[0001] This invention relates to fuel oil compositions, and to additives for use in such
compositions. More especially it relates to diesel, heating, and jet fuel oil compositions,
and to reduction of particulate emissions on combustion.
[0002] Although modern internal combustion engines are highly efficient and give almost
complete combustion of the hydrocarbon fuel used, the slight reduction from total
efficiency leads to the formation of black smoke, a proportion of which is particulate
carbon. Apart from the smoke's being unpleasant to breathe and unsightly, the carbon
particles may have absorbed in them polynuclear hydrocarbons, which also result from
incomplete combustion, some of which are known carcinogens.
[0003] It has been previously proposed to use certain additives to reduce smoke. These additives,
which are based on metal salts, reduce smoke at the expense of increasing particulate
emission, because the additive is emitted in the form of oxide or sulphate which contributes
to the mass of particulates in the exhaust.
[0004] There remains a need for an emission-reducing additive for diesel and jet fuel that
is itself metal-free and combustible without contributing to the weight of particulates
emitted.
[0005] The present invention is based on the observation that certain dispersants, if desired
in combination with cetane enhancers, when incorporated in a diesel, heating or jet
fuel, reduce the emission of particulates.
[0006] In its broadest aspect, therefore, the present invention provides the use of an ashless
oil soluble macrocyclic polyamine dispersant to reduce particulate emission in the
combustion of a fuel oil. More especially, the dispersant is one containing the group
-N=C-N-C=O, of which the -N=C-N group forms part of a ring, and of which the carbon
and nitrogen atoms of the C-N=C=O form part of a different ring.
[0007] The present invention accordingly provides the use as an additive in a fuel oil,
to reduce particulate emission on combustion of the fuel oil, other than the reduction
resulting from a reduction in injector fouling in a diesel engine, of an oil soluble
compound of the formula:
or
R
12R
13N-(CR
16R
17)
n-[NH(CR
18R
19)
u]
b-NR
13R
13 (II)
or mixtures of two or more such compounds, wherein a is from 1 to 150, R
1, R
2 and R
3 may be the same or different and are independently hydrogen or a hydrocarbyl substituent
having from 2 to 600 carbon atoms, or a keto, halo, hydroxy, nitro, cyano, or alkoxy
derivative thereof, provided that at least one of R
1, R
2 and R
3 is a hydrocarbyl substituent having from 2 to 600 carbon atoms or said derivative
thereof, or wherein R
1 and R
2 together form a hydrocarbylene substituent having 4 to 600 carbon atoms or a keto,
halo, hydroxy, nitro, cyano or alkoxy derivative thereof, provided that R
1 and R
2 together with the carbon atom which forms the C-R
1 bond with R
1 and the nitrogen atom which forms the N-R
2 bond with R
2 form a ring having at least 5 members, wherein Z represents
-R
10[NR
11(R
10)]
c-
or
-[R
10R
11N]
dR
10[NR
11R
10]
e
wherein each R
10, which may be the same or different, represents an alkylene group having from 1 to
5 carbon atoms in its chain, each R
11, which may be the same or different, represents a hydrogen atom or a hydrocarbyl
group, and c is from 0 to 6, d is from 1 to 4, e is from 1 to 4, provided that d +
e is at most 5, R
12 is a hydrocarbyl substituent having from 2 to 400 carbon atoms, each R
13 is independently hydrogen or a C
1 to C
12 hydrocarbyl, R
16, R
17, R
18, and R
19 are independently hydrogen, a hydrocarbyl group having from 1 to 10 carbon atoms,
an acyl group having from 2 to 10 carbon atoms, or a monoketo, monohydroxy, mononitro,
monocyano or alkoxy derivative of a hydrocarbyl group having from 1 to 10 carbon atoms
or of an acyl group having from 2 to 10 carbon atoms, n is from 1 to 6, u is from
1 to 6, and b is from 0 to 12.
[0008] Advantageously, when c is zero, there are at least two carbon atoms in the R
10 alkylene chain.
[0009] As used in this specification the term "hydrocarbyl" refers to a group having a carbon
atom directly attached to the rest of the molecule and having a hydrocarbon or predominantly
hydrocarbon character. Among these, there may be mentioned hydrocarbon groups, including
aliphatic, (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl),
aromatic, aliphatic- and alicyclic-substituted aromatic, and aromatic-substituted
aliphatic and alicyclic groups. Aliphatic groups are advantageously saturated. Examples
include methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, octadecyl,
cyclohexyl, and phenyl. These groups may, as indicated above, contain non-hydrocarbon
substituents provided they do not alter the predominantly hydrocarbon character of
the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If
the hydrocarbyl group is substituted, a single (mono) substituent is preferred. Examples
of substituted hydrocarbyl groups include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl,
2-ketopropyl, ethoxyethyl, and propoxypropyl. The groups may also or alternatively
contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms.
Suitable hetero atoms include, for example, nitrogen, oxygen and sulfur. The term
"hydrocarbylene" is used analogously; such a group is attached to the rest of the
molecule at least at one end and preferably at both ends through a carbon atom.
[0010] Advantageously, there is used a compound of the formula:
wherein R
7 is hydrogen or a hydrocarbyl substituent having from 1 to 600 carbon atoms, R
8 is hydrogen or a C
1 to C
12 hydrocarbyl substituent and, if there is more than one R
8 in a compound, they may be the same or different, R
9 is a hydrocarbylene substituent having from 2 to 600 carbon atoms, two of which carbon
atoms are bonded to the α-carbon atoms of the succinic anhydride based ring, X
1 represents hydrogen or an alkyl group having from 1 to 12 carbon atoms, X
2 represents hydrogen, an alkyl group having from 1 to 12 carbon atoms, a hydroxy group,
or an alkoxy group, having from 1 to 12 carbon atoms, or X
1 and X
2 may together represent an oxygen or sulphur atom, Z has the meaning given above,
and h is from 1 to 20. Advantageously h represents 1.
[0011] Although in R
10 the alkylene chain may have at most 5 carbon atoms, it may be branched, and the length
of the branch or branches is not limited. When R
3 represents a hydrocarbyl substituent, and Z contains a nitrogen atom, the hydrocarbyl
substituent is advantageously linked to the, or a, nitrogen atom. The nitrogen-hydrocarbyl
linkage may in that case be, e.g., an amide linkage.
[0012] Preferably there is used a macrocyclic polyamine compound of the formula:
or
or mixtures of two or more such compounds, wherein R
12 is a hydrocarbyl substituent having from 2 to 400 carbon atoms, R
13 is hydrogen or a C
1 to C
12 hydrocarbyl substituent, R
14 is a hydrocarbylene substituent having from 4 to 400 carbon atoms, two of which carbon
atoms are bonded to the α-carbon atoms of the succinic anhydride based ring, and Z
represents -CH
2CH
2CH
2-; -(CH
2CH
2CH
2NH)
nCH
2CH
2CH
2-, where n is 1 to 6, or -(CH
2CH
2CH
2NH)
m(CH
2)
p(NHCH
2CH
2CH
2)
q- where m and q are each at least 1 and m+q = 2 to 5, p is 1 to 5, and a is 1 to 20.
[0013] The invention also provides a method of reducing particulate emission resulting from
the combustion of a fuel oil, which comprises mixing a compound of the formula I or
II, more especially a compound of the formula III, IV, or V, as defined above, with
the fuel oil before burning the fuel oil. Also provided is a method of reducing particulate
emission resulting from burning fuel oil, which comprises the combustion of a fuel
oil containing an above-mentioned compound.
[0014] A method for the preparation of the macrocyclic polyamines of the formulae above
is described, for example, in U.S. Patent No. 4 637 886. Formation of the macrocyclic
and optionally polymacrocyclic compounds proceeds by the aminolysis of hydrocarbyl
succinic anhydride, monocarboxylic acid or polycarboxylic acid, adding the acid or
anhydride to the di or polyamide compound, as described in more detail in the above-referenced
U.S. Patent.
[0015] The hydrocarbyl and hydrocarbylene substituents R
12 and R
14 are advantageously derived from a polymer based on a major amount of a C
2 to C
5 olefin, for example homo or copolymers of ethylene, propylene, butylene (1- or 2-),
pentylene and, especially, isobutylene.
Polyisobutylene is especially preferred. When the polymer is a copolymer, it may be
a copolymer of two or more of the specified monomers, or a copolymer of one or more
of the specified monomers with a copolymerizable unsaturated monomer; when the polymer
is a copolymer it may be a block or a random copolymer.
[0016] The polymer advantageously has from 5 to 300 carbon atoms, preferably 10 to 200 carbon
atoms and most preferably 20 to 100 carbon atoms. Preparation of the alkyl and alkenyl
succinic anhydrides which form convenient reactants for the cyclodehydration reaction
by which the macrocyclic polyamine may be produced is described, for example, in U.S.
Patents Nos. 3 018 250 and 3 024 195.
[0017] Suitable amine reactants are of the formula NH
2-Z-NH
2, where Z has the meaning given above. Preferred amines include 1,3-propane diamine;
3,3'-imino-bis-propylamine, N,N'-bis (3-aminopropyl)ethylene diamine; N,N'-bis(3-aminopropyl)-1,3-propane
diamine; other suitable amines include ethylene diamine, diethylene triamine, triethylene
tetramine, tetraethylene pentamine, pentamethylene hexamine, dipropylene triamine,
tripropylene tetramine, tetrapropylene pentamine and pentapropylene hexamine.
[0018] The mole ratio of alkenyl or alkyl succinic anhydride to polyamine used in the preferred
preparation of the macrocyclic polyamines may vary, for example, from 0.2:1 to 5:1,
and is preferably from 0.5:1 to 2:1, and most preferably from 0.5:1 to 1.5:1.
[0019] As monocarboxylic acid there may be used an acid of the formula:
R
15-COOH
where R
15 is hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl,
or aryl group. Examples of such acids include formic acid, acetic acid, propionic
acid, butyric acid, valeric acid, palmitic acid, stearic acid, cyclohexanecarboxylic
acid, 2-methylcyclohexane carboxylic acid, 4-methylcyclohexane carboxylic acid, oleic
acid, linoleic acid, linolenic acid, cyclohex-2-eneoic acid, benzoic acid, 2-methylbenzoic
acid, 3-methylbenzoic acid, 4-methylbenzoic acid, salicylic acid, 2-hydroxy-4-methylbenzoic
acid, 2-hydroxy-4-ethylsalicylic acid, p-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic
acid, o-aminobenzoic acid, p-aminobenzoic acid, o-methoxybenzoic acid and p-methoxybenzoic
acid.
[0020] As dicarboxylic acid there may be used an acid of the formula:
HOOC-(CH
2)
t-COOH
where t is zero or an integer, including e.g. oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic acid, pimelic acid and suberic acid, or an acid of the
formula:
where t is zero or an integer, y is zero or an integer and x and y may be equal or
different and R
15 is as defined above. Examples of such acids include the alkyl or alkenyl succinic
acids, 2-methylbutanedioic acid, 2-ethylpentanedioic acid, 2-n-dodecylbutanedioic
acid, 2-n-dodecenylbutanedioic acid, 2-phenylbutanedioic acid, and 2-(p-methylphenyl)butanedioic
acid. Also included are polysubstituted alkyl dicarboxylic acids wherein other R
15 groups as described above may be substituted on the alkyl chain. These other groups
may be substituted on the same carbon atom or different atoms. Such examples include
2,2-dimethylbutanedioic acid; 2,3-dimethylbutanedioic acid; 2,3,4-trimethylpentanedioic
acid; 2,2,3-trimethylpentanedioic acid; and 2-ethyl-3-methylbutanedioic acid.
[0021] The dicarboxylic acids also include acids of the formula:
HOOC-(C
rH
2r-2)COOH
where r is an integer of 2 or more. Examples include maleic acid, fumaric acid, pent-2-enedioic
acid, hex-2-enedioic acid; hex-3-enedioic acid, 5-methylhex-2-enedioic acid; 2,3-di-methylpent-2-enedioic
acid; 2-methylbut-2-enedioic acid; 2-dodecylbut-2-enedioic acid; and 2-polyisobutylbut-2-enedioic
acid.
[0022] The dicarboxylic acids also include aromatic dicarboxylic acids e.g. phthalic acid,
isophthalic acid, terephthalic acid and substituted phthalic acids of the formula:
where R
15 is as defined above and n = 1, 2, 3 or 4 and when n > 1 then the R groups may be
the same or different. Examples of such acids include 3-methylbenzene-1,2-dicarboxylic
acid; 4-phenylbenzene-1,3-dicarboxylic acid; 2-(1-propenyl)benzene-1,4-dicarboxylic
acid, and 3,4-dimethylbenzene-1,2-dicarboxylic acid.
[0023] The preparation of such compounds is described for example in U.S. Patents Nos. 3
438 757, 3 565 804, 3 574 576, 3 671 511, 3 898 056, and 3 960 515, and British Patents
No. 1 254 338 and 1 398 067. In this embodiment, the preferred hydrocarbyl substituents
represented by R are as given above with reference to the macrocyclic polyamines.
[0024] The polyamine used to derive the hydrocarbyl polyamine is advantageously a compound
having from 2 to 12 nitrogen atoms and from 2 to 40 carbon atoms. The preferred hydrocarbyl
polyamines for use in this invention are compounds derived from polyalkylene polyamines,
including alkylene diamines and substituted polyalkylene polyamines. Preferably, the
alkylene group contains from 2 to 6 carbon atoms, there being preferably from 2 to
3 carbon atoms between the nitrogen atoms. Examples of such polyamines include ethylene
diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, di(trimethylene)triamine,
propylene diamine, dipropylene triamine, tripropylene tetramine, N-methyl ethylene
diamine, N-N,-dimethyl ethylene diamine, N-methyl-1,3-diamino propane and N,N-dimethyl-1,3-diamino
propane. Such amines include branched chain polyamines and cyclic structures formed
by reaction of linear polyamines. Among the polyalkylene polyamines those containing
from 2 to 12 nitrogen atoms and from 2 to 24 carbon atoms are especially preferred.
[0025] The mole ratios of alkyl or alkenyl halide to polyamine, used in accordance with
the preferred method of making the compounds, are as described above for the succinic
anhydride/polyamine reaction.
[0026] In further embodiments of this invention, the additive used may be a derivative of
the macrocyclic or hydrocarbyl polyamines described above, such derivative being one
obtainable by, and preferably one obtained by, post-treatment with, for example, boron
oxide, boron oxide hydrate, a boron halide, a boron acid, sulphur, a sulphur chloride,
a phosphorus oxide or sulphide, a carboxylic acid or anhydride, an acyl halide, an
epoxide, an episulphide or acrylonitrile. Methods for carrying out such treatment
are well known in the art; for example boration to incorporate 0.1 to 1 atoms of boron
for each nitrogen atom may be carried out as described in U.S. Patent No. 3 254 025.
[0027] A preferred post-treatment for the formation of an additive is treatment with polyisobutylene
succinic anhydride. Advantageously, the macrocyclic or hydrocarbyl polyamine is treated
with 10 to 50 mole % of an anhydride formed from a polyisobutylene of molecular weight
900 to 1200, for example by reaction at 120°C for an hour or until the reaction mixture
contains no free anhydride.
[0028] In a third embodiment, accordingly, the invention provides the use as a particulate-reducing
additive for, and the use in reducing particulate emission in the combustion of, a
diesel or jet fuel of a post-treated macrocyclic or hydrocarbyl polyamine as defined
above, especially one post treated with a polyisobutylene succinic anhydride.
[0029] The additives may be used either alone or in combination with other additives according
to the invention or in combination with other fuel additives. Advantageously the concentration
of the additive according to the invention in the fuel is in the range of from 0.0005
to 2, preferably from 0.001 to 0.5, and more preferably from 0.005 to 0.3%, based
on the weight of the fuel.
[0030] The use of other additives does not adversely affect the performance of the macrocyclic
compound. In some cases the use of another additive or additives may lead to a reduction
in emissions greater than might be expected. Other additives which may be used include,
for example, diesel detergents, antifoam additives, antirust additives, and demulsifiers.
These other additives may be present in the fuel in a total concentration of 0.001
to 1, preferably 0.005 to 0.2, and most preferably a total concentration of 0.005
to 0.05%, based on the total weight of fuel.
[0031] A specific example of such a combination is the use of a macrocyclic compound with
a detergent which is the uncyclized reaction product formed from a hydrocarbyl succinic
anhydride and a polyamine. The detergent is advantageously present in a concentration
of 0.005 to 0.1, preferably 0.005 to 0.5, and most preferably from 0.005 to 0.2%,
based on the total weight of the fuel.
[0032] It has also been unexpectedly found that the use of a combination of one or more
of the additives in accordance with the invention together with a cetane improver
gives enhanced particulate emission reduction. Accordingly, the invention also provides
such use.
[0033] Preferred cetane improvers are organic nitrates; there may also be used, for example,
substituted triazoles and tetrazoles, for example those described in European Patent
Application No. 230783. Preferred organic nitrates are nitrate esters containing aliphatic
or cycloaliphatic groups with up to 30 carbon atoms, preferably saturated groups,
and preferably with up to 12 carbon atoms. As examples of such nitrates, there may
be mentioned methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl,
iso-octyl, 2-ethylhexyl, nonyl, decyl, allyl, cyclopentyl, cyclohexyl, methylcyclohexyl,
cyclododecyl, 2-ethoxyethyl, and 2-(2-ethoxyethoxy) ethyl nitrates.
[0034] The cetane improver is advantageously used at a concentration in the fuel in the
range of from 0.0005 to 1, preferably 0.005 to 0.5 and most preferably from 0.01 to
0.2%, based on the weight of the fuel.
[0035] The following examples, in which all parts and percentages are by weight unless otherwise
indicated, illustrate the invention.
Example A
[0036] Eight batches of polyisobutylene succinic anhydride (PIBSA) were synthesized by treating
450 MW polyisobutylene (PIB:450g:1 mole) with maleic anhydride. The quantities of
maleic anhydride, the reaction times and temperatures and the catalyst concentration
are shown in Table 1. The eight batches of thermal PIBSA were combined to give the
final product. Analysis of the product gave:
Saponification number = 128.7 mg KOH/g
Free Maleic anhydride < 0.1 %.
[0037] The saponification number indicates that the product has an effective molecular weight
of 870. The IR spectrum of the product in the carbonyl region (1900-1500 wavenumbers
or cm
-1) shows two major peaks at 1863 and 1786 wavenumbers.
Table 1
Maleic Anhydride (moles) |
Temperature (°C) |
Reaction Time (hr) |
Catalyst (%) |
1.00 |
200 |
8 |
1.00 |
0.75 |
220 |
8 |
1.00 |
0.75 |
200 |
8 |
0.00 |
0.75 |
200 |
12 |
0.00 |
1.00 |
200 |
12 |
1.00 |
1.00 |
220 |
12 |
0.00 |
1.00 |
220 |
8 |
0.00 |
0.75 |
220 |
12 |
1.00 |
[0038] The catalyst was an alkylaryl sulphonic acid and the percentage is based on the charge
of PIB.
Example B
[0039] A solution of the thermal PIBSA (435g:0.5 moles) from Example A was dissolved in
xylene (200 ml) and slowly added (over 20 hours) to a solution of 1,3-diaminopropane
(37g:0.5 moles) in xylene (150 ml) at 100°C. When the addition was complete the reaction
temperature was increased so that the xylene refluxed and water (16 ml:0.89 moles)
was collected using a Dean and Stark trap. When removal of water was complete, the
xylene was removed by distilling to 180°C. A vacuum was applied to remove the last
traces of solvent. The product was a dark viscous oil containing 2.8% nitrogen (Theory
= 3.08%).
[0040] The IR spectrum of the product had four peaks between 1900 and 1500 wavenumbers at
1772(w), 1738(m), 1705(s) and 1674(vs) wavenumbers. Such a spectrum is indicative
of the presence of a macrocyclic compound. (In contrast the IR spectrum of the uncyclized
additives contains only three peaks in the same region of the spectrum. There is a
weak absorption at 1771-72 wavenumbers, a strong absorption at 1701-04 wavenumbers
and a medium strength absorption at 1667-70 wavenumbers.)
Example C
[0041] A solution of thermal PIBSA (435g:0.5 moles) from Example A was dissolved in xylene
(200 ml) and slowly added (over 8.25 hours) to a refluxing solution of 3,3'-imino-bis-propylamine
(65.6g:0.5 moles) in xylene (150 ml). As the reaction proceeded, the water formed
(16.5 ml: 0.92 moles) was collected using a Dean and Stark trap. When the addition
was complete and no more water was formed the solvent was removed by heating to 180°C
under vacuum. The product was a dark viscous oil containing 4.0% nitrogen (Theory
= 4.35%).
[0042] The IR spectrum of the product has four peaks between 1900 and 1500 wavenumbers at
1771(w), 1732(w), 1702(s) and 1668(s) wavenumbers.
Example D
[0043] The method of Example C was repeated using N,N'-bis-(3-aminopropyl)-ethylenediamine
(87g:0.5 moles). The solution of thermal PIBSA was added over 31.5hr and water (17.5ml:0.97
moles) was removed using a Dean and Stark trap. After removing the volatile solvent
the product (475g) was a dark viscous oil which contained 5.4% nitrogen (Theory =
5.56%).
[0044] The IR spectrum of the product has four peaks between 1900 and 1500 wavenumbers at
1772(w), 1737(vs), 1701(vs) and 1669(vs).
Example E
[0045] A batch of PIBSA was synthesized by reacting 960MW PIB with maleic anhydride at high
temperature. The resulting material was diluted with solvent 150 base oil to produce
a product with a saponification number of 70.7 mg KOH/g. The saponification number
indicates that the product has an effective weight of 1584.
Example F
[0046] The thermal PIBSA from Example E (500g:0.32 moles) was added to a solution of 1,3-diaminopropane
(24g:0.32 moles) in toluene (200 ml) at 25°C. The reaction mixture was heated to reflux
and then the solvent and water of reaction were removed by distilling to a pot temperature
of 170°C. The reaction mixture was held at a temperature of 170°C for 7 hours. During
this time IR spectra of the product were recorded to monitor the formation of the
macrocycle.
[0047] The product was a dark viscous oil which contained 1.5% nitrogen (Theory = 1.75%).
The IR spectrum of the product containing four peaks between 1900 and 1500 wavenumbers
at 1773(w), 1739(m), 1706(s) and 1675(vs).
Example G
[0048] The method used in Example F was repeated using thermal PIBSA from Example E (500g:0.32
moles) and 3,3'-imino-bis-propylamine (42g:0.32 moles). The product was a dark viscous
oil which contained 2.3% nitrogen (Theory = 2.53%). The IR spectrum of the product
contained four peaks between 1900 and 1500 wavenumbers at ca. 1770(w), 1730(m), 1702(s)
and 1670(s).
Example H
[0049] The method used in Example F was repeated using thermal PIBSA from Example E (500g:0.32
moles) and N,N'-bis-(3-aminopropyl)ethylene diamine (56g:0.32 moles). The product
was a dark viscous oil which contained 3.2% nitrogen (Theory = 3.29%). The IR spectrum
of the product contained four peaks between 1900 and 1500 wavenumbers at 1771(w),
1731(m), 1702(vs) and 1668(vs).
Example I
[0050] The method used in Example E was repeated using thermal PIBSA from Example E (500g:0.32
moles) and N,N'-bis-(3-aminopropyl)-1,3-propylene diamine (61g:0.32 moles). The product
was a dark viscous oil which contained 3.0% nitrogen (Theory = 3.26%). The IR spectrum
of the product contained four peaks between 1900 and 1500 wavenumbers at 1770(w),
1735(m), 1699(s) and 1668(vs).
Example J
[0051] The method used in Example F was repeated using thermal PIBSA from Example E (500g:0.32
moles) and pentapropylene hexamine (74g:0.32 moles). The product was a dark viscous
oil which contained 3.8% nitrogen (Theory = 3.98%). The IR spectrum of the product
contained five peaks between 1900 and 1500 wavenumbers at 1769(w), 1732(m), 1701(s),
1668(vs) and 1618(w).
Example K
[0052] A sample of PIBSA was prepared by reacting a 960MW PIB with maleic anhyride. The
resulting PIBSA had a saponification number of 96.3 mg KOH/g, so that the effective
molecular weight of the PIBSA was 1163.
[0053] The PIBSA (300g:0.26 moles) was added to a refluxing solution of N,N'-bis-(3-aminopropyl)ethylene
diamine (44.8g:0.26 moles) in toluene (200 ml). When the addition of the PIBSA was
complete the solvent and water were removed by distilling the reaction mixture of
a temperature of 170°C. The reaction mixture was kept at 170°C under a stream of nitrogen
for seven hours. After that time the IR spectrum of the product showed that no more
macrocycle was being formed. The product was a dark viscous oil which contained 3.9%
nitrogen (Theory = 4.28%). The IR spectrum of the product contained four peaks between
1900 and 1500 wavenumbers at 1771(w), 1733(m), 1701(s) and 1667(vs).
EXAMPLE L
[0054] 3500 g of N,N'-bis(3-aminopropyl)ethylenediamine was dissolved in 4750 g of xylene
and heated to 80°C. Polyisobutylene succinic anhydride (26910g), prepared from polyisobutylene
of Mn 1000 via the "ene" reaction, was added to the amine solution over a period of
2 hours. The reaction mixture was then heated to reflux for 10 hours and water removed.
After refluxing, the solvent was removed by distillation to give a final product with
3.71% nitrogen and a TBN of 97.7 mg KOH/g.
EXAMPLE 1
[0055] The additives from Examples F to K were tested in an engine to determine their effect
on particulate emissions. The engine used was a 6 cylinder 4 stroke naturally aspirated
DI engine with the following specification:
Swept Volume = 5958cc.
Maximum Power = 100 KW at 2800rpm.
Maximum Torque = 402 NM at 1400rpm.
Compression Ratio = 17.25:1
[0056] The fuel used in the tests was a standard UK automotive diesel fuel. A typical analysis
was:
Specific Gravity = 0.849 kg/litre
Cetane Index = 51
Distillation |
°C |
IBP |
162 |
20% |
252 |
50% |
286 |
90% |
338 |
FBP |
369 |
Sulphur Content = 0.23%
Flash Point = 69°C.
[0057] The additives were compared at 500ppm using tests run in the following manner:
1. The engine was conditioned prior to testing each additive by running the engine
on the test fuel at 75% speed and 75% load for 12 hours.
2. The emissions from the engine were then measured using a standard ECE R49 thirteen
mode test.
[0058] The results from the test are shown in Table 2.
Table 2
Additive |
Particulate (g/KWhr) |
nil |
1.08 |
Example F |
0.80 |
Example G |
0.80 |
Example H |
0.86 |
Example I |
0.88 |
Example J |
0.93 |
Example K |
0.87 |
[0059] It is clear from the results in Table 2 that all the additives tested reduce the
mass of particulates emitted by the engine during the R49 test. The reduction varies
from 13.9% to 25.9%. It is apparent that the size of the macrocyclic ring affects
performance. The small ring macrocyclic compounds (Examples F and G) are more effective
than the large ring macrocyclic compounds (Examples H to K).
Example 2
[0060] The engine and fuel of Example 1 were used to determine the effect of additive concentration
on reduction of particulates. The additive from Example L was tested at different
concentrations. The tests were run in the following manner:
1. The engine was warmed up over a period of 90 minutes to full speed and full load.
2. A stabilizing test was run using untreated fuel.
3. A test was run on the untreated fuel and emission data were collected.
4. A test was run on the fuel treated with the additive and emission data were collected.
5. Stages 3 and 4 were repeated using different concentrations of the additive.
[0061] The emissions measured included the quantity of particulate present in the exhaust.
Table 1 shows the % reduction of particulate between stages 4 and 3 with different
concentrations of additive.
TABLE 3
ADDITIVE(ppm) |
REDUCTION IN PARTICULATE(%) |
0 |
0.0 |
125 |
2.6 |
250 |
5.1 |
500 |
10.5 |
1000 |
20.3 |
[0062] The effect of the additive in reducing particulate is apparent.
EXAMPLE 3
[0063] The additive from Example K was tested alone and in combination with a cetane improver.
The cetane improver was an alkyl nitrate made from a C
8 alcohol. The experiments were carried out using the standard ECE R49 thirteen mode
test. The tests were run using a VOLVO TD121/122F engine. The fuel used was similar
to that used in Example 1. The weight of particulate formed in each stage of the test
was measured by collecting the particulate on a pre-weighed filter paper. The overall
amount of particulate from the 13 modes was determined using the standard weighting
factors for each mode. The results are shown in Table 4.
TABLE 4
The Effect of a Macrocyclic Polyamine with and without a Cetane Improver on Particulate
Emissions |
Macrocyclic Polyamine (ppm) |
Cetane Improver (ppm) |
Particulate (g/KWhr) |
0 |
0 |
0.243 |
500 |
0 |
0.226 |
150 |
750 |
0.131 |
[0064] It can be seen that 500ppm of the macrocyclic polyamide alone reduces the weight
of particulate by 7%. Reducing the amount of polyamine to 150ppm and using cetane
improver (750ppm) reduces the particulate by 46%.
EXAMPLE 4
[0065] The additive from Example L was tested alone and in combination with the cetane improver
used in Example 3 using the standard ECE R49 thirteen mode test in a PERKINS PHASER
180 Ti engine. The fuel used was similar to that used in Example 1. The weight of
particulate formed in each stage of the test was measured as in Example 3. The results
are shown in Table 5.
TABLE 5
Macrocyclic Polyamine (ppm) |
Cetane Improver (ppm) |
Particulate (g/KWhr) |
0 |
0 |
0.911 |
500 |
0 |
0.730 |
150 |
750 |
0.696 |
[0066] It can be seen that 500ppm of the macrocyclic dispersant alone reduces the amount
of particulate by 20%. Reducing the amount of dispersant to 150ppm and using cetane
improver (750ppm) reduces the particulate by 24%.
1. The use as an additive in a fuel oil, to reduce particulate emission on combustion
of the fuel oil, other than the reduction resulting from a reduction in injector fouling
in a diesel engine, of an oil soluble compound of the formula:
or
R
12R
13N-(CR
16R
17)
n-[NH(CR
18R
19)
u]
b-NR
13R
13 (II)
or mixtures of two or more such compounds, wherein a is from 1 to 150, R
1, R
2 and R
3 may be the same or different and are independently hydrogen or a hydrocarbyl substituent
having from 2 to 600 carbon atoms, or a keto, halo, hydroxy, nitro, cyano, or alkoxy
derivative thereof, provided that at least one of R
1, R
2 and R
3 is a hydrocarbyl substituent having from 2 to 600 carbon atoms or said derivative
thereof, or wherein R
1 and R
2 together form a hydrocarbylene substituent having 4 to 600 carbon atoms or a keto,
halo, hydroxy, nitro, cyano or alkoxy derivative thereof, provided that R
1 and R
2 together with the carbon atom which forms the C-R
1 bond with R
1 and the nitrogen atom which forms the N-R
2 bond with R
2 form a ring having at least 5 members, wherein Z represents
-R
10[NR
11(R
10)]
c-
or
-[R
10R
11N]
dR
10[NR
11R
10]
e
wherein each R
10, which may be the same or different, represents an alkylene group having from 1 to
5 carbon atoms in its chain, each R
11, which may be the same or different, represents a hydrogen atom or a hydrocarbyl
group, and c is from 0 to 6, d is from 1 to 4, e is from 1 to 4, provided that d +
e is at most 5, R
12 is a hydrocarbyl substituent having from 2 to 400 carbon atoms, each R
13 is independently hydrogen or a C
1 to C
12 hydrocarbyl, R
16, R
17, R
18, and R
19 are independently hydrogen, a hydrocarbyl group having from 1 to 10 carbon atoms,
an acyl group having from 2 to 10 carbon atoms, or a monoketo, monohydroxy, mononitro,
monocyano or alkoxy derivative of a hydrocarbyl group having from 1 to 10 carbon atoms
or of an acyl group having from 2 to 10 carbon atoms, n is from 1 to 6, u is from
1 to 6, and b is from 0 to 12.
2. The use as claimed in claim 1, wherein the compound is a compound of the formula I
and is of the formula:
wherein R
7 is hydrogen or a hydrocarbyl substituent having from 1 to 600 carbon atoms, R
8 is hydrogen or a C
1 to C
12 hydrocarbyl substituent, and, if there is more than one R
8 in a compound, they may be the same or different, R
9 is a hydrocarbylene substituent having from 2 to 600 carbon atoms, two of which carbon
atoms are bonded to the α-carbon atoms of the succinic anhydride based ring, X
1 represents hydrogen or an alkyl group having from 1 to 12 carbon atoms, X
2 represents hydrogen, an alkyl group having from 1 to 12 carbon atoms, a hydroxy group,
or an alkoxy group having from 1 to 12 carbon atoms, or X
1 and X
2 may together represent an oxygen or sulphur atom, Z has the meaning given in claim
1, and h is from 1 to 20.
3. The use as claimed in claim 2, wherein the compound is an oil soluble compound of
the formula
or mixtures of two or more such compounds, wherein R
12 is a hydrocarbyl substituent having from 2 to 400 carbon atoms, R
13 is hydrogen or a C
1 to C
12 hydrocarbon substituent, and, if there is more than one R
13 in a compound they may be the same or different, R
14 is a hydrocarbylene substituent having from 4 to 400 carbon atoms, two of which carbon
atoms are bonded to the α-carbon atoms of the succinic anhydride based ring and -Z-
represents -CH
2CH
2CH
2-; -(CH
2CH
2CH
2NH)
nCH
2CH
2CH
2-, where n is 1 to 6, or -(CH
2CH
2CH
2NH)
m(CH
2)
p(NHCH
2CH
2CH
2)
q- where m and q are each at least 1 and m+q = 2 to 5, p is 1 to 5, and a is 1 to 20.
4. The use as claimed in any one of claims 1 to 3, wherein at least one of R1, R2 and R3, or wherein at least one of R7 and R9, or wherein at least one of R12 or R14 is derived from a C2 to C5 olefin polymer.
5. The use as claimed in claim 4, wherein the polymer is polyisobutylene.
6. The use as claimed in claim 4 or claim 5, wherein the polymer contains from 10, preferably
from 20, to 200 carbon atoms.
7. The use as claimed in any one of claims 1 to 6, wherein -Z- represents -(CH2)3NH(CH2)3-, -(CH2)3NHCH2CH2NH(CH2)3-, or -(CH2)3-.
8. The use as claimed in any one of claims 1 to 7, wherein the oil soluble compound has
been prepared by the reaction of a hydrocarbyl reactant and a polyamine reactant in
a mole ratio of from 0.2:1 to 5:1, preferably from 0.5:1 to 2:1.
9. The use as claimed in any one of claims 1 to 8, wherein the oil soluble compound is
used in the form of a post-treatment derivative, preferably one formed by post-treatment
of the oil soluble compound with boron oxide, boron oxide hydrate, a boron halide,
a boron acid, sulphur, a sulphur chloride, a phosphorus oxide or sulphide, a carboxylic
acid or anhydride, e.g., polyisobutylene succinic anhydride, an acyl halide, an epoxide,
an episulphide or acrylonitrile.
10. The use as claimed in any one of claims 1 to 9, wherein the oil soluble compound is
present in the fuel in a proportion in the range of from 0.0005 to 2%, advantageously
0.001 to 0.5%, preferably 0.005 to 0.3%, by weight, based on the weight of the fuel.
11. The use as claimed in any one of claims 1 to 10, wherein the oil soluble compound
is used in admixture or association with a cetane improver, advantageously an aliphatic
or cycloaliphatic nitrate, preferably an alkyl or cycloalkyl nitrate containing up
to 30 carbon atoms.
12. The use as claimed in claim 11, wherein the cetane improver is present in the fuel
in a proportion in the range of from 0.0005 to 1%, advantageously 0.005 to 0.5%, preferably
0.05 to 0.2%, by weight, based on the weight of the fuel.
13. The use as claimed in any one of claims 1 to 12, wherein the oil soluble compound
is used in the form of a derivative obtainable by treatment thereof with boron oxide,
boron oxide hydrate, a boron halide, a boron acid, sulphur, a sulphur chloride, a
phosphorus oxide or sulphide, a carboxylic acid or anhydride, especially polyisobutylene
succinc anhydride, an acyl halide, an epoxide, an episulphide, or acrylonitrile.
1. Verwendung einer öllöslichen Verbindung mit der Formel
oder
R
12R
13N-(CR
16R
17)
n-[NH(CR
18R
19)
u]
b-NR
13R
13 (II)
oder Mischungen aus zwei oder mehr solchen Verbindungen, wobei a 1 bis 150 ist, R
1, R
2 und R
3 gleich oder unterschiedlich sein können und unabhängig Wasserstoff oder ein Kohlenwasserstoffsubstituent
mit 2 bis 600 Kohlenstoffatomen oder ein Keto-, Halogen-, Hydroxy-, Nitro-, Cyano-
oder Alkoxyderivat derselben sind, mit der Maß-gabe, daß mindestens einer aus R
1, R
2 und R
3 ein Kohlenwasserstoffsubstituent mit 2 bis 600 Kohlenstoffatomen oder das Derivat
desselben ist, oder R
1 und R
2 zusammen einen zweiwertigen Kohlenwasserstoffsubstituenten mit 4 bis 600 Kohlenstoffatomen
oder ein Keto-, Halogen-, Hydroxy-, Nitro-, Cyano- oder Alkoxyderivat desselben bilden,
mit der Maßgabe, daß R
1 und R
2 zusammen mit dem Kohlenstoffatom, das mit R
1 die C-R
1-Bindung bildet, und dem Stickstoffatom, das mit R
2 die N-R
2-Bindung bildet, einen Ring mit mindestens 5 Gliedern bilden, wobei Z
-R
10[NR
11(R
10)]
c-
oder
-[R
10R
11N]
dR
10[NR
11R
10]
e
bedeutet, wobei jedes R
10, das gleich oder unterschiedlich sein kann, eine Alkylengruppe mit 1 bis 5 Kohlenstoffatomen
in seiner Kette bedeutet, jedes R
11, das gleich oder unterschiedlich sein kann, ein Wasserstoffatom oder eine Kohlenwasserstoffgruppe
bedeutet, und c 0 bis 6 beträgt, d 1 bis 4 beträgt, e 1 bis 4 beträgt, mit der Maßgabe,
daß d + e höchstens 5 ist, R
12 ein Kohlenwasserstoffsubstituent mit 2 bis 400 Kohlenstoffatomen ist, jedes R
13 Wasserstoff oder ein C
1- bis C
12-Kohlenwasserstoffsubstituent ist, R
16, R
17, R
18 und R
19 unabhängig Wasserstoff, eine Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen,
eine Acylgruppe mit 2 bis 10 Kohlenstoffatomen oder ein Monoketo-, Mono- hydroxy-,
Mononitro-, Monocyano- oder Alkoxyderivat einer Kohlenwasserstoffgruppe mit 1 bis
10 Kohlenstoffatomen oder einer Acylgruppe mit 2 bis 10 Kohlenstoffatomen ist, n 1
bis 6 ist, u 1 bis 6 ist und b 0 bis 12 ist, als Additiv in einem Brennstofföl zur
Verminderung der Teilchenemission bei Verbrennung des Brennstofföls, die von der Verminderung
verschieden ist, die aus einer Verminderung der Verunreinigung der Einspritzanlage
in einem Dieselmotor resultiert.
2. Verwendung nach Anspruch 1, bei der die Verbindung eine Verbindung mit der Formel
I ist und die Formel
hat, in der R
7 Wasserstoff oder ein Kohlenwasserstoffsubstituent mit 1 bis 600 Kohlenstoffatomen
ist, R
8 Wasserstoff oder ein C
1- bis C
12-kohlenwaserstoffsubstituent ist und, wenn es mehr als ein R
8 in einer Verbindung gibt, diese gleich oder unterschiedlich sein können, R
9 ein zweiwertiger Kohlenwasserstoffsubstituent mit 2 bis 600 Kohlenstoffatomen ist,
von denen zwei Kohlenstoffatome an die α-Kohlenstoffatome des Rings auf Bernsteinsäureanhydridbasis
gebunden sind, X
1 Wasserstoff oder eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen bedeutet, X
2 Wasserstoff, eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen, eine Hydroxygruppe
oder eine Alkoxygruppe mit 1 bis 12 Kohlenstoffatomen bedeutet, oder X
1 und X
2 zusammen ein Sauerstoff- oder Schwefelatom bedeuten können, Z die in Anspruch 1 angegebene
Bedeutung hat und h 1 bis 20 beträgt.
3. Verwendung nach Anspruch 2, bei der die Verbindung eine öllösliche Verbindung mit
der Formel
oder Mischungen aus zwei oder mehr solchen Verbindungen ist, wobei R
12 ein Kohlenwasserstoffsubstituent mit 2 bis 400 Kohlenstoffatomen ist, R
13 Wasserstoff oder ein C
1- bis C
12-Kohlenwasserstoffsubstituent ist, und, wenn es mehr als ein R
13 in einer Verbindung gibt, diese gleich oder unterschiedlich sein können, R
14 ein zweiwertiger Kohlenwasserstoffrest mit 4 bis 400 Kohlenstoffatomen ist, wobei
zwei der Kohlenstoffatome an die α-Kohlenstoffatome des Rings auf Bernsteinsäureanhydridbasis
gebunden sind und -Z--CH
2CH
2CH
2-, -(CH
2CH
2CH
2NH)
nCH
2CH
2CH
2- ist, wobei n 1 bis 6 ist, oder -(CH
2CH
2CH
2NH)
m(CH
2)
p(NHCH
2CH
2CH
2)
q- bedeutet, wobei m und q jeweils mindestens 1 sind und m + q = 2 bis 5 sind, p 1
bis 5 ist und a 1 bis 20 ist.
4. Verwendung nach einem der Ansprüche 1 bis 3, wobei mindestens eines von R1, R2 und R3 oder wobei mindestens eines von R7 und R9 oder wobei mindestens eines von R12 oder R14 von einem C2- bis C5-Olefinpolymer abgeleitet ist.
5. Verwendung nach Anspruch 4, bei der das Polymer Polyisobutylen ist.
6. Verwendung nach Anspruch 4 oder Anspruch 5, bei der das Polymer 10, vorzugsweise 20
bis 200 Kohlenstoffatome enthält.
7. Verwendung nach einem der Ansprüche 1 bis 6, bei der -Z--(CH2)3NH(CH2)3-, -(CH2)3NHCH2CH2NH(CH2)3- oder -(CH2)3- bedeutet.
8. Verwendung nach einem der Ansprüche 1 bis 7, bei der die öllösliche Verbindung durch
Umsetzung eines Kohlenwasserstoffreaktanten und eines Polyaminreaktanten in einem
Molverhältnis von 0,2:1 bis 5:1, vorzugsweise 0,5:1 bis 2:1 hergestellt worden ist.
9. Verwendung nach einem der Ansprüche 1 bis 8, bei der die öllösliche Verbindung in
Form eines Nachbehandlungsderivats verwendet wird, vorzugsweise eines Derivats, das
durch Nachbehandlung der öllöslichen Verbindung mit Boroxid, Boroxidhydrat, einem
Borhalogenid, einer Borsäure, Schwefel, einem Schwefelchlorid, einem Phosphoroxid
oder -sulfid, einer Carbonsäure oder einem Carbonsäureanhydrid, z. B. Polyisobutylenbernsteinsäureanhydrid,
einem Acylhalogenid, einem Epoxid, einem Episulfid oder Acrylnitril hergestellt worden
ist.
10. Verwendung nach einem der Ansprüche 1 bis 9, bei der die öllösliche Verbindung in
dem Brennstoff in einem Anteil im Bereich von 0,0005 bis 2 Gew.%, vorteilhaft 0,001
bis 0,5 Gew.%, vorzugsweise 0,005 bis 0,3 Gew.% vorhanden ist, bezogen auf das Gewicht
des Brennstoffs.
11. Verwendung nach einem der Ansprüche 1 bis 10, bei der die öllösliche Verbindung gemischt
oder zusammen mit einem Cetanverbesserer (Zündbeschleuniger), vorteilhaft einem aliphatischen
oder cycloaliphatischen Nitrat, vorzugsweise einem Alkyl- oder Cycloalkylnitrat, das
bis zu 30 Kohlenstoffatome enthält, verwendet wird.
12. Verwendung nach Anspruch 11, bei der der Cetanverbesserer in dem Brennstoff in einem
Anteil im Bereich von 0,0005 bis 1 Gew.%, vorteilhaft 0,005 bis 0,5 Gew.%, vorzugsweise
0,05 bis 0,2 Gew.%, bezogen auf das Gewicht des Brennstoffs, vorhanden ist.
13. Verwendung nach einem der Ansprüche 1 bis 12, bei der die öllösliche Verbindung in
Form eines Derivats verwendet wird, das durch Behandlung derselben mit Boroxid, Boroxidhydrat,
einem Borhalogenid, einer Borsäure, Schwefel, einem Schwefelchlorid, einem Phosphoroxid
oder -sulfid, einer Carbonsäure oder einem Carbonsäureanhydrid, insbesondere Polyisobutylenbernsteinsäureanhydrid,
einem Acylhalogenid, einem Epoxid, einem Episulfid oder Acrylnitril erhältlich ist.
1. Utilisation, comme additif dans un fuel-oil, pour réduire les émissions de particules
lors de la combustible du fuel-oil, hormis la réduction résultant d'une réduction
de l'encrassement des injecteurs dans un moteur diesel, d'un composé, soluble dans
l'huile, de formule :
R
12R
13N-(CR
16R
17)
n-[NH(CR
18R
19)
u]
b-NR
13R
13 (II)
ou d'un mélange de deux ou plus de deux de ces composés, formule dans laquelle a a
une valeur de 1 à à 150, R
1, R
2 et R
3 peuvent être identiques ou différents et représentent indépendamment l'hydrogène
ou un substituant hydrocarbyle ayant 2 à 600 atomes de carbone, ou un de ses dérivés
à fonction céto, halogéno, hydroxy, nitro, cyano ou alkoxy, sous réserve qu'au moins
un des substituants R
1, R
2 et R
3 représente un substituant hydrocarbyle ayant 2 à 600 atomes de carbone ou un de ses
dérivés, ou dans laquelle R
1 et R
2, conjointement, forment un substituant hydrocarbylène ayant 4 à 600 atomes de carbone
ou un de ses dérivés à fonction céto, halogéno, hydroxy, nitro, cyano ou alkoxy, sous
réserve que R
1 et R
2, conjointement avec l'atome de carbone qui forme la liaison C-R
1 avec R
1 et l'atome d'azote qui forme la liaison N-R
2 avec R
2, forment un noyau constitué d'au moins 5 atomes, Z représente un groupe
-R
10[NR
11(R
10)]
c-
ou
-[R
10R
11N]
dR
10[NR
11R
10]
e
dans lequel chacun des groupes R
10, qui peuvent être identiques ou différents, représente un groupe alkylène ayant 1
à 5 atomes de carbone dans sa chaîne, chacun des groupes R
11, qui peuvent être identiques ou différents, représente un atome d'hydrogène ou un
groupe hydrocarbyle, et c a une valeur de 0 à 6, d a une valeur de 1 à 4, e a une
valeur de 1 à 4, sous réserve que la somme d + e soit au plus égale à 5, R
12 représente un substituant hydrocarbyle ayant 2 à 400 atomes de carbone, chacun des
groupes R
13 représente indépendamment l'hydrogène ou un groupe hydrocarbyle en C
1 à C
12, R
16, R
17, R
18 et R
19 représentent indépendamment l'hydrogène, un groupe hydrocarbyle ayant 1 à 10 atomes
de carbone, un groupe acyle ayant 2 à 10 atomes de carbone, ou un dérivé à fonction
monocéto, monohydroxy, mononitro, monocyano ou alkoxy d'un groupe hydrocarbyle ayant
1 à 10 atomes de carbone ou d'un groupe acyle ayant 2 à 10 atomes de carbone, n a
une valeur de 1 à 6, u a une valeur de 1 à 6, et b a une valeur de 0 à 12.
2. Utilisation suivant la revendication 1, dans laquelle le composé est un composé de
formule I et répond à la formule :
dans laquelle R
7 représente l'hydrogène ou un substituant hydrocarbyle ayant 1 à 600 atomes de carbone,
R
8 représente l'hydrogène ou un substituant hydrocarbyle en C
1 à C
12 et, s'il existe plus d'un substituant R
8 dans un composé, ces substituants R
8 peuvent être identiques ou différents, R
9 représente un substituant hydrocarbylène ayant 2 à 600 atomes de carbone, deux de
ces atomes de carbone étant liés aux atomes de carbone alpha du noyau à base anhydride
succinique, X
1 représente l'hydrogène ou un groupe alkyle ayant 1 à 12 atomes de carbone, X
2 représente l'hydrogène, un groupe alkyle ayant 1 à 12 atomes de carbone, un groupe
hydroxy ou un groupe alkoxy ayant 1 à 12 atomes de carbone, ou bien X
1 et X
2 peuvent, conjointement, représenter un atome d'oxygène ou de soufre, Z répond à la
définition mentionnée dans la revendication 1 et h a une valeur de 1 à 20.
3. Utilisation suivant la revendication 2, dans laquelle le composé est un composé soluble
dans l'huile, de formule
ou consiste en un mélange de deux ou plus de deux de ces composés, formule dans laquelle
R
12 représente un substituant hydrocarbyle ayant 2 à 400 atomes de carbone, R
13 représente l'hydrogène ou un substituant hydrocarboné en C
1 à C
12 et, s'il existe plus d'un substituant R
13 dans un composé, ces substituants peuvent être identiques ou différents, R
14 représente un substituant hydrocarbylène ayant 4 à 400 atomes de carbone, deux de
ces atomes de carbone étant liés aux atomes de carbone α du noyau à base d'anhydride
succinique et -Z- représente un groupe -CH
2CH
2CH
2- ; -(CH
2CH
2CH
2NH)
nCH
2CH
2CH
2-, dans lequel n a une valeur de 1 à 6 ou -(CH
2CH
2CH
2NH)
m(CH
2)
p(NHCH
2CH
2CH
2)
q- dans lequel m et q sont chacun au moins égaux à 1 et la somme m+q est égale à une
valeur de 2 à 5, p a une valeur de 1 à 5 et a a une valeur de 1 à 20.
4. Utilisation suivant l'une quelconque des revendications 1 à 3, dans laquelle au moins
un des groupes R1, R2 et R3, ou au moins un des groupes R7 et R9, ou au moins un groupe R12 et R14 est dérivé d'un polymère d'oléfine en C2 à C5.
5. Utilisation suivant la revendication 4, dans laquelle le polymère est un polyisobutylène.
6. Utilisation suivant la revendication 4 ou la revendication 5, dans laquelle le polymère
contient 10, de préférence 20 à 200 atomes de carbone.
7. Utilisation suivant l'une quelconque des revendications 1 à 6, dans laquelle -Z- représente
un groupe -(CH2)3NH(CH2)3-, -(CH2)3NHCH2CH2NH(CH2)3- ou -(CH2)3-.
8. Utilisation suivant l'une quelconque des revendications 1 à 7, dans laquelle le composé
soluble dans l'huile a été préparé par réaction d'un corps réactionnel hydrocarbylique
et d'un corps réactionnel du type polyamine en un rapport molaire compris dans l'intervalle
de 0,2:1 à 5:1, de préférence de 0,5:1 à 2:1.
9. Utilisation suivant l'une quelconque des revendications 1 à 8, dans laquelle le composé
soluble dans l'huile est utilisé sous forme d'un dérivé post-traité, de préférence
d'un dérivé formé par post-traitement du composé soluble dans l'huile avec l'oxyde
de bore, un oxyde de bore hydraté, un halogénure de bore, un acide dérivé du bore,
le soufre, un chlorure de soufre, un oxyde ou sulfure de phosphore, un acide ou anhydride
carboxylique, par exemple l'anhydride polyisobutylène-succinique, un halogénure d'acyle,
un époxyde, un épisulfure ou l'acrylonitrile.
10. Utilisation suivant l'une quelconque des revendications 1 à 9, dans laquelle le composé
soluble dans l'huile est présent dans le carburant en une proportion comprise dans
l'intervalle de 0,0005 à 2 %, avantageusement de 0,001 à 0,5 %, de préférence de 0,005
à 0,3 % en poids, sur la base du poids du carburant.
11. Utilisation suivant l'une quelconque des revendications 1 à 10, dans laquelle le composé
soluble dans l'huile est utilisé en mélange ou en association avec un agent améliorant
l'indice de cétane, avantageusement un nitrate aliphatique ou cycloaliphatique, de
préférence un nitrate d'alkyle ou de cycloalkyle contenant jusqu'à 30 atomes de carbone.
12. Utilisation suivant la revendication 11, dans laquelle l'agent améliorant l'indice
de cétane est présent dans le carburant en une proportion comprise dans l'intervalle
de 0,0005 à 1 %, avantageusement de 0,005 à 0,5 %, de préférence de 0,05 à 0,2 % en
poids, sur la base du poids du carburant.
13. Utilisation suivant l'une quelconque des revendications 1 à 12, dans laquelle le composé
soluble dans l'huile est utilisé sous forme d'un dérivé pouvant être obtenu en traitant
ce composé avec l'oxyde de bore, un oxyde de bore hydraté, un halogénure de bore,
un acide dérivé du bore, le soufre, un chlorure de soufre, un oxyde ou sulfure de
phosphore, un acide ou anhydride carboxylique, notamment l'anhydride polyisobutylène-succinique,
un halogénure d'acyle, un époxyde, un épisulfure ou l'acrylonitrile.