils and isopropyl alcohol. The mixture was evaporated under heating at 147 ° C and at an absolute pressure of 7 mm Hg. The mixture was filtered on diatomaceous earth to provide an amount of 121 grams of liquid, clear, dark red liquid.

Part C: An amount of 17.7 grams of sodium hydroxide in 108.8 grams of water was mixed. Was mixed 161

an amount of 40 grams of the product of part B, 32 ml of n-butyl alcohol and 27.7 grams of (HONH2) 2H2 SO4 at room temperature. A solution of sodium hydroxide was added to the mixture and the mixture was warmed to 35øC and kept at that temperature for 5 hours under a nitrogen atmosphere. The mixture was allowed to cool to room temperature and kept at that temperature overnight. The mixture was warmed to 35 ° C and held at that temperature for 1 hour. 26.55 grams of acetic acid was added over a period of 0.05 hours. An exothermic reaction was observed in the mixture which caused the temperature to rise to 40øC. The mixture was allowed to cool to room temperature under stirring. 100 ml of toluene was added. The mixture was washed 3 times using in each wash 100 ml of water. The mixture was introduced into a flask equipped with a water condenser, stirred, heated under a nitrogen atmosphere to reflux temperature and kept under reflux conditions until the water was removed. The mixture was cooled and filtered. The filtrate was removed to give an amount of 41 grams of the product as a clear, dark brown liquid.

Part D: An amount of 4.62 grams of copper carbonate and 50 grams of toluene was mixed in a flask equipped with a water condenser. An amount of 38 grams of the product of Part C was mixed with 90 grams 162

of toluene and added to the mixture consisting of copper carbonate and toluene under stirring over a period of 0.2 hours, the mixture always being kept at room temperature. The mixture was heated to reflux temperature and kept under reflux conditions for 1 hour and then cooled to 50Â ° C. An amount of 4.5 grams of ammonium hydroxide was added to the mixture. The mixture was heated to reflux temperature and kept under reflux conditions until 4.6 grams of water were collected in the condenser. The mixture was allowed to cool to room temperature and filtered over diatomaceous earth to afford 42 grams of liquid, viscous, dark brown product and having a copper content corresponding to 6.04% by weight. Weight.

Example 32

Part A: An amount of 842 grams of propylene-phenol tetramer and 300 ml of toluene was mixed in a flask equipped with a water condenser. To the mixture was added 96 grams of ethylene diamine under stirring maintaining the mixture aerated with nitrogen at the rate of 0.0283 m (1 cubic foot) per hour. An exothermic reaction was observed in the mixture which caused the temperature to rise to 40øC. An amount of 96.4 grams of paraformaldehyde was added to the mixture. The mixture was warmed to 110 to 120 ° C under stirring and maintained at that temperature for 4 hours. 163

* 7

An amount between 56 and 57.6 grams of water was collected in the condenser. The toluene was removed from the mixture by maintaining the mixture at a temperature between 90 and 110Â ° C and at the absolute pressure of 10 mm Hg for 1 hour to provide an amount of 960 grams of liquid, viscous and amber colored product.

Part B: A quantity of 121 grams of the product of part A, 130.52 grams of toluene and 13.56 grams of copper carbonate having a copper content corresponding to 56.2% by weight in a flask equipped with a condenser. The mixture was warmed to 50 ° C and 39.3 grams of concentrated aqueous ammonium hydroxide solution was added to the mixture over a period of 0.25 minutes. The mixture was maintained at 50 ° C for a further 0.25 minutes. The mixture was heated to 120Â ° C and so held for 1.5 hours while passing air through the mixture at a rate of 1 cubic feet (0.0283 m) per hour. The mixture was maintained at 120 ° C for 2 hours. 28.9 grams of water was collected in the condenser. The mixture was then further maintained at 120 ° C for 2 hours. The mixture was then warmed to 155 ° C by collecting the toluene in the condenser and then cooled to 100 ° C. An amount of 24.35 grams of dodecyl alcohol was added to the mixture and the mixture was maintained at 100 ° C for 0.25

minutes under stirring. The mixture was filtered on diatomaceous earth at a temperature of 100 ° C to provide an amount of 116.9 grams of product having a copper content corresponding to 5.14% by weight.

Example 33

Part A: An amount of 175 grams of &quot; Duomeen &quot; (an Armak product identified as N-oleyl-1,3-diamino propane) in a flask equipped with a water condenser. 36.5 grams of diethyl oxalate was added thereto and an exothermic reaction was observed in the mixture which caused the temperature to rise to 69øC. The mixture was warmed to 120 ° C and maintained at that temperature for 2 hours. An amount of 17.9 grams of ethanol was collected in the condenser. The mixture was allowed to cool to room temperature to provide 190.8 grams of the product as a white solid.

Part B; A quantity of 177.9 grams of the product of part A was charged into a flask equipped with a water condenser and heated to 80 ° C. To this product was added 70 grams of toluene and 21.7 grams of copper carbonate having a copper content corresponding to 56.2% by weight. To the mixture was added 28.2 grams of concentrated aqueous ammonium hydroxide solution dropwise over a period of 0.1 hours. The mixture was heated to reflux temperature and 165 DEG.

kept at that temperature for 2 hours. The mixture was aerated with nitrogen at the rate of 0.5 cubic feet (0.514 cubic feet) per hour for 0.5 hours. 30 grams of solvent &quot; SC-100 &quot; and 10 grams of diatomaceous earth. 27 grams of dodecyl alcohol was added to the mixture. The mixture was warmed to 100 ° C and filtered to provide 286.5 grams of product as a blue gel having a copper content corresponding to 3.34% by weight.

Example 34

An amount of 195 grams of salicyl aldehyde, 528 grams of "Duomeen O" and 300æl of toluene in a flask equipped with a water condenser. The mixture was warmed to reflux temperature and kept under refluxing conditions with nitrogen aeration for 3 hours. An amount of 30 grams of water was collected in the condenser. The mixture was cooled to 60 ° C. An amount of 59 grams of copper carbonate was added to the mixture. The mixture was heated to reflux temperature and kept under reflux conditions for 3 hours. A quantity of 15 grams of water was collected in the condenser. The mixture was allowed to cool to room temperature. The solvent was removed from the mixture by heating that mixture at 120Â ° C and at the absolute pressure of 10 mm Hg for 3 hours. The mixture was filtered over diatomaceous earth at 120 ° C to afford a

amount of 697 grams of product having a copper content corresponding to 3.6% by weight.

Example 35

Part A: A quantity of 304 grams of p-heptyl phenol, 525 grams of "Duomeen T", 50 grams of paraformaldehyde and 350 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was heated to reflux temperature and kept under reflux conditions for 3 hours. An amount of 35 grams of water was collected in the condenser. The solvent was removed from the mixture in vacuo. The mixture was filtered over diatomaceous earth to provide 729 grams of product as a light brown oil.

Part B: An amount of 112 grams of product of Part A of this Example 35 was blended, 24 grams of product of Example 30, Part A, 23 grams of &quot; 30% Cu Cem All &quot; and 40 grams of solvent &quot; SC-100 &quot; and heated to 80 ° C under stirring and maintained at that temperature for 2 hours under a nitrogen atmosphere. The product was filtered on diatomaceous earth to provide an amount of 185 grams of product as a brown oil having a copper content corresponding to 3.5% by weight.

Example 36

An amount of 25 grams of the product of Example 30, Part A, 112 grams of product of Example 35, Part A, and 79 grams of copper naphthenate having a 167

copper content corresponding to 8% by weight, heated to between 80 and 90 ° C under stirring and maintained at that temperature under a nitrogen atmosphere for 2 hours. The mixture was filtered on diatomaceous earth to provide 200 grams of product as a dark green oil having a copper content corresponding to 2.25% by weight.

Example 37

Part A: An amount of 262 grams of dodecyl succinic anhydride and 150 ml of toluene was mixed in a flask equipped with a water condenser and heated to 70 to 80 ° C. An amount of 60 grams of ethylene diamine was mixed with 50 ml of toluene. The ethylene diamine / toluene mixture was added to the dodecyl succinic anhydride / toluene mixture over a period of from 0.5 to 1 hours. The mixture was warmed to reflux temperature and kept under reflux conditions for 1 hour. The solvent was removed from the mixture by heating the mixture to 130 ° C and the absolute pressure of 20 mm Hg. 50 grams of 100 N mineral oil was added to the mixture under stirring to provide an amount of 350 grams of product as a light orange oil.

Part B: An amount of 186 grams of Part A product and 118 grams of copper naphthenate having a copper content corresponding to 8% by weight was mixed, and heated to 70-80 ° C under stirred and maintained at that temperature for 2 hours to provide 300 grams of product as a blue oil having a copper content corresponding to 3.27% by weight.

Example 38

Part A; An amount of 530 grams of propylene-phenol tetramer, 66 grams of paraformaldehyde, 61 grams of ethanol-amine and 350 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was heated to reflux temperature and kept under reflux conditions for 2 hours. A quantity of 41 grams of water was collected in the condenser. The solvent was evaporated in vacuo. The mixture was filtered over diatomaceous earth to give an amount of 600 grams of product as a viscous oil.

Part B: A quantity of 131 grams of dodecyl succinic anhydride was mixed with 100 ml of toluene. The mixture was warmed to 70 to 80 ° C and 15 grams of ethylene diamine was added over a period of 0.5 hours. The mixture was warmed to between 100 and 110 ° C and kept at that temperature under stirring for 1 hour. The solvent was removed from the mixture in vacuo. The mixture was allowed to cool to room temperature. An amount of 118 grams of copper naphthenate having a content of 169

Ϊ copper corresponding to 8% by weight and 31 grams of the product of Part A of this Example 38 with stirring. The mixture was warmed to 80 ° C and kept at that temperature for 2 hours under stirring to provide 290 grams of product having a copper content corresponding to 3.16% by weight.

Example 39

Part A: A quantity of 203 grams of p-heptyl phenol, 350 grams of "Duomeen O", 33 grams of paraformaldehyde and 200 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was heated under reflux conditions for a period of from 3 to 4 hours. A quantity of 21 grams of water was collected in the condenser. The solvent was removed from the mixture in vacuo. The mixture was pelleted on diatomaceous earth to give an amount of 558 grams of product as a light yellow oil.

Part B: An amount of 56.5 grams of product of Part A of this Example 39 was blended, 61.6 grams of the product of Example 38, Part A and 78.7 grams of copper naphthenate having a copper content corresponding to 8% by weight and heated to 80-90 ° C and maintained at that temperature under stirring for 2 hours. The mixture was filtered through diatomaceous earth to provide an amount of 170 grams of product as a dark brown oil having a 170

copper content corresponding to 2.99% by weight.

Example 40

Part A: An amount of 175 grams of &quot; Duomeen &quot; and 76 grams of carbon disulfide with 150 ml of toluene and 100 ml of isopropyl alcohol at a temperature below 15 ° C. 53 grams of 2,4-dicyano-butene-1 was added to the mixture. The mixture was warmed to room temperature and kept at that temperature for 1 hour. The mixture was then warmed to 40-50 ° C and maintained at that temperature for 2 hours. The solvent was removed in vacuo. The mixture was filtered over diatomaceous earth to provide 245 grams of product as a dark orange oil.

Part B: An amount of 133 grams of the product of Part A and 157 grams of copper naphthenate having a copper content corresponding to 8% by weight was blended, heated to 80 ° C and held at that temperature under stirring for 2 hours. The mixture was filtered on diatomaceous earth to give 266 grams of product as a dark oil and having a copper content corresponding to 3.5% by weight.

Example 41

An amount of 200 grams of product of Part A of Example 6 was blended, 36 grams of copper carbonate and 171 grams

250 ml of toluene in a flask equipped with a water condenser. The mixture was heated to 60 ° C and 38 grams of an aqueous ammonium hydroxide solution was added. The mixture was kept under nitrogen aeration at the rate of 0.085 m (3 cubic feet) per hour for 2 hours. The mixture was heated to 80-90 ° C. 25 grams of water was collected in the condenser. The mixture was warmed to reflux temperature and kept under reflux conditions for 0.5 hours. The toluene was removed from the mixture by heating the mixture to 120 ° C and the absolute pressure of 20 mm Hg. The mixture was filtered to provide an amount of 150 grams of product as a brownish oil and having a copper content corresponding to 0.77% by weight.

Example 42

An amount of 37 grams of glycidol, 76 grams of carbon disulfide and 100 ml of toluene were mixed in a flask equipped with a water condenser. The flask was kept in an ice bath at a temperature below 15 ° C. Then 100 ml of isopropyl alcohol was added. For 1 hour 175 grams of &quot; Duomeen O &quot; was added dropwise. The mixture was stirred at room temperature for 1 hour. The mixture was warmed to 40-50 ° C and maintained at that temperature for 2 hours. The solvent was removed in vacuo. An amount of 393 grams of 172

naphthenate having a copper content corresponding to 8% by weight. The mixture was warmed to 70 to 80 ° C and kept at that temperature for 2 hours under stirring. The mixture was filtered to provide an amount of 630 grams of product as an oil and having a copper content corresponding to 4.88% by weight.

Example 43

An amount of 103 grams of o-nitrophenol and 33 grams of paraformaldehyde in toluene was mixed in a flask equipped with a water condenser. Over a period of 0.5 hours 262 grams of &quot; Duomeen O &quot; was added. The mixture was warmed to reflux temperature and kept under reflux conditions for a period of 2 to 3 hours. A quantity of 15 grams of water was collected in the condenser. The mixture was allowed to cool to room temperature. An amount of 33 grams of copper carbonate was added. The mixture was heated to reflux temperature and kept at that temperature for 2 hours until the water was removed. 25 ml of volatiles were removed from the mixture by evaporation in vacuo. The mixture was filtered on diatomaceous earth to afford 380 grams of product as a green oil and having a copper content corresponding to 4.14% by weight. 173

Example 44

Part A: An amount of 108 grams of phenylhydrazine was mixed with 20 ml of ethanol at room temperature. An amount of 128 grams of 2-ethylhexanal was added dropwise to the mixture under stirring. An exothermic reaction was observed in the mixture which raised the temperature to 25 ° C. The mixture was stirred for 0.5 hour and allowed to cool to room temperature. Additional ethanol was added until a clear yellow solution was obtained.

Part B: An amount of 130 grams of dodecyl aniline was mixed with 300 ml of toluene at room temperature. The mixture was cooled to 0 ° C. To the mixture was added 60 grams of concentrated hydrochloric acid (38% by weight) and an exothermic reaction was observed in the mixture which raised the temperature to 22 ° C. The mixture was cooled to 0 ° C. An amount of 40 grams of NaNO2 was dissolved in 100 ml of water. The resulting NaNO2 solution was added to the mixture dropwise over a period of 0.75 hours with the temperature of the mixture below 5 ° C. To the mixture was added 100 ml of textile essences (a low boiling hydrocarbon solvent) to facilitate the dissolution of NaNO2-

Part C: An amount of 300 grams of a concentrated aqueous NaOH solution (50% by weight) was mixed with 174

1000 ml of ethanol to form a solution. Simultaneously, 109 grams of the product of Part A and 136 grams of the product of Part B were added to the stirred NaOH / ethanol solution. The resulting mixture was kept at room temperature overnight. An amount of 500 ml of hexane and 500 ml of water was added to the mixture, resulting in the formation of an aqueous layer and an organic layer. The organic layer was separated from the aqueous layer, washed three times with water, dried, filtered and stripped to provide an amount of 60 grams of product.

Part D: An amount of 48.8 grams of the product of Part C was dissolved in 50 ml of acetone and heated to 50 ° C to provide a first solution. 10 grams of cupric acetate was dissolved in a mixture of 150 ml of water and 50 ml of methanol to provide a second solution. The second solution was heated at 50 ° C. The first solution was mixed with the second solution to provide a third solution. 100 ml of water and 100 ml of naphtha were added to the third solution, followed by the formation of an aqueous layer and an organic layer. The organic layer was separated from the aqueous layer. 100 ml of water and 100 ml of naphtha were added to the separated organic layer, followed by the formation of an aqueous layer and an organic layer. The organic layer was separated from the aqueous layer 175. The separated organic layer was dried, filtered and removed to give an amount of 44 grams of product having a copper content corresponding to 2.21% by weight.

Example 45

An amount of 63 grams of the product of Part A of Example 30 was 56.5 grams of product of Part A of Example 39 and 78.7 grams of copper naphthenate having a copper content corresponding to 8% by weight, warmed to 70 to 80 ° C under stirring and maintained at that temperature for 2 hours. The mixture was filtered on diatomaceous earth to give an amount of 180 grams of product as a green oil having a copper content corresponding to 3.2% by weight.

Example 46

Part A: 265 grams of propylene-phenol tetramer, 350 grams of "Duomeen O", 33 grams of formaldehyde and 200 ml of toluene were mixed in a flask equipped with a water condenser. The mixture was heated under reflux conditions for a period of from 3 to 4 hours. 22 grams of water was collected in the condenser. The solvent was removed from the mixture in vacuo. The mixture was filtered over diatomaceous earth to provide an amount of 628 grams of product as an oil. 176

Part B: An amount of 63 grams of product of Part A of this Example 46 was blended, 63 grams of the product of Part A of Example 30 and 708.7 grams of copper naphthenate having a copper content corresponding to 8% by weight , warmed to 70 to 80 ° C under stirring and maintained at that temperature for 2 hours. The mixture was filtered over diatomaceous earth to provide an amount of 195 grams of product as a dark green oil having a copper content corresponding to 2.98% by weight.

Example 47

An amount of 144 grams of the borane product of the ethylene polyamine reaction and polyisobutenyl succinic anhydride (950 average molecular weight) and 196 grams of copper naphthenate having a copper content corresponding to 8% by weight, in 250 ml of toluene was heated to reflux temperature and kept at that temperature under an atmosphere of nitrogen for 1 hour. The mixture was removed in vacuo and filtered over diatomaceous earth to provide an amount of 305 grams of product as a green oil.

Example 48

Part A: An amount of 561 grams of the reaction product of polyisobutenyl succinic anhydride (950 average molecular weight) and a commercially available polyamine which is a fractional distillation residual product is mixed with 500 ml of toluene. 23 grams of H3 BO3 was added thereto. The mixture was heated at 60 ° C under stirring to a flask equipped with a water condenser. The mixture was heated to reflux temperature and kept under reflux conditions until 30 grams of water was collected in the condenser. The temperature of the mixture was adjusted to 200Â ° C and an additional 5 grams of water was collected in the condenser. The solvent of the mixture was removed in vacuo. The mixture was filtered over diatomaceous earth to give an amount of 722 grams of product as a brown oil.

Part B: An amount of 152 grams of Part A product and 158 grams of copper naphthenate having a copper content corresponding to 8% by weight was blended / heated to a temperature comprised between 80 and 90 ° C and was maintained at that temperature under a nitrogen atmosphere for a period of from 2 to 3 hours under stirring. The mixture was filtered on diatomaceous earth to give an amount of 320 grams of product as a green oil.

Example 49

An amount of 110 grams of salicylaldehyde, 297 grams of &quot; Duomeen T &quot; and 400 ml of xylene in a flask equipped with a water condenser. The mixture was heated under a nitrogen atmosphere to its reflux temperature and kept under reflux for 4 hours.

hours. An amount of 18.5 grams of water was collected in a water condenser. The mixture was cooled to the temperature of 149Â ° C. 149 grams of copper carbonate was added. The mixture was warmed to its reflux temperature and kept under reflux conditions for 8 hours. An amount of 16.5 grams of water was collected in the water condenser. The mixture was allowed to cool to room temperature. The mixture was filtered and then evaporated by heating at 130øC and at the absolute pressure of 30 mm Hg for 3 hours. The mixture was filtered on diatomaceous earth at 130 ° C to provide 393 grams of product having a copper content corresponding to 7.56% by weight.

Example 50

An amount of 130.28 grams of 2-hydroxyacetophenone, 315.72 grams of &quot; Duomeen T &quot; and 400 ml of xylene in a flask equipped with a water condenser. The mixture was heated to reflux under stirring under a nitrogen atmosphere and kept under reflux conditions for 3 hours. An amount of 16.2 grams of water was collected in the water condenser. 74.25 grams of copper carbonate was added thereto. The mixture was warmed to its reflux temperature under a nitrogen atmosphere and kept under reflux conditions for 3 hours. An amount of 13.6 grams of water was collected in the water condenser. An amount of 179

of 500 ml of toluene. The mixture was allowed to cool to room temperature to afford 345.7 grams of product having a copper content of 6.154% by weight.

Example 51

An amount of 122 grams of salicylaldehyde, 265 grams of &quot; Duomeen C &quot; and 120 ml of xylene in a flask equipped with a water condenser. The mixture was warmed to its reflux temperature under a nitrogen atmosphere and kept under reflux conditions for 3 hours. A quantity of 17 grams of water was collected in the water condenser. 608 grams of copper carbonate was added thereto. The mixture was warmed to its reflux temperature under a nitrogen atmosphere and kept under reflux conditions for 6 hours. A quantity of 13 grams of water was collected in the water condenser. The mixture was allowed to cool to room temperature. The mixture was pelleted and the solvent was removed. The mixture was filtered on diatomaceous earth at 80 ° C to provide 384 grams of product having a copper content corresponding to 5.80% by weight.

Example 52

Part A: An amount of 132.8 grams of propylene-phenol tetramer, 53.3 grams of (NH2 OH) 2H2 SO4 and 98.8 grams of toluene were mixed. An amount of 52 grams of a concentrated aqueous solution (at 180 DEG C.) was added to the mixture.

50% by weight) of NaOH. An exothermic reaction raising the temperature to 40 ° C was formed in the mixture and an aqueous layer containing white solids formed. The mixture was stirred for 10 minutes. The aqueous layer was separated from the mixture. The remaining organic layer was added to a flask equipped with a water condenser and heated to 70 ° C under stirring. An amount of 17.45 grams of paraformaldehyde was added to the organic layer and an exothermic reaction was conducted in the mixture which raised the temperature to 87øC. This mixture was then heated to 100 ° C for 1 hour. The mixture was then warmed to its reflux temperature and kept under reflux conditions until 14.8 grams of water were collected in the condenser. 211.72 grams of product were thus obtained. The product was obtained in the liquid state and with a red color.

Part B: A quantity of 211.72 grams of Part A product was blended, 19.21 grams of copper carbonate having a copper content corresponding to 56.2% by weight and 78 grams of toluene in a flask equipped with a condenser. The mixture was warmed to 50 ° C. 48.2 grams of a concentrated aqueous ammonium hydroxide solution was added dropwise to the mixture. The mixture was warmed to the reflux temperature corresponding to 70 ° C and maintained at that temperature with atomospheric aeration at the rate of 0.0182 m (0.5 cubic feet) per hour until 181

38.2 grams of NH 4 OH and 86.27 grams of an organic substance were collected in the condenser. 68.8 grams of iso-octanol was added to the mixture. The mixture was warmed to 150Â ° C and then cooled to 90Â ° C. The mixture was filtered on diatomaceous earth to provide an amount of 195.3 grams of liquid and dark brown product having a copper content of 1.64% by weight.

Example 53

An amount of 150 grams of salicylaldehyde, 332 grams of &quot; Armeen OL &quot; and 500 ml of toluene in a flask equipped with a water condenser. The mixture was heated to reflux temperature and kept under reflux conditions (maximum temperature is 125øC) with nitrogen aeration for 4 hours. 22 grams of water was collected in the condenser. The mixture was allowed to cool to room temperature. An amount of 98 grams of copper acetate was added to the mixture. The mixture was heated to its reflux temperature which is 125øC and kept under reflux conditions for 7 hours. The mixture was allowed to cool to room temperature. The solvent was removed from the mixture by heating that mixture at 115øC and at the absolute pressure of 25 mm Hg for 3 hours. The mixture was filtered on diatomaceous earth at 90-95øC to provide an amount of 469-182

grams of product having a copper content corresponding to 6.30% by weight.

Example 54

Part A: 212.5 grams of propylene-phenol tetramer, 24 grams of ethylene diamine and 108 grams of toluene were mixed in a flask equipped with a water condenser. The mixture was warmed to 70 ° C and 27.4 grams of paraformaldehyde was added thereto. An exothermic reaction was conducted in the mixture which raised the temperature to 95 ° C. The mixture was warmed to its reflux temperature and kept under reflux conditions for 3.5 hours. Airless air was maintained at a rate of 0.0182 m (0.5 cubic feet) per hour and at 136 ° C for 0.5 hours. An amount of 16.8 grams of water was collected in the condenser to provide 326.4 grams of product. The product was obtained in the liquid state and with an orange-red color.

Part B: An amount of 256 grams of the product of Part A was blended, 23.7 grams of copper carbonate having a copper content corresponding to 56.2% by weight and 69.2 grams of toluene in a flask equipped with a condenser. The mixture was warmed to 50 &quot; and 29.6 grams of an aqueous ammonium hydroxide solution was added dropwise over a period of 15 minutes. Air was passed through the mixture at a rate of 0.0182 m (0.5 cubic feet) per hour. The mixture was heated to 120 ° C and maintained at that temperature for 3 hours. The mixture was allowed to cool to room temperature and then warmed to 120 ° C and maintained at that temperature for 2 hours. An amount of 50 ml of toluene was removed from the mixture. 74.8 grams of solvent &quot; SC-100 &quot; was added. 63.3 grams of dodecyl alcohol was added. The mixture was warmed to 150 ° C and held at that temperature for 4 hours. The mixture was filtered on diatomaceous earth to give an amount of 287.9 grams of product having a copper content corresponding to 3.47% by weight.

Example 55

A: 212.15 grams of propylene-phenol tetramer and 60 grams of t-butyl amine were mixed in a flask equipped with a water condenser. The mixture was warmed to 70 ° C and 27.8 grams of paraformaldehyde was added thereto. A foam was formed into the mixture and a foam separator was added. The mixture was warmed to 90 ° C and held at that temperature for 15 minutes. A quantity of 150 ml of foam was collected from the foam separator. The foamless material was again introduced into the flask. The mixture was purified with a nitrogen stream at the rate of 0.0745 m (2.5 cu.ft.) per hour with the final temperature being 140Â ° C. A quantity of 14.8 grams of water was collected in the condenser. Removed from the mixture 184

104.2 ml of toluene to provide an amount of 339 grams of product in the liquid state and a golden yellow color.

Part B; An amount of 169.5 grams of the product of Part A, 15.02 grams of copper carbonate having a copper content corresponding to 56.2% by weight, 34.5 grams of iso-octanol and 67.8 grams grams of toluene in a flask equipped with a water condenser. The mixture was heated to 50 ° C and dropwise over a period of 15 minutes, to which was added 36.6 grams of aqueous ammonium hydroxide solution (29% by weight of ammonia) . The mixture was kept under atmospheric aeration at the rate of 0.0182 m (0.5 cubic feet) per hour and was heated to the reflux temperature corresponding to 120 ° C. The mixture was maintained at 120 ° C for 2 hours and then allowed to cool to room temperature. The mixture was then warmed to reflux temperature and held at that temperature for 7 hours. The mixture was allowed to cool to room temperature and kept at that temperature for 3 days. The mixture was heated to 150 ° C. An amount of 31.4 grams of water was removed. The mixture was allowed to cool to 80Â ° C and 57.5 grams of solvent &quot; SC-100 &quot;. The mixture was filtered on diatomaceous earth to afford 215 grams of product having a copper content corresponding to 2.88% by weight. 185

Example 56

An amount of 169.5 grams of the product of Part A of Example 55, 26.61 grams of copper acetate and 103.4 grams of toluene was mixed in a flask equipped with a water condenser. Air was passed through the mixture at the rate of 0.0182 m (0.5 cubic feet) per hour. The mixture was heated to the reflux temperature corresponding to 120 ° C and kept under reflux conditions for 3 hours. The mixture was allowed to cool to room temperature and then warmed to reflux temperature and kept at that temperature for 7 hours. The mixture was allowed to revert to room temperature and held at that temperature for 3 days. The mixture was heated to 145øC and 9.35 grams of a mixture of acetic acid and water was collected in the condenser.

Example 57

Amount of 11.66 parts of "30% Cu Cem All", 37.33 parts of "Henkel Aloxime 800" was mixed. (a Henkel product identified as being 90 wt% per dodecyl-salicyl aldoxime, the remainder being unreacted substances and by-products) and 37.96 parts of solvent &quot; SC-100 &quot;, to room temperature. To the mixture was added 13.05 parts of the product of Part A of Example 7 under stirring to provide the desired product.

Example 58

An amount of 5912 grams of 186 &quot; Henkel Aloxime 800 &quot; and 1601 grams of solvent &quot; SC-100 &quot; in a flask equipped with a water condenser. Nitrogen was passed through the mixture at the rate of 0.00566 m (0.2 cu.ft.) per hour. The mixture was heated to 50 ° C under stirring. 200 grams of distilled water was added thereto.

The passage of nitrogen was stopped by the mixture. An amount of 876 grams of basic copper carbonate in successive amounts of 20-40 grams was added to the mixture over a period of 2.5 hours. The mixture was kept at 50 ° C for one hour. A stream of nitrogen was passed through the mixture at the rate of 0.0566 m (0.2 cubic feet) per hour. The mixture was heated to 125Â ° C for a period of 3 hours and 423 grams of water was collected. The mixture was cooled to 60 ° C. 60 grams of diatomaceous earth was added thereto. The mixture was filtered to provide 7718 grams of a fairly dark brown filtrate having a copper content of 6.09% by weight.

Example 59

A quantity of 400 grams of solvent was introduced into a flask equipped with a water condenser &quot; SC-100 &quot; and heated to 50 ° C under stirring. 219 grams of basic copper carbonate was added thereto. An amount of 1478 grams of &quot; Henkel Aloxime 800 &quot; at the temperature of 60 ° C and added to the mixture over a period of two hours. The mixture was heated to 120 ° C under nitrogen.

shaking. The reaction water was collected on the condenser. The mixture was cooled to 60 ° C. The mixture was filtered to provide an amount of 1902 grams of the filtered product having a copper content corresponding to 6.34% by weight.

Example 60

Part A: 609 grams of heptyl phenol, 1050 grams of "Duomeen T", 99 grams of paraformaldehyde and 500 ml of toluene were blended and heated under reflux conditions in a flask equipped with a water condenser for 3 hours. A quantity of 68 ml of water was collected in the condenser. The mixture was evaporated in vacuo and filtered to provide 1700 grams of product as an oil.

Part B; An amount of 1590 grams of propylene-phenol tetramer, 183 grams of ethanolamine, 198 grams of paraformaldehyde and 800 ml of toluene were mixed and heated under reflux conditions in a flask equipped with a water condenser for a period of time 2 and 3 hours. A quantity of 122 ml of water was collected in the condenser. The mixture was evaporated in vacuo and filtered to provide an amount of 1800 grams of product as an oil.

Part C: An amount of 292 grams of Part A product, 99 grams of Part B product and 49 grams of basic copper carbonate was blended and heated to a temperature between 40 and 50 ° C in a flask equipped with a water condenser. 50 ml of an aqueous ammonium hydroxide solution was added thereto. The mixture was heated under reflux conditions for 4 hours. An amount of 47 ml of water was collected in the condenser. 100 grams of solvent &quot; SC-100 &quot; was added to the blend. The mixture was kept at 100 ° C under stirring for 0.5 hours. 25 grams of diatomaceous earth was added to the mixture. The mixture was filtered through diatomaceous earth at a temperature of 60 ° C to provide an amount of 680 grams of product as a dark green substance having a copper content corresponding to 2.73% by weight.

Anti-oxidants

According to one aspect of the invention the diesel fuel compositions of the present invention contain a minor amount of at least one anti-oxidant agent to stabilize the organometallic complex in the diesel fuel until such fuel is used. Such anti-oxidant agents encompass the blocked phenol or amine antioxidants known in the art. Examples are 2,6-di-tert-butyl-4-methyl-phenol, 4,4'-methylenebis (2,6-di-tert-butylphenol) 4'-thiobis (2-methyl-6-tert-butylphenol), N-phenyl-alpha-naphthylamine, N-phenyl-beta-naphthylamine, tetramethyl diamine diphenylmethane, anthranilic acid and phenothiazine and its alkylated derivatives.

A class of useful antioxidants is constituted by metal deactivators. Examples are the ethylene diamine tetraacetic acid derivatives and the Î ±, β-disalicylidene-1,2-propane diamine compound. Still further such agents are lecithin, derivatives of heterocycles such as thiadiazole, imidazole and pyrazole, as well as derivatives of citric acid and gluconic acid.

According to one aspect of the present invention, the anti-oxidant comprises one or more aromatic hydroxy-oximes or one or more previously described Schiff bases and considered useful as component (i) for the preparation of the organometallic complexes of the present invention.

According to another aspect of the present invention, the anti-oxidant agent is a compound represented by the general formula

OHAr-R (LV)

In Formula (LV) Ar represents an aromatic group which is preferably a benzene or naphthalene nucleus 1 and more preferably a benzene nucleus. R is hydrogen, a hydrocarbyl group preferably having up to about 40 carbon atoms, 190

preferably between 10 and 30 carbon atoms and 1

preferably between 14 and 20 carbon atoms. R 34 may also be -COOR, -OR or R 6 -R 5 -N-R 7 2 3 4 6 7

Each of R 1, R 2, R 3, R 4 and R 5 independently represents hydrogen, an aliphatic hydrocarbyl group or a hydroxy substituted aliphatic hydrocarbyl group having up to about 40 carbon atoms, more preferably up to about 30 carbon atoms of carbon and more preferably up to about 20 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, rafts preferably an alkylene group having up to about 40 carbon atoms, ratios of preferably up to about 30 carbon atoms, and most preferably up to about 20 carbon atoms . J is from zero to about 4, preferably from zero to about 2, more preferably 1. Examples include the following compounds: 4-t-butyl catechol; 2,6-di-t-butyl-p-cresol; 2,6-di-t-butyl-4- (dimethylamino-methyl) -phenol; 2,5-di-t-amylhydroquinone; and 4- (hydroxy-methyl) -2,6-di-t-butyl-phenol.

According to a variant the anti-oxidant agent is a compound represented by the general formula 191

OH

OH (LVI) (R 1 -Ar -R 3 -A 1 - (R 2) k

In General Formula (LVI) Ar and Ar independently represent aromatic groups which are preferably benzene or naphthalene nuclei, more preferably benzene nuclei. R 2 represents -CH 2 -, -S-, -S-S-, -CH 2 -O-CH 2 - or -CH 2 NNR 2 -CH 2. Each of R1, R2 and R3 is independently hydrogen or an aliphatic hydrocarbyl group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, more preferably up to about 10 carbon atoms . Any of k is independently a number from zero to about 4, preferably from zero to about 2 and more preferably represents zero or 1. Examples 1 include the following compounds: 2,2-methylene bis ( 4-methyl-6-cyclohexyl-phenol); and 2,2-thio-bis (4-methyl-6-t-butylphenol).

According to a variant the anti-oxidant agent is a compound represented by the general formula R1 (• H) I • Ar

N (R) (LVII) 192

In General Formula (LVII) Ar represents an aromatic group which is preferably a benzene or naphthalene nucleus, more preferably a benzene nucleus. P is zero or 1, q is 1, 2 or 12 3, r is 3-q. R, R and R are independently hydrogen or hydrocarbyl groups preferably having up to about 40 carbon atoms / more preferably up to about 20 carbon atoms, more preferably up to about 10 carbon atoms. Examples include the following compounds: 4-dodecyl-2-aminophenol; dinonyl diphenyl amine; and phenyl-beta-naphthylamine.

According to a variant the anti-oxidant agent is a compound represented by the general formula

, 5

In General Formula (LVIII) R is -CH 2 -, -S-, -NR 6 or -O-. Each of R1, R2, R3, R4 and R4 is independently hydrogen, hydroxy or alkoxy or aliphatic hydrocarbyl group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms and more 193

A is preferably up to about 10 carbon atoms. S is 0, 1 or 2, preferably 1. Examples include the following compounds: dioctyl-phenothiazine; and dinonyl-phenoxazine.

According to a variant the anti-oxidant agent is a compound represented by the general formula

12 3 5

In General Formula (LVIX) each of R 1, R 2, R 3 and R 4 independently represents a hydrogen atom or an aliphatic hydrocarbyl group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, and more preferably to about 10 carbon atoms. T is 1 or 2. In the case where t is 1, R 2 is hydrogen, or an aliphatic or aromatic hydrocarbyl group preferably having up to about 20 carbon atoms, more preferably up to about 10 carbon atoms, more preferably up to about 6 carbon atoms, and most preferably up to about 3 carbon atoms. Where t is 2, 194

R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylene group, more preferably an alkylene group. Where t is 2, R may represent -O2 C-R-CO2 wherein R is hydrocarbylene or hydrocarbylidene, preferably alkylene or alkylidene, and more preferably a alkylene. The groups represented by R 5 and R 6 preferably contain up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, and most preferably up to about 10 carbon atoms. Examples include the following compounds: 2,6-tetramethyl-4-octyl-piperidine and bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

According to a variant the anti-oxidant agent is a compound represented by the general formula

1 2 3 4 5

In the general Formula (LX) each of R 1, R 2, R 3, R 4 and R 5 are independently hydrogen,

hydrocarbyl moieties having preferably up to about 40 carbon atoms, are preferably up to about 20 carbon atoms and most preferably up to about 10 carbon atoms. As an example the trimethyl-dihydroquinoline compound is mentioned.

According to a variant the anti-oxidant agent is a compound represented by the general formula

(LXI) 12 3

In General Formula (LXI) each of R 1, R 2 and R 3 is independently hydrogen or an aliphatic hydrocarbyl group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, and most preferably up to about of 10 4 carbon atoms. Any of R 2 is independently hydrogen or hydroxy, -R 2 OH, R 2 CN, or -CH (R 2) 2 wherein any of R 5 and R 6 is independently a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group, more preferably an alkylene group.

Any of the groups R 5 and R 6 preferably has up to about 100 carbon atoms, more preferably up to about 50 carbon atoms and more 196

preferably between 6 and 30 carbon atoms. Each of the symbols independently represents the hydrogen atom or an aliphatic hydrocarbyl group preferably having up to about 40 carbon atoms, more preferably up to about 20 carbon atoms, and most preferably up to about 10 carbon atoms. Examples are the dodecyl-amine and N-dodecyl-N-hydroxy-propylamine compounds.

According to a variant the anti-oxidant agent is a compound represented by the general formula R 2 R 4 R 1 -NR 3-N-R 5 O-X 1 I)

In the general Formula (LXII) R 1, R 2, R 3 and R 4 are independently hydrogen or aliphatic hydrocarbyl groups preferably having up to about 40 carbon atoms, more preferably up to about 30 carbon atoms, more preferably up to about 20 carbon atoms, and most preferably up to about 10 carbon atoms. R represents a hydrocarbylene or hydrocarbylidene group, preferably an alkylene or alkylidene group and more preferably an alkylene group preferably having up to about 20 carbon atoms and more preferably up to about 10 carbon atoms. In accordance with one embodiment R 2 represents the group 197

2-phenylene; R 1 and R 2 are hydrogen atoms; R is an aliphatic hydrocarbyl group preferably having from 6 to 10 carbon atoms, preferably a straight or branched chain alkyl group having up to about 8 carbon atoms; and R is phenyl. In a variant R is phenylene; the symbols 2 4 15

R 2 and R 3 represent the hydrogen atom; and R 1 and R 2 are independently substituted diphenyl groups, any substituent on each of the phenyl groups being an aliphatic hydrocarbyl group, preferably an alkyl group preferably having from about 6 to 12 carbon atoms and more preferably about 8 atoms of carbon.

Examples include the following compounds: N, N'-bis (dioctylphenyl) -p-phenylene diamine; and N-phenyl-N '- (1-methylheptyl) -p-phenylene diamine.

Fuel type diesel

Diesel fuels which are useful within the scope of the present invention may be any diesel fuel having a sulfur content of not more than about 0.1% by weight and preferably not more than about 0.05% by weight in accordance with determinations made by the test method specified in ASTM D 2622-87 under the heading &quot; Standard Test Method for Sulfur in Petroleum Products by X-Ray

Spectometry &quot;. Any fuel having the stated sulfur content and boiling temperatures and 198 viscosity values suitable for use in diesel engines may be used. These fuels typically have a value corresponding to 90% of the distillation point temperature in the range approximately between 300 ° C and 390 ° C, and preferably in the range of approximately 330 ° C to 350 ° C. The viscosity values of these fuels typically range from 1.3 to 24 centistokes at the temperature of 40 ° C. These diesel fuels can be classified with any of the 1-D, 2-D OR 4-D scale values as specified in ASTM D 975 under the heading &quot; Standard Specification for Diesel Puel Oils &quot;. These diesel fuels may contain alcohols and esters.

The diesel fuel compositions of the present invention contain an effective amount of one or more organometallic complexes previously described to lower the ignition temperature of the small exhaust particles that form when the diesel fuel is burned. The concentration of these organometallic complexes in the diesel fuels of the present invention is usually expressed in terms of the level of metal addition of such complexes. These diesel fuels preferably contain between 1 and about 5 parts of that metal per million parts of the fuel, more preferably between 1 and 500 parts of metal per million parts of the fuel and more preferably between 1 and 100 parts per million parts of the metal. 199

These diesel type fuels may also contain one or more of the anti-oxidant agents described above. These fuels generally contain an effective amount of the anti-oxidant agent to stabilize the above-described organometallic complex incorporated in the fuel until that fuel is burned in the diesel engine. Typically diesel fuel contains up to about 5000 parts of anti-oxidant agent per million parts of diesel fuel, most preferably up to about 500 parts of anti-oxidant agent per million parts of the fuel, and most preferably up to about of 100 parts of anti-oxidant agent per million parts of the fuel.

The diesel fuel compositions of the present invention may contain, in addition to the organometallic complexes and antioxidant agents referred to above, other additives well known to those skilled in the art. These include, among other things, coloring agents, cetane indices improving agents, rust inhibiting agents such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum formation inhibitors, metal deactivators, demulsifying agents, part lubricants cylinders and antifreeze agents.

These diesel-type fuel compositions can be combined with ash-free dispersants. Suitable ash-free dispersants include esters of 200

mono- or polyols and the acylating agents of high molecular weight mono- or polycarboxylic acids containing at least about 30 carbon atoms in the acyl radical. Such esters are well known to those skilled in the art. See for example French patent no. 1396645; English Patents Nos. 981850; 1055337 and 1306529; and US Patents Nos. 3255108; 3311558; 3331776: 3346354; 3,522,179; 3579450; 3542680; 3381022; 3639242; 3697428; and 3708522. These patents are expressly incorporated herein by reference with respect to what they reveal about suitable esters and methods for their preparation. If such dispersants are used, the weight ratio of the aforementioned organometallic complexes to the aforementioned ash-free dispersing agents may range from about 0.1: 1 to 10: 1, preferably from 1: 1 to 10 :1.

The organometallic complexes of the present invention may be added directly to the fuel or may be diluted with a substantially inert organic diluent, usually in the liquid state such as naphtha, benzene, toluene, xylene or a normally liquid fuel, to provide a concentrated additive. Similarly, the aforementioned anti-oxidant agents may be added directly to the fuel or may also be incorporated into the concentrate. These concentrates generally contain from 1% to 90% by weight of the organo-metalic complexes 201 of the present invention. Such concentrates may also contain up to about 90% by weight, generally between 1% and 90% by weight of one or more of the antioxidant agents referred to above. Such concentrates may also optionally contain one or more conventional additives known in the art or selected from the additives previously described. According to one aspect of the present invention, the organometallic complex is combined with the diesel fuel by direct addition or as a component of a concentrated as described above and the diesel fuel is used to run a diesel engine equipped with a separator of the small particles of the exhaust system. The diesel fuel having the organometallic complex is contained in a fuel tank, is transmitted to the diesel engine where it is burned and the organometallic complex reduces the ignition temperature of the exhaust particles collected in the particulate separator of the exhaust system. According to another variant the operating procedure described above is used except that the organometallic complex is maintained on board the machine to be driven with the diesel engine (for example, a car, a bus, a lorry, etc.) in a separate device to provide the fuel additive completely independently of the diesel fuel. The organometallic complex is blended or blended with the diesel fuel during the operation of the diesel engine. According to this latter variant, complex 202

organometallic compound which is maintained in the fuel additive dispensing device may be a component of a concentrated fuel additive of the type described above, that concentrate being combined with the diesel fuel during the operation of the diesel engine.

The concentrated formulations given below are provided for the purpose of exemplifying the present invention. In each of these formulations the indicated copper complex of Examples 1-56 is used, the treatment level being expressed in parts by weight based on the amount of the product of said examples which is added to the concentrate. For each of the products of Examples 1-56 two concentrated formulations are provided, one of which is the formation -1 (eg, concentrated formulation Al) which contains an anti-oxidant agent and the other is the formulation -2 ( for example, the concentrated formulation A-2) which does not contain any anti-oxidant agent. The anti-oxidant agent is the compound 5-dodecyl salicyl aldoxime. The level of treatment for the anti-oxidant agent is expressed in parts by weight. For all formulations the remainder is xylene which is expressed in terms of parts by weight. 203

Copper complex

Formulation Treatment Antioxidant Concentrated Xylitol Example (parts) (parts) (part &lt; Al 1 350 35 385 A-2 1 350 - 350 Bl 2 409 35 444 B-2 2 409-409 Cl 3 377 35 412 CN 1 O 3 377-377 D-1 4 465 35 500 D-2 4 465-465 El 5 435 35 470 E-2 5 435 - 435 F-1 6 417 35 452 F-2 6 417-417 Gl 7 571 35 606 G- 2 7 571 - 571 Hl 8 521 35 556 H-2 8 521 - 521 1-1 9 395 35 430 1-2 9 395 - 395 Jl 10 425 35 460 J-2 10 425-425 204 Kl 11 455 35 490 Κ 2 11 455 - 455 L-1 12 408 35 443 L-2 12 408-408 Μ-1 13 531 35 566 Μ-2 13 531 - 531 Ν-1 14 549 35 584 Ν-2 14 549-549 * 1 I ο 15 280 35 315 ο I Μ 15 280 - 280 Ρ-1 16 541 35 576 Ρ-2 16 541 - 541 Q-1 17 456 35 491 Q-2 17 456 - 456 R-1 18 417 35 452 R 2 18 417-417 S-1 19 427 35 462 S-2 19 427-427 Τ-1 20 465 35 500 Τ-2 20 465-465 U-1 21 461 35 496 U-2 21 461-461 V- 1 22 645 35 680 V-2 22 645-645 W-1 23 513 35 548 W-2 23 513 __ 513

205 24 513 35 24 513 - 25 587 35 25 587 - 26 645 35 26 645 - 27 893 35 27 893 - 28 9091 35 28 9091 - 29 1036 35 29 1036 - 30 503 35 30 503 - 31 331 35 31 331-32 389 35 32 389 - 33 599 35 33 599 - 34 556 35 34 556 - 35 571 35 35 571 __ 206 JJ-1 36 784 35 819 JJ-2 36 784 - 784 KK-1 37 612 35 647 KK-2 37 612 - 612 LL-1 38 633 35 668 LL-2 38 633 - 633 MM-1 39 669 35 704 MM-2 39 669-669 NN-1 40 571 35 606 NN-2 40 571-571 00-1 41 2597 35 2632 00-2 41 42597-2597 PP-1 42 410 35 445 PP-2 42 410-410 QQ-1 43 483 35 518 QQ-2 43 483-483 RR-1 44 905 35 940 RR-2 44 905-905 SS-1 45 625 35 660 SS-2 45 625-625 TT-1 46 671 35 706 TT-2 46 671-671 UU-1 47 417 35 452 UU-2 47 417-417 Wl 48 488 35 523 W-2 48 488 __ 488

1 2 3 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 10 15 20 25 25 25 52 1220 35 1255 ZZ-2 52 1220-1220 AAA-1 53 317 35 352 AAA-2 53 317-317 BBB-1 54 576 35 611 BBB-2 54 576-576 CCC-1 55 694 35 729 CCC-2 55 694-694 DDD-1 56 1667 35 1702 DDD-2 56 1667-1667

The following fuel formulations are provided for the purpose of exemplifying the present invention. In any of the following diesel-type fuel formulations a 2-D grade diesel fuel having a sulfur content corresponding to 0.05% by weight is used. In each formulation the copper complex shown in Examples 1-56 is used, the treatment level being expressed in parts 208 /

y per million (ppm) based on the amount of product of said examples which is added to the fuel. For each of the products of Examples 1-56 two diesel fuel formulations are provided, one of which is the formulation -1 (for example, the Al-diesel fuel formulation) which contains an anti-oxidant agent and the the other formulation -2 (for example the diesel fuel formulation A-2) which does not contain any anti-oxidant agent. The anti-oxidant agent is the 5-dodecyl-salicyl-aldoxime compound. The level of treatment for the anti-oxidant is expressed in parts per million. With all formulations the remainder is the low sulfur diesel fuel referred to above which is expressed in percentages by weight. 209

Copper complex

Concentrated formulation

Treatment Example (parts)

Anti-oxidant Diesel fuel (% w / w) A-1 1 350 35 A-2 1 350 - B-1 2 409 35 B-2 2 409 - Cl 3 377 35 C-2 3 377 - Dl 4 465 35 D-2 4 465 - E-1 5 435 35 E-2 5 435 - Fl 6 417 35 F-2 6 417 - Gl 7 571 35 G-2 7 571 - Η-1 8 521 35 H- 2 8 521 - 1-1 9 395 35 H 1 to 9 395 - J 10 1025 25 J - 2 10 425 - K 11 455 35 K - 2 11 455 - 99.9615 99.9650 99.9556 99.9591 99, 9588 99.9623 99.9500 99.9535 99.9530 99.9565 99.9548 99.9583 99.9394 99.9429 99.9444 99.9479 99.9570 99.9605 99.9540 99.9575 99.9510 99 , 9545 210; L 12 408 35 99.9557 L-2 12 408 - 99.9592 Μ-1 13 531 35 99.9434 M-2 13 531 - 99.9469 Nl 14 549 35 99.9416 N-2 14 549 - 99.9451 0-1 15 280 35 99.9685 0-2 15 280 - 99.9720 Pl 16 541 35 99.9424 P-2 16 541 - 99.9459 Qi 17 456 35 99.9509 Q-2 17 456 - 99.9544 Rl 18 417 35 99,9548 R-2 18 417 - 99,9583 Sl 19 427 35 99,9538 S-2 19 427 - 99,9573 Tl 20 465 35 99,9500 T-2 20 465 - 99,9535 461 35 99.9504 U-2 21 461 - 99.9539 Vl 22 645 35 99.9320 V-2 22 645 - 99.9355 wl 23 513 35 99.9452 W-2 23 513 - 99.9487 211 Xl 24 513 35 99.9452 Χ-2 24 513 - 99.9487 Υ-1 25 587 35 99.9378 Υ-2 25 587 - 99.9413 Ζ-1 26 645 35 99.9320 Ζ-2 26 645 - 99.9355 ΑΑ -1 27 893 35 99.9072 ΑΑ-2 27 893 - 99.9107 ΒΒ-1 28 9091 35 99.0874 ΒΒ-2 28 9091 - 99.0909 CC-1 29 1036 35 99.8929 CC-2 29 1036 - 99.8964 DD-1 30 503 35 99.9462 DD-2 30 503 - 99.9497 ΕΕ-1 31 331 35 99.9634 ΕΕ-2 31 331 - 99.9669 FF-1 32 389 35 99.9 576 FF-2 32 389 - 99.9611 GG-1 33 599 35 99.9366 GG-2 33 599 - 99.9401 ΗΗ-1 34 556 35 99.9409 ΗΗ-2 34 556 - 99.9444 ΙΙ-1 35 571 35 99.9394 II-2 35 571 - 99.9429 JJ-1 36 784 35 99.9181 JJ-2 36 784 - 99.9216 212 ΚΚ-1 37 612 35 99.9353 ΚΚ-2 37 612-99, 9388 LL-1 38 633 35 99.9332 LL-2 38 633 - 99.9367 ΜΜ-1 39 669 35 99.9296 ΜΜ-2 39 669 - 99.9331 ΝΝ-1 40 571 35 99.9394 ΝΝ-2 40 571 - 99.9429 00-1 41 2597 35 99.7368 00-2 41 42597 - 99.7403 ΡΡ-1 42 410 35 99.9555 ΡΡ-2 42 410 - 99.9590 QQ-1 43 483 35 99.9482 Q-2 43 483 - 99,9517 RR-1 44 905 35 99,9060 RR-2 44 905 - 99,9095 SS-1 45 625 35 99.9340 SS-2 45 625 - 99.9375 ΤΤ-1 46 671 35 99.9294 ΊΤ-2 46 671 - 99.9329 UU-1 47 417 35 99,9548 UU-2 47 417 - 99,9583 W-1 48 488 35 99.9477 W-2 48 488 - 99.9512

213

ww-i 49 265 35 99.9700 WW-2 49 265 - 99.9735 XX-1 50 325 35 99.9640 XX-2 50 325 - 99.9675 YY-1 51 345 35 99.9620 YY-2 51 345 - 99.9655 ZZ-1 52 1220 35 99.8745 ZZ-2 52 1220 - 99.8780 AAA-1 53 317 35 99.9648 AAA-2 53 317 - 99.9683 BBB-1 54 576 35 99.9389 BBB -2 54 576 - 99.9424 CCC-1 55 694 35 99.9271 CCC-2 55 694 - 99.9306 DDD-1 56 1667 35 99.8298 DDD-2 56 1667 - 99.8333 Example DDD- the product of Example 57 was cooled with low-sulfur grade 2-D grade diesel fuel, the sulfur content being 0.05 wt%. The copper content of the resulting diesel fuel composition is 77 ppm.

While the present invention has been described with reference to the preferred aspects thereof,

note that upon reading the present specification there are several modifications which are apparent to those skilled in the art. Accordingly, it will be appreciated that the present invention now described is intended to embrace all of the modifications contained within the scope of the appended claims. 215

Claims (122)

A diesel fuel composition for use in a diesel engine equipped with a device for capturing the small particles of the exhaust system,. characterized in that it comprises: a main amount of a diesel fuel having a sulfur content of not more than about 0.1% by weight; and a minor amount effective to lower the ignition temperature of the exhaust gas particles collected in said trap for at least one organometallic complex, said complex being derived from: (i) at least one organic compound containing a hydrocarbon bridge and at least two functional groups, each of which functional groups are independently X = -XR, -NR,, -NO =, = NR = = NXR = = NR--XR, -N (R * N) (X) XR, -N = CR0 -CN or -N = NR12 R XR wherein X is oxygen or sulfur; R is hydrogen or hydrocarbyl; R4 is hydrocarbyl or hydrocarbylidene; A is a number from 0 to about 10; and (ii) at least one metal group reactant capable of complexing with component (i), said metal being capable of reducing the ignition temperature of said exhaust gas particles. 2. Composition according to Claim 1, characterized in that the sulfur content of said diesel-type fuel is not more than 0.05% by weight. 3. The composition of claim 1, wherein said metal complex is dissolved or stably dispersed in said diesel fuel. 4. The composition of claim 1, wherein said functional groups cross each other on different carbon atoms of the hydrocarbon bond. (R * N) R or -CN. \ 3. 5. A composition according to claim 1, wherein said functional groups are = X, -OH, -nr2, -no2, = NR1 = NOH, - R A composition according to claim 1, wherein component (i) is at least one compound represented by the general formula: (R) d (I) b is from zero to about 10; the symbol has a number of about 219. ·. 219 ,. ·. from 1 to about 1000; d is zero or 1; in the case where c is greater than 1, d is 1; R1 is a hydrocarbyl group or G; R2 and R3 are each independently hydrogen, hydrocarbyl groups or together may form a C1 -C4 double bond; R1 is hydrogen, hydrocarbyl, or G; R 2, R 2, R 3 and R 4 may together form a triple bond between and C 2 &gt; R 2 and R 3 may form together with and C 2 is an alicyclic, aromatic, heterocyclic, alicyclic-heterocyclic, alicyclic-aromatic, heterocyclic-aromatic, heterocyclic-alicyclic, aromatic-alicyclic or aromatic-heterocyclic alicyclic group; or a substituted, hydrocarbyl aromatic hydrocarbyl-substituted alkyclic hydrocarbyl group; substituted or unsubstituted or substituted hydrocarbyl-alkyclic-substituted-heterocyclic, substituted-hydrocarbyl-alicyclic-aromatic, substituted-hydrocarbyl-alicyclic-aromatic, substituted-hydrocarbyl-heterocyclic- heteroaryl, each of R4 and R8 is independently hydrogen, hydrocarbyl, or G; R7 represents a hydrocarbyl or hydrocarbylidene group; each of the substituents G 1 independently is X, -XR, -NR 2 &gt; (R) = X, -C (R) = NR, -RgC = NR, -C = NXR, -RgC (R ) = NXR, -C (R) = N-R 9 -XR, -Rg -C (R) = N-R 9 -XR, -N (R 10 N) (X) XR, -R (X) XR, -N = CR 2, -R 2 N = CR 2;  € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒR1 R2 NR1 R2 NR1 R2 NR1 R2 R3 NR1 R2 NR1 R2 R3 NR1 R2 R3 NR1 R3 R3 NR 221- ' in the case where d is zero, T is = x, -xr, -nr2, -no2, -c (R) = x, -c (R) = nr, -C (R) = NXR, -C ( (X) XR, -N = CR ", = NXR, -CN, -N (R9) I! (R9N) eQ or -N (R1q) -QJ RR in the case where d is one, T is -X-, -NR-, -c-, -c-, -CR, - (R 9 N): R 1, R 2 and R 3 are each independently selected from the group consisting of hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl, - (X) XR, -P (X) X-, -P (X) X- or -P (X) XR; G and T together with and C2 form a group of general formula The symbols and are each independently a number comprised in &quot; 222 222 &quot; to about 10; each R6 is a hydrocarbylene or hydrocarbylidene group, a hydroxy-hydrocarbylene or a substituted hydrocarbylidene group, or an amine-hydrocarbylene or substituted-hydrocarbylidene group; each R6 is a hydrocarbylene or a hydrocarbylidene group; R 1q represents a hydrogen atom or a hydrocarbyl group or a substituted hydroxyhydrocarbyl group; Q is a group of formula II wherein: g is 0 to about 10; R1 is a hydrocarbyl or G group; 2.23 &lt; ¥ &gt; R4 and R4 are each independently hydrogen, hydrocarbyl groups or together may form a double bond between and; the symbol represents a hydrogen atom, a hydrocarbyl group or G; R4 and R4 may together form an alicyclic, aromatic, heterocyclic, alicyclic-heterocyclic group, and R3 and R4 can form together with an alicyclic, aromatic, heterocyclic, alicyclic-heterocyclic group. aromatic, heterocyclic-aromatic, heterocyclic-alicyclic, aromatic-alicyclic or aromatic-heterocyclic ring; or a substituted hydrocarbyl-alicyclic-substituted, substituted hydrocarbyl-heterocyclic, substituted hydrocarbyl-heterocyclic-substituted heterocyclic, hydrocarbyl-alicyclic-substituted aromatic hydrocarbyl-alicyclic aromatic group, substituted hydrocarbyl heterocyclic-aromatic group, substituted hydrocarbyl-heterocyclic-alicyclic hydrocarbyl group substituted aromatic or hydrocarbyl aromatic heterocyclic substituted aromatic heterocyclic; R1 and R2 are each independently hydrogen, hydrocarbyl, or G. Composition according to Claim 6, characterized in that one or more of the symbols R 1, R 2, R 3, R 4, R 11 and R 13 are as defined above. independently, hydrocarbyl groups having up to about 250 carbon atoms. 8. A composition according to claim 6, wherein one or more of R1, R2, R3, R6, R6, R12, R5, R5 and R16 are independently hydrocarbyl groups having up to about 20 carbon atoms. 9. A composition according to claim 6, wherein R 1, R 2 and R 3 independently have up to about 0 carbon atoms. A composition according to claim 6, characterized in that one or more of the symbols Ry, Rg and Rg are 225. are independently alkylene groups having from about 2 to about 4 carbon atoms. A composition according to claim 6, wherein G is = X, -XR, -m2, -m2, -C (R) = X, -C (R) = NR, -C (R) = NXR, -N = CR 2, -R 2 N = CR 2. 12. A composition according to claim 6, wherein X is -XR, -nr2, -no2, -c (R) = x, -ccr) = nr, -c (R ) = nxr, -n = cr2, -N (R1q) -Q or -N (RqN) R11 and RR 13. The composition of claim 6, wherein T is -X-, -RR-, -CR, RXR is N -CR-, -N (RqN) R or -R (R q R) -li. i 9i and i 9i NX-R RR 14. The composition of claim 6, wherein R1 is a substituted hydroxy-hydrocarbyl group. here Composition according to Claim 5, characterized in that component (i) is a compound represented by the general formula (II) in which i is a number from zero to about 10; the symbols R 2q, and R 22 are: ain &gt; each independently, a hydrogen atom or hydrocarbyl groups; (R) = X, -C (R) = NR, -C (R) = NXR, -N * CR 2, -N (R 10) ) -Q or -N (RgN) eR. The composition according to claim 1, wherein component (i) is an aromatic Mannich compound, said Mannich aromatic compound being the reaction product of (A-1) an aromatic comonomer of the hydrido radical and / or thiol of formula I-Ar-X- (XH) m (Al) wherein Ar is an aromatic group; m is an integer 1, 2 or 3; n is 1 to 4; the symbols each independently represent a hydrogen atom or a hydrocarbyl group having from 1 to about 100 carbon atoms; R6 is hydrogen, amino or carboxyl; and X represents an oxygen or sulfur atom or both in case m is 0 or 2; (A-2) is an aldehyde or a ketone having the general formula or a precursor thereof, R 2 and R 3 each independently represent a hydrogen atom or saturated hydrocarbyl groups having 1 to about 18 carbon atoms; and R 2 may also represent a hydrocarbyl group containing a carbonyl radical and having 1 to about 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amino group. 17. The composition according to claim 1, wherein component (i) is an aromatic Mannich component, said Mannich aromatic compound being the reaction product of: (Al) an aromatic compound containing a hydroxy and / or thiol having the general formula (R 1) -Ar- (XH) (Al) 1 nm wherein Ar is an aromatic group; m is 1, 2 or 3; ·. 229 ' n is a number from 1 to about k; each R4 is independently hydrogen or C1-4 alkyl. a hydrocarbyl group having from 1 to about 100 carbon atoms; R2 is hydrogen, amino or carboxyl; and X represents an oxygen or sulfur atom or both in the case where m is 0 or 2; (A-2) is an aldehyde or a ketone having the general formula or the precursor thereof, wherein R 1 and R 2 are each independently hydrogen or saturated hydrocarbyl groups having from 1 to about 18 carbon atoms; and R 2 may also represent a hydrocarbyl group containing a carbonyl radical and having 1 to 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amino group, said amine being characterized by the absence of hydroxyl and / or thiol groups. The composition of claim 1, wherein component (i) is an aromatic Mannich compound represented by the general formula XR, (III): wherein Ar and Ar are each independently aromatic groups; R3, R5, R6 and R6 are each independently hydrogen atom or aliphatic hydrocarbyl groups; R4 may represent a substituted or unsubstituted aliphatic hydrocarbyl group; / hydroxyl moiety; R1, R2 and Ry are each independently hydrocarbyl or hydrocarbylidene groups; X is oxygen or sulfur; and i is a number from zero to about 10. 19. The composition according to claim 1, wherein the component (i) is an aromatic Mannich compound represented by the general formula (IV) wherein R 1 and R 2 are each independently hydrogen or aliphatic hydrocarbyl groups; and R2 is a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group. Composition according to Claim 1, characterized in that component (i) is an aromatic Mannich compound represented by the general formula in which R 1, R 2, R 3 and R 4 are each independently hydrogen or aliphatic hydrocarbyl groups; and R 2, R 2, R 2 and R 3 independently represent hydrocarbylene or hydrocarbylidene groups. A composition according to claim 1, wherein component (i) is an aromatic Mannich compound represented by the general formula 233 · &quot; . (I.e. in which (VI) the s rmbo lo s &gt; â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ29 â € ƒâ € ƒâ € ƒand â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ129 are each independently hydrogen or aliphatic hydrocarbyl groups; and R1, R2, R3, R4 and R8 are independently hydrocarbyl or hydrocarbylidene groups. 22. The composition of claim 1, wherein component (i) is a compound represented by the general formula, in which R 1, R 2, R 2, R 2, R 2, R 3 and R 4 are each independently hydrogen or aliphatic hydrocarbyl groups; R 2, R 3 and R 4 independently represent hydrocarbylene or hydrocarbylidene groups; and i is 0 to about 10. Composition according to Claim 1, characterized in that component (i) is an aromatic Mannich compound represented by the general formula 235 (VIII) wherein R 1, R 2, R 2, R 2, R 2, R 2 and R 3 are each independently hydrogen or hydrocarbyl groups; and Ry and Rg are independently hydrocarbylene or hydrocarbylene groups. 24. The composition according to claim 1, wherein component (i) is an aromatic Mannich compound represented by the general formula (IX) 236 in which R1 and R2 are each independently hydrogen or hydrocarbyl groups; the symbols R 1, R 2, R 3 and R 4 are independently selected from alkyl, or alkylidene groups; and i and j are each independently from 1 to about 6. 25. A composition according to claim 1, wherein component (i) is an aromatic Mannich compound represented by the general formula in which R 1 is hydrogen or C 1 -C 4 -alkyl. Ar is an aromatic group; R1 and R2 are independently hydrocarbylene or hydrocarbylidene groups; R3 is hydrogen or lower hydrocarbyl; 237 R1 and R2 are each independently hydrogen, aliphatic hydrocarbyl groups, hydroxy substituted aliphatic hydrocarbyl groups, amine substituted aliphatic hydrocarbyl groups or alkoxy substituted aliphatic hydrocarbyl groups; and R6 is hydrogen or an aliphatic hydrocarbyl group. A composition according to claim 1, characterized in that component (i) is an aromatic Mannich compound represented by the general formula wherein R 1, R 2, R 3, R 4, Ar is an aromatic group; R4 is hydrogen or aliphatic hydrocarbyl; and R2, R3 and R4 are independently hydrocarbylene or hydrocarbylidene groups. 27. The composition of claim 1, wherein component (i) is a compound represented by the general formula Ar-NOH11 C-R1 (XII) R 2 wherein Ar is an aromatic group; and R1, R2 and Rg are each independently hydrogen or hydrocarbyl groups. A composition according to claim 1, wherein component (i) is a compound represented by the general formula, in which the symbol represents a methyl group; R2 is a tetramer of prc; pileno; and R4 represents a hydrogen atom. 29. The composition of claim 1, wherein component (i) is a compound represented by the general formula (R2) j (XIII) in which R1 and R2 are each independently hydrogen, aliphatic hydrocarbyl groups or groups of the general formula wherein the symbol represents the hydrogen atom or an aliphatic hydrocarbyl group; i is a number from 0 to 4; and j is a number comprising between zero and 5. Composition according to Claim 1, characterized in that component (i) is selected from the group consisting of dodecyl-salicylaldoxime, 4,6-di-tert-butyl-salicylaldoxime, methyl-dodecyl- 2-hydroxy-3-methyl-5-ethyl-benzophenone oxime, 5-heptyl-salicylaldehyde, 5-nonyl-salicylaldoxime, 2-hydroxyl-3,5-dinonyl-benzophenone oxime, 2- hydroxy-5-nonyl-benzophenone oxime and polyisobutylnyl-salicylaldoxime. 31. A composition according to claim 1, wherein component (i) comprises at least one compound represented by the general formula wherein X Ar represents an aromatic group: R 1 and R 2 are each independently hydrogen or hydrocarbyl groups; R 9 is hydrogen, hydrocarbyl, or a group of general formula (XV) in which R4 is a hydrocarbylene or hydrocarbylidene group; R g and Rg are each independently hydrogen or hydrocarbyl groups; Ar represents an aromatic group. A composition according to claim 1, wherein component (i) is a compound represented by the general formula wherein the compounds of formula (I) Ar and Ar are independently aromatic groups; R1 and R2 are each independently hydrogen or hydrocarbyl groups; and R9 is a hydrocarbyl group; or hydrocarbylidene. A composition according to claim 1, wherein component (i) is a compound represented by the general formula wherein Ar and Ar (O) independently represent aromatic groups; and R1 is a hydrocarbyl group. A composition according to claim 1, wherein component (i) is a compound represented by the general formula OH (XVII-1) wherein R3 is hydrogen; represents a polybenzenyl or polyisobutenyl group. O The composition according to claim 1, wherein component (i) is a compound represented by the general formula wherein Ar and Ar- are independently aromatic groups; and R1 and R2 are each independently hydrogen or hydrocarbyl groups. A composition according to claim 1, wherein component (i) is a compound represented by the general formula wherein R 1, R 2, R 3, R 4, Ar and Ar are independently aromatic groups; R1 and R2 are each,. .244 independently, a hydrogen atom or hydrocarbyl groups; and K-2 is hydrocarbylene or hydrocarbylidene. The composition according to claim 1, wherein component (i) is a compound represented by the general formula (XX) wherein R1 is hydrocarbylene or hydrocarbylidene; and R2, R2, R3 and R4 are each independently hydrogen or hydrocarbyl groups. A composition according to claim 1, wherein component (i) is a compound represented by the general formula 245 ' h (XXI) 0 = C-C-C = N-Rn-N = C-C-C = O (R11 R7 R8 R5 R6 in which R 1, R 2, R 3, R 4, R 5, R 6, R 6, R 7 and R 8 are each independently hydrogen or hydrocarbyl groups; R 5 is hydrocarbyl or hydrocarbylidene. 39. A composition according to claim 1, wherein component (i) is a compound represented by the general formula In which R 1, R 2, R 3 and R 4 are independently selected from the group consisting of hydrogen, hydrocarbyl groups; R 2 is hydrocarbylene, or hydrocarbylidene; and i is from 1 to about 1000. 40. A composition according to claim 1, wherein component (i) is a compound represented by the general formula wherein R 1 and R 2 are each independently hydrogen, independently, a hydrogen atom or hydrocarbyl groups, at least equal to 60 total number of carbon atoms contained in the radicals represented by the symbols R 1 and R 2 A composition according to claim 1, wherein component (i) is a compound of formula (XXIV) represented by the general formula wherein R1 is hydrocarbyl group having from 6 to about 200 carbon atoms. Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula in which R 1, R 2, R 3, R 4, R 6 and R 7 each independently are hydrogen, hydrocarbyl groups; R 2 represents a hydrocarbylene or hydrocarbylidene group; and the symbol i returns zero or 1. .248 f &amp; The composition according to claim 1, wherein component (i) is represented by the general formula ## STR4 ## in which R 1 is hydrogen, Ar is an aromatic group; R1 and R2 are each independently hydrogen atom or hydrocarbyl groups; R2 is hydrocarbylene or hydrocarbylidene; R1 and R2 are each independently hydrogen, aliphatic hydrocarbyl groups, hydroxyl substituted aliphatic hydrocarbyl groups, aliphatic substituted aliphatic hydrocarbyl groups or alkoxy substituted aliphatic hydrocarbyl groups. A composition according to claim 1, ca. 249 characterized in that the component (1) comprises at least one compound selected from the group consisting of: dodecyl-N, N '-disalicylidene-1,2-propane diamine; dodecyl-N, N'-disyllicylidene-1,2-ethanediamine; Ν, Ν-, -disyllicylidene-1,2-propane diamine; N-salicylidene aniline; N-N-diiscarboxylidene-ethylenediamine; salicylal-beta-N-anino-ethyl-pyrazine; and N-salicylidene-N-dodecylamine. The composition according to claim 1, wherein component (i) is a compound represented by the general formula R. 1 (XXVII) wherein R 1, R 2, R 3 and R 4 are independently selected from the group consisting of H, genus or hydrocarbyl groups. The composition according to claim 1, wherein component (i) is a compound represented by the general formula in which R 1, R 2, R 3, R 4 and R 5 are each independently hydrogen or hydrocarbyl groups. A composition according to claim 1, wherein component (i) is a compound represented by the general formula in which R 1, R 2, R 2, R 2, R 2 and R 2 are each independently hydrogen or hydrocarbyl groups. Composition according to Claim 1, characterized in that component (i) is one or more compounds represented by any of the general formulas (ΧΧΧ-1) (XXX-2) R, Wherein the symbols are each a hydrogen atom or a hydrocarbyl group or any of R4 is a group of the general formula wherein R4 and R4 are each one, independently, a hydrogen atom or hydrocarbyl groups; and 253 R4 is hydrocarbylene or hydrocarbylidene. The composition of claim 1, wherein component (i) is a compound represented by the general formula OH (XXXI) wherein the symbol represents a group NR2 R2, OR2 or NO2 wherein R3 is a hydrogen atom or a hydrocarbyl group. A composition according to claim 1, wherein the component (i) is a compound represented by the general formula (XXXII): R 1, -CH 2 -O-C -COOR 2 wherein R 1, R 2 and R 3 are, one, independently a hydrogen atom or hydrocarbyl groups; R6 is a hydrocarbylene or a hydrocarbylidene group; and i is from 1 to about 10. A composition according to claim 1, wherein component (i) is a compound represented by the general formula R, -CH = COOR.SR ' Wherein X, R2 and R3 are each independently hydrogen, hydrocarbyl groups; and R4 is a hydrocarbyl group. or hydrocarbylidene. Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula (XXXIV) (XXXIV) wherein R 1, R 2, R 3 and R 4 are independently selected from the group consisting of hydrogen, hydrocarbyl groups, Composition according to Claim 1, characterized in that the component (i) is a compound represented by the general formula (XXXV) in which R 1 is hydrogen, C 1 -C 4 -alkyl, which R1, R2, R3 and R4 are independently selected from hydrogen, hydrocarbyl groups; and R2 is hydrocarbyl or hydrocarbylidene. : 256. A composition according to claim 1, wherein component (i) is a compound represented by the general formula R, -CH-C-OR-R 2 -CH 2 -R 2 -CH 2 R 3 -CH 2 R 3, R 2, R 3 and R 4 are independently selected from the group consisting of hydrogen, genus or hydrocarbyl groups; and R 2 represents a hydrocarbyl or hydrocarbylidene group. A composition according to claim 1, wherein component (i) is a compound represented by the general formula R 1 -N-R 7 -N- Wherein R 1, R 2, R 2, R 2, R 2, R 2 and R 3 are each independently hydrogen, hydrocarbyl groups; 2 / ': 257¾. . · R1 and R2 are independently benzyl or hydrocarbylene groups. A composition according to claim 1, wherein component (i) is a compound represented by the general formula R 2, R 2, R 3, R 4, R 5 and R 8 are each independently hydrogen, halogen, C 1-4 alkyl, C 1-4 alkoxy, hydrocarbyl. Composition according to Claim 1, characterized in that the component (i) is a compound represented by the general formula wherein R 1 and R 2 represent , each independently hydrogen atom. -, 258 hydrocarbyl groups, with at least 6 being the total number of carbon atoms present in the radicals represented by R 1 and R 2. Composition according to claim 1, characterized in that component (i) is a compound represented by the general formula R1 and R2 are each independently hydrogen or hydrocarbyl groups. A composition according to claim 1, wherein component (i) is a compound represented by the general formula. R 1 NR 2 NCH- (CH) z COOH (XLI) in which R 2 represents a hydrogen atom or a hydrocarbyl group; R2 has the meanings of the symbol R1- or represents an acyl group; R1 and R2 are each independently hydrogen or lower alkyl; and z is zero or 1. Composition according to Claim 1, characterized in that the component (i) is a compound represented by the general formula R 1 -C (O) -CH 2 -C (O) -R 2 (XLII) in which the symbols R 2 and R 2 are individually and independently hydrocarbyl groups. Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula (O) -NHOH (XLIII) in which R4 is a hydrocarbyl group having from about 6 to about 200 carbon atoms. A composition according to claim 1, wherein component (i) is a compound represented by the general formula OH (XLIV) wherein R1 and R2 are independently hydrocarbyl groups; and R 2 is CH 2 or CH 2 OCH 2 or a sulfur atom. Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula (XLV) wherein R4 is a hydrocarbyl group having from 1 to about 100 carbon atoms; i is a number from zero to 4; the symbol is in the ortho or meta position relative to G1; and are independently OH, NR 2, COOR, SH or C (O) H groups, wherein R 2 is hydrogen or hydrocarbyl. 64. A composition according to claim 63, wherein in the formula (XLV) â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ- OH represents the R 1 is represented by the general formula  € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒwherein R1 and R2 are each independently hydrogen or hydrocarbyl groups; and R 1 and R 2 are independently alkylene or alkylidene groups having from 1 to about 6 carbon atoms. Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula (XLVI) wherein R1 and R2 are each independently hydrogen or hydrocarbyl groups; are each and R4 are each an alkylene group; and symbols 2 an OH or CN group. A composition according to claim 1, wherein the component (i) is a compound represented by the general formula wherein the symbol represents a compound of formula (I) hydrogen atom or a hydrocarbyl group; e are each an alkylene group; and e are each independently OH or CN. Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula (XLVIII): -N-NH-Ar- R3 in which Ar and Ar are independently aromatic groups; and R1, R2 and R3 are each independently hydrogen or hydrocarbyl groups. Composition according to Claim 1, characterized in that component (i) is the reaction product of at least one acylated amine with at least one boron compound selected from the group consisting of boron trioxides, boron halides, boron acids, boride amides, and boron acid esters. Composition according to Claim 1, characterized in that the component (i) is the reaction product of (Pl) at least one carboxylic acid acylating agent, (P-2) at least an amine characterized by the presence within its structure of at least one HN =, and (P-3) group at least one phosphorus-containing acid of the general formula. in which each of X1, X3 and X2 are independently oxygen or sulfur, any of m is zero or 1 and any of R1 and B2 is independently a hydrocarbyl group . Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula H (L1) wherein the symbol represents an OH, NH2, NR2, COOR, SH or C (O) H group, wherein R6 is a hydrogen atom or a hydrocarbyl group. Composition according to Claim 1, characterized in that component (i) is a compound represented by the general formula in which R 2, R 2 &gt; R 2, R 2, R 2, R 3, R 4, R 5 and R 8 each independently represent a hydrogen atom, hydrocarbyl groups, hydroxyl-substituted hydrocarbyl groups or hydrocarbyl groups substituted by -COOH. A composition according to claim 1, wherein component (i) is a compound represented by the general formula wherein R1 is a hydrocarbyl group. Composition according to claim 1, characterized in that component (i) is a compound represented by the general formula ## STR4 ## : N-CH2 CH2 -N ch2-coor2 (LIV) in which R 1, R 2, R 3 and R 4 are independently selected from the group consisting of hydrogen, hydrocarbyl groups. A composition according to claim 1, ca. wherein said metal is selected from the group consisting of Na, K, Mg, Ca, Sr, Ba, Ti, Zr, V, Cr, Mo, Fe, Co, Cu, Zn, B, Pb and Sb , and blends of two or more of these metals. Composition according to Claim 1, characterized in that said metal is copper. A composition according to claim 1, wherein said metal is constituted by Cu in combination with one or more metals selected from 268 A composition according to claim 1, wherein said metal is selected from the group consisting of Cu, Ti, Mn, Fe, B, Zn, Mg, Ca, Na, K, Sr, Ba and Zr, and mixtures of two or more of these metals. O The composition according to claim 1, wherein said metal is composed of Cu in combination with one or more metals selected from Ti, Mn, Fe, B, Zn, Mg, Ca, Na, K, Sr, Ba or Zr. The composition of claim 1, wherein said metal derivative (ii) is a nitrate, nitrite, halide, carboxylate, phosphate, phosphite, sulfate, sulfite, carbonate, borate, hydroxide or oxide. Composition according to Claim 1, characterized in that said metal is different from Ti or Zr. The composition of claim 1, wherein component (i) is other than an N, N'-di- (3-alkenyl-salicylidene) diaminoamido compound. 82. A composition according to claim 1, wherein component (i) is different from the Ν, Ν'-di-salicylidene-1,2-ethane diamine compound. 83. A composition according to claim 1, wherein said metal is different from a rare earth metal. 84. A composition according to claim 1, wherein said metal is different from Ce, Mn or a mixture of Ce and Mn. 85. A composition according to claim 1, wherein a minor amount of at least one antioxidant is added to stabilize said organometallic complex in said diesel fuel. The composition of claim 85, wherein said antioxidant is selected from the group consisting of 2,6-di-tert-butyl-4-methyl-phenol, 4,4 ' (2,6-di-tert-butylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), N-phenyl-alpha- naphthyl-amine, N-phenyl-beta-naphthylamine, tetra-ethyl-dithio-270 diphenyl methane, anthranilic acid and phenothiazine and their alkylated derivatives. The composition of claim 85, wherein said antioxidant is a metal-derived deactivator. 88. A composition according to claim 85, wherein said antioxidant is a derivative of ethylene diamine tetraacetic acid or N, N-disalicylidene-1,2-propane diamine. A composition according to claim 85, wherein said antioxidant is a hydroxyaromatic or a Schiff base. Composition according to Claim 85, characterized in that said antioxidant is at least one compound represented by the general formula Ar (R 2): wherein Ar represents a group aromatic; • 271 R4 is hydrogen, hydrocarbyl, -COOR3, -OR4, or -R5 -N- each of R 2, R 3, R1, R2 and R3 independently are hydrogen, aliphatic hydrocarbyl or aliphatic hydrocarbyl groups substituted by hydroxy; R1 is a hydrocarbyl group; and j "represents a number from zero to 4. A composition according to claim 85, wherein said antioxidant is at least one compound represented by the general formula wherein R 1, R 2, R 3, wherein R4 is -O2-2, -S-, -SS-, -CH2-O-CH2- or -CH9-NR4-CH2-; each R 4, R 9 and R 4 independently represents a hydrogen atom or an aliphatic hydrocarbyl group; and any of k is independently a number from zero to about 4. A composition according to claim 85, wherein said antioxidant is at least one compound represented by the general formula (OH). R 1, -N (R 3) r (LVII) 1 wherein p is zero or 1; q is 1, 2 or 3; r is 3-q; and any of R1, R2 and R3 is independently hydrogen or hydrocarbyl groups. A composition according to claim 85, wherein said antioxidant is at least one compound represented by the general formula (LVIII) wherein R6 is oxygen or sulfur or -CH2 - or -m6-; R1, R2, R3 and R4 and R4 are each independently hydrogen, hydroxy, alkoxy or aliphatic hydrocarbyl; and s is 0, 1 or 2. The composition of claim 85, wherein said antioxidant is at least one compound represented by the general formula 274 in which any of R1, R2, R2 and R3 is independently hydrogen or aliphatic hydrocarbyl; t is 1 or 2; in the case where t is 1; R4 is hydrogen, aliphatic or aromatic hydrocarbyl; in the case where t is 0; R 2 represents a hydrocarbyl or hydrocarbylidene group or a group of the formula -C? -C? in which R8 is a hydrocarbyl group; or hydrocarbylidene. The composition of claim 85, wherein said antioxidant is at least one compound represented by the general formula any of R 1, R 2, R 3, R 4 and R 5 independently represents a hydrogen atom or a hydrocarbyl group. The composition according to claim 85, wherein said antioxidant is at least one compound represented by the general formula (LXI) -N (R4) 2R, in which any of R1- , R2 and R3 independently are a hydrogen atom; Or an aliphatic hydrocarbyl group; and R 2 are each independently hydrogen or a hydroxy group, -R 2 OH, -R 2 CN, or -CH (Ry) 2, wherein any of R 2 and R 3 is independently hydrogen, a hydrocarbylene or hydrocarbylidene group; and R 3 are each independently hydrogen or an aliphatic hydrocarbyl group. The composition of claim 85, wherein said antioxidant is at least one compound represented by the general formula R 1 Wherein R1, R2, R3 and R4 are independently selected from hydrogen, aliphatic hydrocarbyl groups; and R4 is a hydrocarbylene or hydrocarbylidene group. A composition according to claim 85, ca. characterized in that said antioxidant is at least one compound selected from the group consisting of: 4-t-butyl catechol; 2,6-di-t-butyl-p-cresol; 2,6-di-t-butyl-4- (dimethylamino-methyl) -phenol; 2,5-di-t-amyl-hydroquinone; and 4- (hydroxy-methyl) -2,6-di-t-butyl-phenol. The composition of claim 85, wherein said antioxidant is at least one compound selected from the group consisting of: 2,2'-methylene-bis (4-methyl-6-cyclohexyl -phenol); and 2,2-thio-bis (4-methyl-6-t-butylphenol). Composition according to Claim 85, characterized in that said antioxidant is at least one compound selected from the group consisting of: 4-dodecyl-2-aminophenol; dinonyl diphenyl amine; N, N'-bis (dioctylphenyl) -p-phenylene diamine; phenyl-betanaphthyl amine; and N-phenyl-N '- (1-methylheptyl) -p-phenylene diamine. A composition according to claim 85, wherein said antioxidant is at least one compound selected from the group consisting of: dioctyl-phenothiazine; and dinonyl-phenoxazine. Composition according to Claim 85, characterized in that said antioxidant is at least one compound selected from the group consisting of: 2,6-tetramethyl-4-octyl-piperidine; and bis (2,2,6,6-tetramethyl-A-piperidinyl) sebacate. A composition according to claim 85, characterized in that said antioxidant is trimethyl-dihydroquinoline. A composition according to claim 85, wherein said antioxidant is dodecylamine or N-dodecyl-N-hydroxypropylamine. 105. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles of the exhaust gas, characterized in that it consists of: a main amount of a diesel fuel having a non-sulfur content greater than 0.05% by weight; 279 a smaller amount effective to lower the ignition temperature of the exhaust particles rec &lt;gt; obtained by said capture device of at least one copper complex derived from at least one compound selected from the group consisting of: dodecyl-salicyl-aldoxime; 4,6-di-tert-butyl sali-cil-aldoxime; methyl-dodecyl-salicyl-ketoxime; dodecyl-Î ±, β-di-salicylidene-1,2-propane diamine; dodecyl-Î ±, β-di-salicylidene-1,2-ethanediamine; N, N'-di-salicylidene-1,2-propane diamine; N-salicylidene aniline; N, N'-di-salicylidene-ethylene diamine; salicylal-beta-N-aminoethylpiperazine; and N-salicylidene-N-dodecyl-amine; and a lower fuel stabilizing amount of at least one compound selected from the group consisting of: 4-t-butyl catechol; 2,6-di-t-butyl-4- (dimethylaminoethyl) -phenol; 2,5-di-t-amylhydroquinone; 4- (hydroxy-methyl) -2,6-di-t-butylphenol; 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol); 2,2-thio-bis (4-methyl-6-t-butylphenol); 4-dodecyl-2-aminophenol; dinonyl diphenyl amine; Î ±, β-bis (dioctyl-phenyl) -β-phenylene diamine; phenyl-beta-naphthyl-amine; N-phenyl-N 1 - (1-methylheptyl) -p-phenylene diamine; Dioctyl-phenothiazine; dinonyl-phenoxazine; 2,6-tetramethyl-4-octyl-piperidine; bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate; trimethyl-dihydroquinoline; dodecylamine; and N-dodecyl-N-hydroxy-propylamine. 106. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles of the exhaust gas, characterized in that it consists of: a main quantity of a diesel fuel having a sulfur content not exceeding to about 0.05% by weight; an effective minor amount of at least one copper complex derived from at least one compound selected from the group consisting of: dodecyl-salicyl-aldoxime; 4,6-di-tert-butyl-salicylaldoxime; methyl-dodecyl-salicyl-ketoxime; dodecyl-N, N'-di-s-licilidene-1,2-propane diamine; dodecyl-N, N -di-salipylidene-1,2-ethane diamine; Î ±, β-di-salicylidene-1,2-propane diamine, N-salicylidene aniline; N, N'-di-salicylidene-ethylene diamine; salicylal-beta-N-aminopentyl-piperazine; and N-salicylidene-N-dodecylamino; and 281 a smaller amount effective to lower the ignition temperature of the exhaust gas particles recovered by said capture device, at least one organocobel comprope derived from at least one compound selected from the group consisting of: 4-t-butyl -catechol; 2,6-di-t-butyl-4- (dimethylaminoethyl) -phenol; 2,5-di-t-amyl hydroquinone; 4-Chloro-methyl) -2,6-di-t-butylphenol; 2,2-Î ± -methylene-bis (4-methyl-6-cyclohexyl-phenol); 2,2-thio-bis (4-methyl-6-t-butylphenol); 4-dodecyl-2-aminophenol; dinonyl-diphenyl-amine; Î ±, β-bis (dioctyl-phenyl) -β-phenylene diamine; phenyl-beta-naphthyl-amine; N-phenyl-N '- (1-methyl-heptyl) -p-phenylene diamine; dioctyl phenothiazine; dinonyl-phenoxazine; 2,6-tetramethyl-4-octyl-piperidine; bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate; trimethyl-dihydroquinoline; dodecylamine; and N-dodecyl-N-hydroxy-propylamine. 107. A diesel fuel composition for use in a diesel engine equipped with a device for capturing the small particles of the exhaust system, characterized in that it consists of: a main quantity of a type 282 &lt; diesel having one. sulfur content not exceeding about 0,1% by weight; a smaller amount effective to lower the ignition temperature of the exhaust gas particles recovered by said trap system of at least one organoproplet complex, said complex being derived from: (i) at least one aromatic Mannich compound , wherein said aromatic Mannich compound is the reaction product of (Al) an aromatic compound containing a hydroxy radical and / or thiol having the general formula ## STR3 ## in which Ar is an aromatic group; m is 1, 2 or 3; n is 1 to 4; the symbol independently represents a hydrogen atom or a hiarocarbonyl group having from 1 to about 100 carbon atoms; 283 R 2 represents a hydrogen atom or an amino or carboxyl group; and X represents an oxygen or sulfur atom or both in the case where m is 2 or a higher number; (A-2) is an aldehyde or a ketone having the general formula or a precursor thereof; in which R4 and R4 are each independently hydrogen, saturated hydrocarbyl groups having 1 to about 18 carbon atoms; and the symbol may also represent a hydrocarbyl group containing a carbonyl radical and having from 1 to about 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amine group; and (ii) at least one copper derivative can be converted to a bond with the like 284 (i). 108. A diesel fuel composition for use in a diesel engine equipped with a device for capturing the small particles of the exhaust system, characterized in that it comprises: a major amount of a diesel fuel having a sulfur content not exceeding 0,1% by weight; a minor amount effective to lower the ignition temperature of the exhaust gas particles collected by said capture system of at least one organoproplet complex, said complex being derived from: (i) at least one aromatic Mannich compound, the aromatic compound containing the aromatic compound containing a hydroxy radical and / or thiol having the general formula R 9 ????? (R 1 -) - Ar - (XH) (Al) wherein the Ar represents an aromatic group; m is 1, 2 or 3; n is 1 to 4; R1 is independently hydrogen or hydrocarbyl having from 1 to about 100 carbon atoms; the symbol represents a hydrogen atom or an amino or carboxyl group; and X represents an oxygen or sulfur atom or both in the case where m is 0 or 2; (A-2) an aldehyde or a ketone having the general formula or a precursor thereof; in which the symbols and R4 are each independently a hydrogen atom or saturated hydrocarbyl groups having from 1 to 18 carbon atoms; and R4 may also represent a group hydrocarbyl containing a carbonyl radical and having from 1 to about 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amino group; which amide is characterized by the presence of hydroxide and / or thiol groups; and (ii) at least one copper derivative capable of forming a complex with component (i). A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles from the exhaust system, characterized in that it consists of: a major amount of a diesel fuel, a sulfur content of not more than about 0.1% by weight; a smaller amount effective to lower the ignition temperature of the recovered exhaust particles in said capture device of at least one organoproplex complex, said complex being derived from (i) at least one compound represented by the general formula in which Ar is an aromatic group; and R1, R2 and R3 are each independently hydrogen or hydrocarbyl groups; and (ii) at least one copper derivative reagent capable of forming a complex with component (i). 110. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles from the exhaust system, characterized in that it comprises: a major amount of a diesel fuel having a in sulfur of not more than about 0.1% by weight; a smaller amount effective to lower the ignition temperature of the exhaust gas particles collected in said hair catcher and an organoproplet complex, said complex being derived from (i) at least one compound represented by the general formula in which the symbol represents a methyl group; R2 is a tetrapropene tetramer; and R4 is hydrogen; and (ii) at least one copper derivative capable of forming a complex with the component (i). 111. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles from the exhaust system, characterized in that it comprises a main amount of a diesel fuel having a sulfur content of not more than about 0.1% by weight; a minor amount effective to lower the ignition temperature of the recovered exhaust particles in said trap of at least one organoproplet complex, said complex being derived from (i) at least one aromatic Mannich compound, the aromatic Mannich compound is the reaction product of (Al) an aromatic compound containing a hydroxy radical and / or thiol having the general formula ## STR2 ## in which Ar represents an aromatic group; m is 1, 2 or 3; n is 1 to 4; R1 is independently hydrogen or hydrocarbyl group having 1 to about 100 carbon atoms; B &gt; 2 represents a hydrogen atom or an amino or carboxyl group; and X represents an oxygen or sulfur atom or both in the case where m is 2 or a higher number; (A-2) is an aldehyde or a ketone having the general formula or a precursor thereof; in which R 1 and R 2 are each independently hydrogen atom or saturated hydrocarbyl groups having 1 to about 18 carbon atoms; and R 2 may also represent a hydrocarbyl group containing a carbonyl radical and having 1 to about 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amine group; and ; - '291 · (ii) at least one copper derivative reagent capable of forming a complex with component (i); and a lower stabilizer amount of the fuel, of at least one compound represented by the general formula. (XII) wherein Ar is an aromatic group; and R1, R2 and R3 are each independently hydrogen or hydrocarbyl groups. A composition according to claim 111, characterized in that the compound represented by the general formula (XII) has the general formula OH (XII-1) in which R4 is methyl; R2 is a tetrapropene tetramer; and R6 is hydrogen. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles from the exhaust system, characterized in that it is constituted by: a major amount of a diesel fuel having a in sulfur of not more than about 0.1% by weight; a minor amount effective to lower the ignition temperature of the exhaust gas particles collected in said capture device of at least one organoproplet complex, said complex being derived from (i) at least one aromatic Mannich compound, said compound of Mannich aromatic the reaction product of (Al) an aromatic compound containing a hydroxy radical and / or thiol having the general formula 293 .. (A-1) in which Ar is an aromatic group; m is 1, 2 or 3; n is 1 to 4; R4 is independently hydrogen or hydrocarbyl group having 1 to about 100 carbon atoms; R2 is hydrogen, amino or carboxyl; and X represents an oxygen or sulfur atom or both in the case where m is 2 or a higher number; (A-2) is an aldehyde or a ketone having the general formula or a precursor thereof; in which R 1 and R 2 are each in a hydrogen atom or saturated hydrocarbyl groups having from 1 to about 18 carbon atoms; and R4 may also represent a hydrocarbyl group containing a carbonyl radical and having from 1 to about 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amino group, said amine being characterized by the presence of hydroxyl and / or thiol groups; and (ii) at least one copper derivative reagent capable of forming a complex with the component (i); and a lower stabilizer amount of the fuel of at least one compound represented by the general formula R 3 -Ar C-R 2 (XXX) r 2 in which Ar is an aromatic group; and R 9 and R 9 are each independently a hydrogen atom or hydrocarbyl groups. The composition of claim 113, wherein the compound represented by formula (XII) has the general formula OH (XII-1) wherein the symbol represents a methyl group; R 2 is a tetraene of propylene; and R6 is hydrogen. 115. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles from the exhaust system, characterized in that it consists of *. a principal amount of a diesel fuel, 296 having a sulfur content of not more than about 0.1% by weight; A lower effective amount for lowering the ignition temperature of the exhaust gas particles collected in said trap for at least one organoproplex complex, said complex being derived from (i) at least one compound represented by the general formula OH NOH I II R, - Ar CR. (XII) 3.1 wherein Ar is an aromatic group; and the symbols e3 represent &gt; each independently, a hydrogen atom or hydrocarbyl groups; and (ii) at least one copper derivative reagent capable of forming a complex with the component (i); a lower stabilizer of the fuel of at least one aromatic Mannich compound, said Mannich compound being aromatic with the reaction product of (Al) an aromatic compound containing a hydroxy radical and / or thiol having the general formula (Ar) (XH) m (Al) wherein Ar is an aromatic group; m is 1, 2 or 3; n is 1 to 4; R1 is independently a hydrogen atom or a hydrocarbyl group having from 1 to about 100 carbon atoms; R2 is hydrogen, amino or carboxyl; and X represents an oxygen or sulfur atom or both in the case where m is 2 or a higher number; (A-2) an aldehyde or a ketone having the general formula. 2-9-8 (A-2) or a precursor thereof; in which R 1 and R 2 are each independently hydrogen, saturated hydrocarbyl groups having 1 to about 18 carbon atoms; and R 2 may also represent a hydrocarbyl group containing a carbonyl radical and having 1 to about 18 carbon atoms; and (A-3) an amine containing at least one primary or secondary amine group. Composition according to Claim 115, characterized in that the compound represented by the general formula (XII) has the general formula OH C = NOH R (XII-1) 1 299 in which R1 is methyl; R2 is a tetrapropene tetramer; and R4 is hydrogen. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles from the exhaust system, characterized in that it comprises: a major amount of a diesel fuel, having a sulfur content of not more than about 0.1% by weight; a minor amount effective to lower the ignition temperature of the exhaust gas particles collected in said trap of at least one organoproplet complex, said complex being derived from (i) at least one compound represented by the general formula. 300 (XII) in which Ar is an aromatic group; and R1, R2 and R3 are each independently hydrogen or hydrocarbyl groups; and (ii) at least one copper derivative capable of forming a complex with the component (i); and a lower stabilizer of the fuel of at least one aromatic Mannich compound, said Mannich aromatic compound being the reaction product of (Al) an aromatic compound containing a hydroxy radical and / or thiol having the general formula R 9 I 2 (R-ι) -Ar- (X H) (Al) 1 nm wherein Ar is an aromatic group; m is 1, 2 or 3; n is a standard number 301. between 1 and 4; R1 is independently a hydrogen atom or a hydrocarbyl group having from 1 to about 100 carbon atoms; ο (A-2) R2 is hydrogen, amino or carboxyl; and X represents an oxygen or sulfur atom or both in case m is 0 or 2; an aldehyde or a ketone having the general formula or a precursor thereof; in which 1 and about 18 atoms R 1 and R 2 each independently represent a hydrogen atom or saturated hydrocarbyl groups having 1 to about 18 carbon atoms; and R4 may also represent a hydrocarbyl group containing a carbonyl radical and having from .302 carbon; and (A-3) an amine containing at least one amino group. in the primary or secondary, which amine is characterized by the absence of hydroxyl and / or thiol groups. The composition of claim 117, wherein the compound represented by formula (XII) has the general formula OH (XII-1) wherein R1 is methyl; the symbol represents a tetramer of pro-pylene; and R4 is hydrogen. With a method for operating a diesel engine equipped to capture the small particles of system 303. 303. with the aim of reducing the formation of particulates of the exhaust gases collected in said catching device, characterized in that said diesel engine is operated with a diesel-type fuel composition comprising: a main quantity of a diesel fuel having a sulfur content of not more than about 0.1% by weight; a smaller amount effective to lower the temperature. (i) at least one organic compound containing a hydrocarbon linkage and at least two functional groups, each of said groups being functional groups independently = X, -XR, -NR 2, -NO 2, -NR 2, NR 2, NXR, = NR 2 -XR, -N- (R * N) -R, (X) XR, -N = CR2, -CN or -N = NR; Wherein X is oxygen or sulfur-, R is hydrogen or hydrocarbyl; R4 is hydrocarbyl or hydrocarbylidene; a is a number from 0 to about 10; and (ii) at least one metal reagent capable of forming a complex with component (i), said metal being capable of reducing the ignition temperature of the exhaust particles. 120. A method for operating a diesel-powered equipment and equipped with a device for supplying additives to a fuel and with a device for capturing the small particles of the exhaust system, characterized in that: said diesel engine using a diesel-type fuel having a sulfur content not higher than about 0.11 by weight; the fuel additive in said device is maintained to provide additives to the fuel and oor mixing said fuel additive - 305-305 with said diesel fuel during the operation of said diesel engine, said additive being for the fuel comprised of at least one metal complex derived from (i) at least one organic compound containing a hydrocarbon linkage and at least two groups functional groups, each of which functional groups being independently X, -XR, -NR2, -NO2, = NR1, NXR, = NR * -XR, -N- (R * N) aR, RR- (X ) XR, -P (X) XR, -N = CR ', -CN or -N = NR; Wherein X is oxygen or sulfur; R 2 is hydrogen or a hydrocarbyl group; R4 is hydrocarbylene or hydrocarbylidene; a is a number from 0 to about 10; and at least one metal reagent capable of forming a complex with component (i), (ii) the metal being capable of reducing the ignition temperature of the exhaust particles. A composition according to claim 1, ca. characterized in that component (i) is a compound represented by the general formula (XLIX) / As in which one or more of the ring carbon atoms may be substituted by a hydrocarbyl group. A composition according to claim 1, wherein component (i) is a compound represented by the general formula COORn / 1 (L) in which the symbol represents a hydrogen atom, or a hydrocarbyl group and one or more of the ring carbon atoms may be substituted by a hydrocarbyl group. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles of the exhaust system, characterized in that it comprises: a main amount of a diesel fuel having a sulfur content not exceeding about 0,05% by weight; and a minor amount effective to lower the ignition temperature of the exhaust gas particles collected in said capture device of at least one organoclonal complex, said complex being prepared according to the following steps: (1) carboxylate with dodecylsalicyl aldoxime in the presence of a hydrocarbon solvent to provide an intermediate composition and then (2) admixture with such intermediate composition of an aromatic Mannich compound derived from propylene tetramerophenol, paraformaldehyde and 308-308 ethanolamine. 124. A diesel fuel composition for use in a diesel engine equipped with a device for capturing small particles of the exhaust gas system, characterized in that it consists of: a main amount of a diesel fuel having a in sulfur, not exceeding 0,05% by weight; and a minor amount effective to lower the ignition temperature of the exhaust gas particles collected in said capture device from at least one organocop complex, said complex being prepared by reacting alkaline copper carbonate with dodecyl-salicyl aldoxime in the presence of a hydrocarbon solvent. 125. - Fuel type composition for use as fuel. in a diesel engine equipped with a device for capturing small particles of the exhaust system, characterized in that it consists of: a main quantity of a diesel fuel having a sulfur content not exceeding about 0.05% by weight; and a minor amount effective to lower the ignition temperature of the exhaust gas particles collected in said capture device from at least one organocop complex, said complex being prepared by reacting alkaline copper carbonate with a first aromatic Mannich component derived from heptyl phenol, N-tallow-1,3-diamino propane and paraformaldehyde and with a second aromatic Mannich component derived from the tetramer of propylene, phenol, ethanolamine and paraformaldehyde. Lisbon, October 19, 1992 • Official Agent of Industrial Practices