U.S. patent application number 17/272069 was filed with the patent office on 2021-11-04 for composition of additives, comprising at least one copolymer, one cold-flow improver and one anti-settling additive.
This patent application is currently assigned to Total Marketing Services. The applicant listed for this patent is Total Marketing Services. Invention is credited to Thomas DUBOIS, Frederic TORT.
Application Number | 20210340453 17/272069 |
Document ID | / |
Family ID | 1000005779847 |
Filed Date | 2021-11-04 |
United States Patent
Application |
20210340453 |
Kind Code |
A1 |
TORT; Frederic ; et
al. |
November 4, 2021 |
COMPOSITION OF ADDITIVES, COMPRISING AT LEAST ONE COPOLYMER, ONE
COLD-FLOW IMPROVER AND ONE ANTI-SETTLING ADDITIVE
Abstract
The present invention relates to a composition of additives,
comprising: at least one copolymer having at least one motif of
formula (I) and at least one motif of formula (II); at least one
cold-flow improver selected from the copolymers of ethylene and
unsaturated ester(s); and at least one anti-settling and/or
paraffin dispersant additive. ##STR00001##
Inventors: |
TORT; Frederic; (Brignais,
FR) ; DUBOIS; Thomas; (Lyon, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Total Marketing Services |
Puteaux |
|
FR |
|
|
Assignee: |
Total Marketing Services
Puteaux
FR
|
Family ID: |
1000005779847 |
Appl. No.: |
17/272069 |
Filed: |
August 23, 2019 |
PCT Filed: |
August 23, 2019 |
PCT NO: |
PCT/EP2019/072602 |
371 Date: |
February 26, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 1/146 20130101;
C10L 2200/0446 20130101; C10L 2200/0476 20130101; C10L 10/16
20130101 |
International
Class: |
C10L 1/14 20060101
C10L001/14; C10L 10/16 20060101 C10L010/16 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 28, 2018 |
FR |
1857717 |
Claims
1. A composition of additives comprising: at least one copolymer
comprising: at least one unit having the following formula (I):
##STR00008## in which R.sub.1 represents a hydrogen atom or a
methyl group, X represents --O--CO--, or --CO--O-- or --NH--CO-- or
--CO--NH--, and R.sub.2 represents a C.sub.6 to C.sub.24 alkyl
group; and at least one unit having the following formula (II):
##STR00009## in which R represents a C.sub.2 to C.sub.34 group,
comprising at least one nitrogen heterocycle; at least one cold
flow improver chosen from the copolymers of ethylene and of
unsaturated ester(s); at least one anti-settling additive and/or
paraffin dispersant.
2. The composition according to claim 1, characterised in that the
group R contains at least one nitrogen heterocycle having from one
to three nitrogen atoms, more preferably two nitrogen atoms, even
more preferably the group R is chosen from the following cycles: a
substituted or non-substituted imidazole cycle, a substituted or
non-substituted triazole cycle, a substituted or non-substituted
pyrrolidone cycle; and even more preferably the group R is a
substituted or non-substituted imidazole cycle.
3. The composition according to claim 1, characterised in that said
copolymer contains only units having the formula (I) and units
having the formula (II).
4. The composition according to claim 1, characterised in that said
copolymer is a statistical copolymer, or a block copolymer, and
preferably said copolymer is a statistical copolymer.
5. The composition according to claim 1, characterised in that it
comprises from 0.1 to 30% by weight of said copolymer, preferably
from 1 to 20% by weight, more preferably from 2 to 10% by weight
relative to the total weight of the composition of additives.
6. The composition according to claim 1, characterised in that it
comprises from 50 to 90% by weight of said cold flow improver,
preferably from 60 to 90% by weight, more preferably from 70 to 90%
by weight relative to the total weight of the composition of
additives.
7. The composition according to claim 1, characterised in that it
comprises from 1 to 50% by weight of said anti-settling additive
and/or of said paraffin dispersant, preferably from 2 to 30% by
weight, more preferably from 5 to 20% by weight relative to the
total weight of the composition of additives.
8. The composition according to claim 1, characterised in that the
cold flow improver is chosen from the copolymers of ethylene and of
vinyl and/or acrylic ester(s), preferably from the copolymers of
ethylene and of vinyl ester(s), more preferably from the
ethylene/vinyl acetate copolymers, the ethylene/vinyl propionate
copolymers and the terpolymers of ethylene, of vinyl acetate and of
another vinyl ester, even more preferably the ethylene/vinyl
acetate copolymers and their mixtures with a terpolymer of
ethylene, of vinyl acetate and of another vinyl ester, in
particular such as vinyl neodecanoate.
9. The composition according to claim 1, characterised in that the
anti-settling additive is chosen from the group consisting of the
(meth)acrylic acid/alkyl (meth)acrylate copolymers amidified by a
polyamine, the polyamine alkenylsuccinimides, the derivatives of
phthalamic acid and of two-chain fatty amine, the products of
condensation of one or more carboxylic acids with one or more
polyamines, modified alkylphenol-aldehyde resins and optionally
grafted alkylphenol resins, preferably the alkylphenol resins and
the grafted alkylphenol resins.
10. A use, to improve the cold resistance properties of a fuel or
combustible composition, of the composition of additives as defined
in claim 1.
11. The use according to claim 10, characterised in that the fuel
or combustible composition is chosen from the diesel fuels, the
biodiesels, the diesel fuels of the B.sub.x type containing x %
(v/v) of esters of vegetable or animal oils or of fatty acids, the
hydrogenated vegetable oils, and the fuel oils such as the heating
oils.
12. The use according to claim 10 to lower the cold filter plugging
point measured according to the standard NF EN 116 and/or the pour
point measured according to the standard ASTM D 7346, and/or to
delay or prevent the settling of crystals, and preferably to lower
the cold filter plugging point measured according to the standard
NF EN 116.
13. A concentrate of additives comprising a composition of
additives as defined in claim 1, in a mixture with an organic
liquid.
14. A fuel or combustible composition, comprising: (1) at least one
cut of hydrocarbons coming from one or more sources chosen from the
group consisting of the mineral, animal, plant and synthetic
sources, and (2) at least one composition of additives as defined
in claim 1.
15. A fuel according to claim 14, characterised in that it contains
the copolymer(s) in a concentration of at least 0.0001% by weight,
preferably in a concentration ranging from 0.0001 to 0.01% by
weight, more preferably from 0.0002 to 0.005% by weight relative to
the total weight of the composition.
Description
[0001] The present invention relates to a composition of particular
additives and its use to improve the cold resistance properties of
fuels and combustibles during their storage and/or their use at low
temperature.
[0002] The present invention also relates to fuel and combustible
compositions containing such a composition of additives.
PRIOR ART
[0003] The fuels or combustibles containing paraffinic compounds,
in particular compounds containing n-alkyl, iso-alkyl or n-alkenyl
groups such as paraffinic waxes, are known for having deteriorated
flow properties at low temperature, typically below 0.degree. C. In
particular, it is known that the middle distillates obtained by
distillation from crude oils of petroleum origin like diesel fuel
or heating oil contain various quantities of n-alkanes or
n-paraffins according to their origin. These compounds tend to
crystallise at low temperature, plugging hoses, pipes, pumps and
filters, for example in the circuits for the fuel of motor
vehicles. In winter or in conditions of use of the fuels or
combustibles at a temperature lower than 0.degree. C., the
phenomenon of crystallisation of these compounds can lead to a
reduction in the flow properties of the fuels or combustibles and
consequently cause difficulties during their transport, their
storage and/or their use. The cold operability of the fuels or
combustibles is a very important property, in particular to ensure
the cold starting of engines. If the paraffins are crystallised at
the bottom of the tank, they can be brought upon starting into the
fuel circuit and clog in particular the filters and prefilters
positioned upstream of the injection systems (pump and injectors).
Likewise, for the storage of heating oils, if paraffins precipitate
at the bottom of the tank, they can be transported and block the
ducts upstream of the pump and of the system for supplying the
boiler (nozzle and filter).
[0004] These problems are well known in the field of fuels and
combustibles, and numerous additives or mixtures of additives have
been proposed and marketed to reduce the size of the crystals of
paraffins and/or change their shape and/or delay their formation.
The smallest possible crystal size is preferred since it minimises
the risks of plugging or clogging of the filters.
[0005] The usual agents for improving flow called cold flow
improvers or CFIs are in general co- and ter-polymers of ethylene
and of vinyl and/or acrylic ester(s), used alone or in a mixture.
These cold flow improvers (CFIs), intended to lower the cold filter
plugging point (CFPP) and the pour point (PP), inhibit and/or delay
the growth of the crystals at low temperature by favouring the
dispersion of the crystals of paraffin; these are for example the
polymers of ethylene and of vinyl acetate and/or of vinyl
propionate (EVA or EVP), also commonly called CFPP additives. This
type of additives, very widely known to a person skilled in the
art, is systematically added to the conventional middle distillates
at refinery output during the winter seasons. These
additive-containing distillates are used as a diesel-engine fuel or
as a heating fuel. Additional quantities of these additives can be
added to the fuels sold in service stations in particular to
satisfy winter specifications ("Grand Froid").
[0006] To improve both the CFPP and the pour point of the
distillates, it is known to add to these CFI additives additional
additives or "boosters" having the function of acting in
combination with the CFI additives in such a way as to increase the
effectiveness thereof. The prior art abundantly describes such
combinations of additives.
[0007] For example, mention can be made of the U.S. Pat. No.
3,275,427 describing a middle distillate of a distillation cut
between 177 and 400.degree. C. containing an additive consisting of
90 to 10% by weight of a copolymer of ethylene comprising 10 to 30%
vinyl acetate units having a molar mass by weight between 1000 and
3000 gmol.sup.-1 and of 10 to 90% by weight of a lauryl
polyacrylate and/or of a lauryl polymethacrylate having a molar
mass by weight varying from 760 to 100.000 gmol.sup.-1.
[0008] The document EP0857776 proposes using alkylphenol-aldehyde
resins coming from the condensation of alkylphenol and of aldehyde
in association with ethylene/vinyl ester copolymers or terpolymers
to improve the fluidity of mineral oils.
[0009] The patent application WO 2008/006965 describes the use of a
combination of a homopolymer obtained from an olefinic ester of
carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol
comprising a chain of more than 16 carbon atoms and optionally an
olefinic double bond and a cold flow improver (CFI) of the EVA or
EVP type to increase the effectiveness of the CFI additives by
amplifying their effect on the CFPP.
[0010] The patent application WO 2016/128379 describes the use, as
a cold flow additive for a fuel or combustible, of a block
copolymer comprising:
[0011] (i) a block A consisting of a chain of structural units
derived from one or more alkyl acrylate or methacrylate
.alpha.,.beta.-unsaturated monomers,
[0012] (ii) a block B consisting of a chain of structural units
derived from one or more .alpha.,.beta.-unsaturated monomers
containing at least one aromatic ring.
[0013] This additive is in particular useful as a CFPP booster in
association with a cold flow improver (CFI).
[0014] Besides the improvement of the flow of the fuel or
combustible composition, another goal of the cold resistance
additives is to ensure the dispersion of the crystals of paraffins,
in such a way as to delay or prevent the settling of such crystals
and avoid the formation of a layer rich in paraffins at the bottom
of the containers, tanks or storage tanks; these
paraffin-dispersing additives are called wax anti-settling
additives or WASAs.
[0015] Modified alkylphenol-aldehyde resins have been described in
the document FR2969620 as an anti-settling additive in combination
with a CFPP additive.
[0016] Because of the diversification of the sources of fuels and
combustibles, there is still a need to find new additives to
improve the properties of the fuels or combustibles at low
temperature also called cold resistance properties, and in
particular their flow properties during their storage and/or their
use at low temperature.
[0017] This need is particularly important for the fuels or
combustibles comprising one or more paraffinic compounds, for
example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups
having a tendency to crystallise at low temperature.
[0018] In particular, the distillates used in the fuels and
combustibles increasingly come from refining operations that are
more complex than those coming from the direct distillation of the
petroleum, and can come in particular from the methods of cracking,
hydrocracking, catalytic cracking and from the methods of
visbreaking. With the increasing demand for diesel fuels, a refiner
tends to introduce into these fuels cuts that are more difficult to
use, like the heavier cuts coming from the methods of cracking and
of visbreaking that are rich in long-chain paraffins.
[0019] Moreover, synthetic distillates coming from the
transformation of gases such as those coming from the
Fischer-Tropsch process, as well as distillates resulting from the
treatment of biomasses of plant or animal origin, in particular
like NexBTL and distillates comprising esters of vegetable or
animal oils, have appeared on the market, and form a new range of
products usable as a base to formulate fuels and/or heating oils.
These products also comprise hydrocarbons with long paraffinic
chains.
[0020] Moreover, the arrival of new crude oils on the market, much
richer in paraffins than those commonly refined and for which the
filter plugging point of the distillates coming from direct
distillation was difficult to improve by conventional filterability
additives in the same way as those mentioned above, has been
noted.
[0021] It has been noted that the cold resistance properties of the
distillates obtained by combining old bases and these new sources
was difficult to improve by the addition of conventional
filterability additives, inter alia because of the significant
presence of long-chain paraffins and the complex distribution of
paraffins in their composition. In these new combinations of
distillates, discontinuous distributions of paraffins, in the
presence of which the known filterability additives are not always
sufficiently effective, have been noted.
[0022] There is therefore a need to adapt the cold resistance
additives to these new types of bases for fuels and combustibles,
considered to be particularly difficult to process.
[0023] The present invention applies to the fuels and combustibles
containing not only conventional distillates such as those coming
from the direct distillation of crude oils, but also to the bases
coming from other sources, such as those described above.
[0024] Thus, the goal of the present invention is to propose a new
composition of additives that can advantageously be used to improve
the cold resistance properties, in particular the cold flow
properties of these fuels or combustibles, during their storage
and/or their use at low temperature, typically less than 0.degree.
C.
[0025] The goal of the present invention is moreover to propose a
new composition of additives for fuels and combustibles, and
concentrates containing such a composition, acting on the cold
filter plugging point (CFPP), the pour point (PP), and delaying
and/or preventing the settling of crystals of hydrocarbon
compounds, in particular of the paraffins.
[0026] Finally, another goal of the invention is to propose a fuel
or combustible composition having improved cold resistance
properties, in particular at temperatures of less than 0.degree.
C., preferably less than -5.degree. C.
Object of the Invention
[0027] The applicant has now discovered than a composition of
particular additives, such as those described below, had unexpected
properties for improving the cold resistance of the compositions of
fuels and of combustibles, including those that are particularly
difficult to process.
[0028] An object of the present invention is therefore a
composition of additives comprising: [0029] at least one copolymer
comprising: [0030] at least one unit having the following formula
(I):
##STR00002##
[0031] in which
R.sub.1 represents a hydrogen atom or a methyl group, X represents
--O--CO--, or --CO--O-- or --NH--CO-- or --CO--NH--, and R.sub.2
represents a C6 to C24 alkyl group; and [0032] at least one unit
having the following formula (II):
##STR00003##
[0032] in which R represents a C2 to C34 group, comprising at least
one nitrogen heterocycle; [0033] at least one cold flow improver
chosen from the copolymers of ethylene and of unsaturated ester(s);
[0034] at least one anti-settling additive and/or paraffin
dispersant.
[0035] Another object of the invention is the use of the
composition of additives according to the invention to improve the
cold resistance properties of a fuel or combustible
composition.
[0036] Another object of the invention is a concentrate of
additives containing such a composition, as well as a fuel or
combustible composition.
[0037] Other objects, features, aspects and advantages of the
invention will appear even more clearly upon reading the
description and the examples that follow.
[0038] Hereinafter, and unless otherwise indicated, the limits of a
range of values are comprised in this range, in particular in the
expressions "between" and "ranging from . . . to . . . ".
[0039] Moreover, the expressions "at least one" and "at least" used
in the present description are respectively equivalent to the
expressions "one or more" and "greater than or equal".
[0040] Finally, in a manner known per se, a C.sub.N compound or
group designates a compound or a group containing in its chemical
structure N carbon atoms.
DETAILED DESCRIPTION
[0041] The Composition of Additives:
[0042] The invention implements a composition of additives
comprising at least one copolymer comprising at least one unit
having the following formula (I):
##STR00004##
in which R.sub.1 represents a hydrogen atom or a methyl group, X
represents --O--CO--, or --CO--O-- or --NH--CO-- or --CO--NH--, and
R.sub.2 represents a C6 to C24 alkyl group.
[0043] The group X of formula (I) is chosen from: [0044]
X=--O--CO--, with it being understood that X is thus bound to the
vinylic carbon by the oxygen atom; [0045] X=--CO--O--, with it
being understood that X is thus bound to the vinylic carbon by the
carbon atom; [0046] X=--NH--CO--, with it being understood that X
is thus bound to the vinylic carbon by the nitrogen atom; and
[0047] X=--CO--NH--, with it being understood that X is thus bound
to the vinylic carbon by the carbon atom.
[0048] According to a first embodiment, the group X of formula (I)
is chosen from: --O--CO-- and --NH--CO--, with it being understood
that the group X=--O--CO-- is bound to the vinylic carbon by the
oxygen atom and that the group X=--NH--CO-- is bound to the vinylic
carbon by the nitrogen atom. In this embodiment, the group X of
formula (I) is preferably the group --O--CO--.
[0049] According to a second embodiment, the group X of formula (I)
is chosen from: --CO--O-- and --CO--NH--, with it being understood
that the group X is bound to the vinylic carbon by the carbon atom.
In this embodiment, the group X of formula (I) is preferably the
group --CO--O--.
[0050] According to a particularly preferred embodiment, the group
X is a --CO--O-- group, X being bound to the vinylic carbon by the
carbon atom.
[0051] The group R.sub.2 of formula (I) is a C.sub.6 to C.sub.24
alkyl radical. This alkyl radical can be linear or branched, cyclic
or acyclic. This alkyl radical can comprise a linear or branched
part and a cyclic part.
[0052] Advantageously, the group R.sub.2 of formula (I) is a
C.sub.8-C.sub.24, preferably C.sub.10-C.sub.22, more preferably
C.sub.12-C.sub.22 linear or branched acyclic alkyl radical.
According to a specific embodiment, the group R.sub.2 of formula
(I) is a C.sub.12-C.sub.14 linear or branched acyclic alkyl
radical. According to another specific embodiment, the group
R.sub.2 of formula (I) is a C.sub.18-C.sub.22 linear or branched
acyclic alkyl radical.
[0053] Mention can be made, as non-limiting examples of preferred
groups R.sub.2, of the alkyl groups such as octyl, decyl, dodecyl,
ethyl-2-hexyl, isooctyl, isodecyl, isododecyl, lauryl, stearyl,
octadecyl, behenyl, the C.sub.14 alkyl groups.
[0054] According to a particularly preferred embodiment, the group
X is a --CO--O-- group, X being bound to the vinylic carbon by the
carbon atom, and the group R.sub.2 is a C.sub.8-C.sub.24,
preferably C.sub.10-C.sub.22, more preferably C.sub.12-C.sub.22
linear or branched acyclic alkyl radical.
[0055] The units according to this embodiment correspond to those
coming from monomers chosen from the C.sub.8-C.sub.24, preferably
C.sub.10-C.sub.22, more preferably C.sub.12-C.sub.22 alkyl
acrylates and methacrylates.
[0056] According to a specific embodiment, the group X is a
--CO--O-- group, X being bound to the vinylic carbon by the carbon
atom, and the group R.sub.2 is a C.sub.12-C.sub.14 linear or
branched acyclic alkyl radical. The units according to this
embodiment corresponds to those coming from monomers chosen from
the C.sub.12-C.sub.14 alkyl acrylates and methacrylates.
[0057] According to another specific embodiment, the group X is a
--CO--O-- group, X being bound to the vinylic carbon by the carbon
atom, and the group R.sub.2 is a C.sub.18-C.sub.22 linear or
branched acyclic alkyl radical. The units according to this
embodiment corresponds to those coming from monomers chosen from
the C.sub.18-C.sub.22 alkyl acrylates and methacrylates.
[0058] The copolymer used in the present invention also comprises
at least one unit having the following formula (II):
##STR00005##
in which R represents a C.sub.2 to C.sub.34, preferably C.sub.2 to
C.sub.12, more preferably C.sub.2 to C.sub.6 group, preferably
comprising at least one nitrogen heterocycle.
[0059] Nitrogen heterocycle designates in a manner known per se a
cyclic group comprising carbon atoms and at least one nitrogen atom
in the cycle.
[0060] The group R can be saturated or unsaturated, monocyclic or
polycyclic, and the cycle(s) can be substituted or non-substituted.
The substituent(s) possibly present in the cycle(s) can be
saturated or unsaturated, and in particular be chosen from the
hydrocarbon, oxygen, nitrogen, halogen . . . substituents.
[0061] According to a preferred embodiment, the nitrogen
heterocycle(s) are chosen from the cycles formed by 5 to 7 atoms
among which 1, 2, 3 or 4 atoms are nitrogen atoms, these cycles
being saturated or unsaturated, substituted or non-substituted.
[0062] As non-limiting examples of nitrogen heterocycles mention
can be made of the following cycles: pyrrolidine, pyrroline,
pyrrole, pyrazolidine, imidazolidine, pyrazoline, imidazoline,
pyrazole, imidazole, triazole, tetrazole, piperidine, pyridine,
piperazine, pyridazine, pyrimidine, pyrazine, triazine.
[0063] The nitrogen heterocycle(s) can also contain, in addition to
the carbon and nitrogen atoms, one or more other heteroatoms such
as in particular one or more oxygen atoms, which can be part of the
cycle or be attached to it. For example, mention can be made of the
following cycles: pyrrolidone, caprolactam.
[0064] According to a preferred embodiment, the group R contains at
least one nitrogen heterocycle having from one to three nitrogen
atoms, more preferably two nitrogen atoms. Preferred groups R are
in particular chosen from the following cycles: a substituted or
non-substituted imidazole cycle, a substituted or non-substituted
triazole cycle, a substituted or non-substituted pyrrolidone
cycle.
[0065] According to a particularly preferred embodiment, the group
R is a substituted or non-substituted imidazole cycle.
[0066] According to one embodiment, the units having the formula
(II) come from one or more vinyl monomers carrying a group R as
described above.
[0067] As examples of preferred monomers mention can be made of:
[0068] the 1,2,3 and the 1,2,4 N-vinyltriazoles, [0069]
N-vinylpyrrolidone, [0070] 1-vinylimidazole (or N-vinylimidazole),
the latter being particularly preferred.
[0071] The copolymer used in the present invention can be
cross-linked or not. Preferably, it is not cross-linked.
[0072] The copolymer according to the invention advantageously
contains from 50 to 99% in moles of units having the formula (I),
preferably from 60 to 95% in moles, more preferably from 70 to 90%
in moles, and even better from 75 to 85% in moles.
[0073] The copolymer according to the invention advantageously
contains from 1 to 50% in moles of units having the formula (II),
preferably from 5 to 40% in moles, more preferably from 10 to 30%
in moles, and even better from 15 to 25% in moles.
[0074] Preferably, the copolymer used in the present invention
contains only units having the formula (I) and units having the
formula (II).
[0075] The copolymer used in the present invention is
advantageously a statistical copolymer or a block copolymer.
According to a particularly preferred embodiment, it is a
statistical copolymer.
[0076] The copolymer used in the present invention can be obtained
by copolymerisation of: [0077] at least one monomer having the
following formula (IA):
##STR00006##
[0077] in which R.sub.1, X and R.sub.2 are as defined above, the
preferred alternatives of R.sub.1, X and R.sub.2 according to the
formula (I) described above also being preferred alternatives of
the formula (IA), and [0078] at least one monomer having the
following formula (IIA):
##STR00007##
[0078] in which R is as defined above, the preferred alternatives
of R according to the formula (II) described above also being
preferred alternatives of the formula (IIA).
[0079] When the group X of the monomer having the formula (IA) is
the group --O--CO--, with it being understood that the group
--O--CO-- is bound to the vinylic carbon by the oxygen atom, the
monomer having the formula (IA) is, preferably, chosen from the
C.sub.8 to C.sub.24, preferably C.sub.10 to C.sub.24, more
preferably C.sub.12 to C.sub.22 vinyl alkyl esters. According to a
specific embodiment, the monomer having the formula (IA) is chosen
from the C.sub.12 to C.sub.14 vinyl alkyl esters. According to
another specific embodiment, the monomer having the formula (IA) is
chosen from the C.sub.18 to C.sub.22 vinyl alkyl esters. The alkyl
radical or alkyl vinyl ester is linear or branched, cyclic or
acyclic, preferably acyclic.
[0080] Among the alkyl vinyl ester monomers, mention can be made
for example of vinyl octanoate, vinyl decanoate, vinyl dodecanoate,
vinyl tetradecanoate, vinyl 2-ethylhexanoate.
[0081] When the group X of the monomer having the formula (IA) is
the group --CO--O--, with it being understood that the group
--CO--O-- is bound to the vinylic carbon by the carbon atom, the
monomer having the formula (IA) is typically chosen from the
C.sub.8 to C.sub.24, preferably C.sub.10 to C.sub.24, more
preferably C.sub.12 to C.sub.22 alkyl acrylates and methacrylates.
According to a specific embodiment, the monomer having the formula
(IA) is chosen from the C.sub.12 to C.sub.14 alkyl acrylates and
methacrylates. According to another specific embodiment, the
monomer having the formula (IA) is chosen from the C.sub.18 to
C.sub.22 alkyl acrylates and methacrylates.
[0082] Among the alkyl (meth)acrylates capable of being used as
monomers in the manufacturing of the copolymer used in the
invention, mention can be made of the C.sub.6 to C.sub.24 alkyl
acrylates and the C.sub.6 to C.sub.24 alkyl methacrylates, and in
particular, as non-limiting examples: n-octyl acrylate, n-octyl
methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl
acrylate, n-dodecyl methacrylate, ethyl-2-hexyl acrylate,
ethyl-2-hexyl methacrylate, isooctyl acrylate, isooctyl
methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl
acrylate, stearyl acrylate, octadecyl acrylate, behenyl acrylate,
the C.sub.12 to C.sub.14 alkyl acrylates and the C.sub.12 to
C.sub.14 alkyl methacrylates. It is particularly preferred to use
the C.sub.12 to C.sub.14 alkyl acrylates and the C.sub.12 to
C.sub.14 alkyl methacrylates and also the C.sub.18 to C.sub.22
alkyl acrylates and the C.sub.18 to C.sub.22 alkyl
methacrylates.
[0083] The monomers having the formula (IIA) are vinyl monomers
carrying a group R as described above.
[0084] According to a particularly preferred embodiment, the group
R contains at least one unsaturated nitrogen heterocycle having
from one to three nitrogen atoms, more preferably two nitrogen
atoms, such as in particular an imidazole cycle, substituted or
non-substituted.
[0085] As a particularly preferred monomer having the formula (IIA)
mention can be made of 1-vinylimidazole (or N-vinylimidazole).
[0086] It is understood that it would not be beyond the invention
if the copolymer used in the invention was obtained from monomers
different than those having the formula (IA) and (IIA) above,
insofar as the final copolymer corresponds to a polymer comprising
units having the formula (I) and units having the formula (II) as
defined above. For example, it would not be beyond the invention if
the polymer was obtained by polymerisation of different monomers,
followed by a post-functionalisation. For example, the units having
the formula (I) can be obtained from acrylic acid, by a
transesterification reaction.
[0087] The copolymer used in the invention can be prepared via any
known polymerisation method. The various polymerisation and
cross-linking techniques and conditions are broadly described in
the literature and are part of the general knowledge of a person
skilled in the art.
[0088] In the case of a statistical copolymer, conventional
free-radical polymerisation can in particular be used: in general a
mixture of the various monomers in a suitable solvent is carried
out, and the copolymerisation is initiated via a free-radical
polymerisation agent.
[0089] In the case of a block copolymer, sequenced and controlled
polymerisation can in particular be used. Such a polymerisation is,
advantageously, chosen from the controlled free-radical
polymerisation; for example, by atom transfer radical
polymerisation (ATRP); nitroxide-mediated polymerisation (NMP); the
degenerative transfer processes such as iodine transfer radical
polymerisation (ITRP) or reversible addition-fragmentation chain
transfer (RAFT); the polymerisations derived from ATRP such as the
polymerisations using initiators for continuous activator
regeneration (ICAR) or using activators regenerated by electron
transfer (ARGET).
[0090] The copolymer used in the invention has, advantageously, a
weight-average molecular weight (M.sub.w) between 1,000 and 50,000
gmol.sup.-1, more preferably between 1,000 and 20,000 gmol.sup.-1,
even more preferably between 3,000 and 15,000 gmol.sup.-1.
[0091] The copolymer according to the invention has,
advantageously, a number-average molecular weight (Mn) between
1,000 and 50,000 gmol.sup.-1, more preferably between 1,000 and
20,000 gmol.sup.-1, even more preferably between 2,000 and 10,000
gmol.sup.-1.
[0092] The number- and weight-average molecular weights are
measured by Size Exclusion Chromatography (SEC).
[0093] The composition of additives according to the invention can,
advantageously, comprise from 0.1 to 30% by weight of a copolymer
as described above, preferably from 1 to 20% by weight, more
preferably from 2 to 10% by weight relative to the total weight of
the composition of additives.
[0094] The composition of additives according to the invention also
comprises at least one cold flow improver (CFI) chosen from the
copolymers of ethylene and of unsaturated ester(s).
[0095] Preferably, the cold flow improver is chosen from the
copolymers of ethylene and of vinyl and/or acrylic ester(s), such
as the copolymers ethylene/vinyl acetate (EVA), ethylene/vinyl
propionate (EVP), ethylene/vinyl ethanoate (EVE), ethylene/methyl
methacrylate (EMMA) and ethylene/alkyl fumarate described, for
example, in the documents U.S. Pat. Nos. 3,048,479, 3,627,838,
3,790,359, 3,961,961 and EP261957. Mention can also be made of the
terpolymers of ethylene, of vinyl acetate and of another vinyl
ester, for example vinyl neodecanoate.
[0096] According to a preferred embodiment, the cold flow improver
(CFI) is chosen from the copolymers of ethylene and of vinyl
ester(s), preferably from the ethylene/vinyl acetate (EVA)
copolymers, the ethylene/vinyl propionate (EVP) copolymers and the
terpolymers of ethylene, of vinyl acetate and of another vinyl
ester; even more preferably the ethylene/vinyl acetate copolymers
and their mixtures with a terpolymer of ethylene, of vinyl acetate
and of another vinyl ester, in particular such as vinyl
neodecanoate.
[0097] The composition of additives according to the invention can,
advantageously, comprise from 50 to 90% by weight of a cold flow
improver (CFI) as described above, preferably from 60 to 90% by
weight, more preferably from 70 to 90% by weight relative to the
total weight of the composition of additives.
[0098] The composition of additives according to the invention also
comprises at least one anti-settling additive and/or paraffin
dispersant.
[0099] The anti-settling additive and/or paraffin dispersant (WASA)
can in particular, but not limitingly, be chosen from the group
consisting of the (meth)acrylic acid/alkyl (meth)acrylate
copolymers amidified by a polyamine, the products of condensation
of one or more carboxylic acids with one or more polyamines, the
polyamine alkenylsuccinimides, the derivatives of phthalamic acid
and of two-chain fatty amine; the optionally grafted alkylphenol
resins, the modified alkylphenol-aldehyde resins. Examples of such
additives are given in the following documents: EP261959, EP593331,
EP674689, EP327423, EP512889, EP832172; US2005/0223631; U.S. Pat.
No. 5,998,530; WO93/14178; WO2012/085865.
[0100] The anti-settling additive and/or paraffin dispersant (WASA)
particularly preferred is chosen from the alkylphenol resins and
the alkylphenol resins grafted for example by functional groups
such as polyamines.
[0101] The composition of additives according to the invention can,
advantageously, comprise from 1 to 50% by weight of anti-settling
additive and/or paraffin dispersant as described above, preferably
from 2 to 30% by weight, more preferably from 5 to 20% by weight
relative to the total weight of the composition of additives.
[0102] The composition of additives according to the invention can
also comprise one or more other additives routinely used in fuels
or combustibles, different from the copolymer, the cold-resistance
additives, and the anti-settling additive described above.
[0103] The composition of additives can, typically, comprise one or
more other additives chosen from the detergents, the anti-corrosion
agents, the dispersants, the demulsifiers, the biocides, the
reodorants, the cetane improvers, the friction modifiers, the
lubricity additives, the combustion aids (catalytic promoters of
combustion and of soot), the anti-wear agents and/or the agents
modifying the conductivity.
[0104] Among these additives, mention can be made in particular
of:
[0105] a) the cetane improvers, in particular (but not limitingly)
chosen from the alkyl nitrates, preferably 2-ethyl hexyl nitrate,
the aryl peroxides, preferably benzyl peroxide, and the alkyl
peroxides, preferably tert-butyl peroxide;
[0106] b) the anti-foaming additives, in particular (but not
limitingly) chosen from the polysiloxanes, the oxyalkylated
polysiloxanes, and the amides of fatty acids coming from vegetable
or animal oils. Examples of such additives are given in EP861882,
EP663000, EP736590;
[0107] c) the detergent and/or anti-corrosion additives, in
particular (but not limitingly) chosen from the group consisting of
the amines, the succinimides, the alkenylsuccinimides, the
polyalkylamines, the polyalkyl polyamines, polyetheramines, the
quaternary ammonium salts and the derivatives of triazole; examples
of such additives are given in the following documents: EP0938535,
US2012/0010112 and WO2012/004300. The block copolymers formed from
at least a polar unit and an apolar unit, for example such as those
described in the patent application FR 1761700 in the name of the
applicant can also advantageously be used;
[0108] d) the lubricity additives or anti-wear agents, in
particular (but not limitingly) chosen from the group consisting of
the fatty acids and their ester or amide derivatives, in particular
glycerol monooleate, and the derivatives of mono- and polycyclic
carboxylic acids. Examples of such additives are given in the
following documents: EP680506, EP860494, WO98/04656, EP915944,
FR2772783, FR2772784.
[0109] Use
[0110] Another object of the present invention is the use, to
improve the cold resistance properties of a fuel or combustible
composition, of the composition of additives according to the
invention.
[0111] Said fuel or combustible composition can be a composition
chosen from the diesel fuels, the biodiesels, the diesel fuels of
the B.sub.x type containing x % (v/v) of esters of vegetable or
animal oils or of fatty acids, the hydrogenated vegetable oils, and
the fuel oils such as the heating oils, x being a number strictly
greater than 0 and less than or equal to 100.
[0112] The fuel or combustible composition is as described below
and advantageously comprises at least one cut of hydrocarbons
coming from one or more sources chosen from the group consisting of
the mineral sources, preferably petroleum, the animal, plant and
synthetic sources.
[0113] Advantageously, said composition of additives is used to
improve the flow properties at low temperature of the fuel or of
the combustible during its storage and/or its use at low
temperature, by lowering its cold filter plugging point (or CFPP,
measured according to the standard NF EN 116) and/or its pour point
(or PP, measured according to the standard ASTM D 7346) and/or by
delaying or by preventing the settling of crystals, and preferably
by lowering its cold filter plugging point (or CFPP, measured
according to the standard NF EN 116).
[0114] The composition of additives according to the invention can
be used to delay or prevent the settling of the crystals of
paraffins and more particularly of n-alkanes, preferably the
n-alkanes containing at least 12 carbon atoms, more preferably at
least 20 carbon atoms.
[0115] Concentrate of Additives:
[0116] Another object of the present invention is a concentrate of
additives comprising the composition of additives according to the
invention, in a mixture with an organic liquid. The organic liquid
is advantageously inert with respect to the components of the
composition of additives, and miscible with the fuels or
combustibles, in particular those coming from one or more sources
chosen from the group consisting of the mineral, preferably
petroleum, animal, plant and synthetic sources.
[0117] The organic liquid is preferably chosen from the aromatic
hydrocarbon solvents such as the solvent marketed under the name
"Solvesso 150", the alcohols, the ethers and other oxygenated
compounds, and the paraffinic solvents such as hexane, pentane or
the isoparaffins, alone or in a mixture.
[0118] Fuel or Combustible Composition:
[0119] The invention also relates to a fuel or combustible
composition, comprising:
[0120] (1) at least one cut of hydrocarbons coming from one or more
sources chosen from the group consisting of the mineral, animal,
plant and synthetic sources, and
[0121] (2) at least one composition of additives according to the
invention.
[0122] The mineral sources are preferably petroleum.
[0123] The fuel or combustible composition according to the
invention advantageously comprises the copolymer(s) in a
concentration of at least 0.0001% by weight, relative to the total
weight of the fuel or combustible composition. Preferably, the
concentration of copolymer(s) ranges from 0.0001 to 0.01% by
weight, more preferably from 0.0002 to 0.005% by weight relative to
the total weight of the fuel or combustible composition.
[0124] The fuel or combustible composition according to the
invention advantageously comprises the cold flow improver(s) in a
concentration ranging from 0.0005 to 0.2% by weight, preferably
from 0.001 to 0.1% by weight, more preferably from 0.0015 to 0.05%
by weight relative to the total weight of the fuel or combustible
composition.
[0125] The fuel or combustible composition according to the
invention advantageously comprises the anti-settling additive
and/or paraffin dispersant(s) in a concentration ranging from
0.0001 to 0.1% by weight, preferably from 0.0005 to 0.05% by
weight, more preferably from 0.001 to 0.02% by weight, relative to
the total weight of the fuel or combustible composition.
[0126] The fuels or combustibles can be chosen from the liquid
hydrocarbon fuels or combustibles, alone or in a mixture. The
liquid hydrocarbon fuels or combustibles comprise in particular
middle distillates having a boiling temperature between 100 and
500.degree. C. These distillates can for example be chosen from the
distillates obtained by direct distillation of crude hydrocarbons,
the vacuum distillates, the hydrotreated distillates, the
distillates coming from the catalytic cracking and/or from the
hydrocracking of vacuum distillates, the distillates resulting from
conversion methods of the ARDS type (by atmospheric residue
desulphurisation) and/or from visbreaking, the distillates coming
from the use of the Fischer-Tropsch cuts, the distillates resulting
from the BTL (biomass to liquid) conversion of plant and/or animal
biomass, taken alone or in combination, and/or the biodiesels of
animal and/or plant origin and/or the oils and/or esters of
vegetable and/or animal oils.
[0127] The concentration of sulphur in the fuels or combustibles
is, preferably, less than 5,000 ppm, more preferably less than 500
ppm, and even more preferably less than 50 ppm, or even less than
10 ppm, and advantageously without sulphur.
[0128] The fuel or combustible is, preferably, chosen from the
diesel fuels, the biodiesels, the diesel fuels of the Bx type and
the fuel oils, preferably heating oil (HHO).
[0129] Diesel fuel of the Bx type for a diesel engine (compression
engine) means a diesel fuel that contains x % (v/v) of esters of
vegetable or animal oils (including used cooking oils) transformed
by a chemical method called transesterification reacting this oil
with an alcohol in order to obtain fatty acid esters (FAE). With
methanol and ethanol, fatty acid methyl esters (FAME) and fatty
acid ethyl esters (FAEE) are obtained, respectively. The letter "B"
followed by a number indicates the percentage of FAE contained in
the diesel fuel, x being a number strictly greater than 0 and less
than or equal to 100. Thus, a B.sub.99 contains 99% FAE and 1%
middle distillates of fossil origin, B.sub.20, 20% FAE and 80%
middle distillates of fossil origin, etc. A distinction is thus
made between the diesel fuels of the B.sub.0 type which do not
contain oxygenated compounds, diesel fuels of the Bx type which
contain x % (v/v) of esters of vegetable or animal oils or of fatty
acids, most often methyl esters (VOME or FAME). When the FAE is
used alone in the engines, the fuel is designated by the term
B100.
[0130] The fuel or combustible can also contain hydrogenated
vegetable oils, known to a person skilled in the art by the name
HVO or HDRD (from "hydrogenation-derived renewable diesel").
[0131] According to a specific development, the fuel or combustible
is chosen from the diesel fuels, the biodiesels and the diesel
fuels of the B.sub.x type, the hydrogenated vegetable oils (HVOs),
and the mixtures thereof.
[0132] The fuel or combustible composition can also contain one or
more additional additives, different than the copolymers, the cold
flow improver and the anti-settling additive described above. Such
additives can be in particular chosen from the detergents, the
anti-corrosion agents, the dispersants, the demulsifiers, the
anti-foaming agents, the biocides, the reodorants, the cetane
improvers, the friction modifiers, the lubricity additives, the
combustion aids (catalytic promoters of combustion and of soot),
the anti-wear agents and/or the agents modifying the
conductivity.
[0133] These additional additives can be in general present in a
quantity ranging from 0.005 to 0.1% by weight, relative to the
total weight of the fuel or combustible composition (each).
[0134] Another object of the invention is a method for improving
the cold resistance properties of a fuel or combustible composition
involving adding a composition of additives as described above.
[0135] The examples below are given for purposes of illustrating
the invention, and should not be interpreted in such a way as to
limit the scope thereof.
EXAMPLES
Example 1: Synthesis of Various Polymers
[0136] The various polymers were synthesised by free-radical
polymerisation in solution. In a typicxal example, the monomers
were solubilised in a solvent chosen from toluene or dioxane, and
the transfer agent was added to the mixture. The system was
degassed under a flow of nitrogen for 40 minutes and then heated
until 70.degree. C. was reached. Once at this temperature, the
initiator was added to start the polymerisation. The reaction was
left for 6 h. The system was then opened to air and left to cool
until the ambient temperature was reached. The polymer formed was
recovered by drying under vacuum.
[0137] The polymer recovered was characterised by NMR spectroscopy
and gas chromatography (GC) in order to determine the composition
and the molar mass of the copolymer, respectively.
[0138] The characteristics of the polymers synthesised according to
the operating mode above are brought together in table I below:
TABLE-US-00001 TABLE I Monomer Monomer Type of having the having
the M.sub.W M.sub.n polymer formula (I) formula (II) (g mol.sup.-1)
(g mol.sup.-1) Homo- C.sub.12/C.sub.14 alkyl -- 7750 4920 polymer
acrylate Statistical C.sub.12/C.sub.14 alkyl N-vinylimidazole 8100
5700 copolymer 1 acrylate 20% in moles 80% in moles Statistical
C.sub.12/C.sub.14 alkyl N-vinylimidazole 10230 6220 copolymer 2
acrylate 10% in moles 90% in moles
Example 2: Evaluation of the Cold Resistance Performance
[0139] A composition G of fuel of the type diesel fuel that is
particularly difficult to process, and the characteristics of which
are described in detail in table II below:
TABLE-US-00002 TABLE II Characteristic Method Value Density at
15.degree. C. ISO 12185 836.8 kg/m.sup.3 Cloud point (CP).degree.
EN 23015 -9.degree. C. Cold filter plugging point (CFPP) EN 116
-11.degree. C. Pour point (PP) ASTM D 7346 -15.degree. C.
Concentration of paraffins 18.8% by weight Concentration of C16+
n-paraffins 8.51% by weight D86 Distillation profile ISO 3405
Initial point 172.degree. C. Point at 5% vol. 194.degree. C. Point
at 10% vol. 203.degree. C. Point at 20% vol. 219.degree. C. Point
at 30% vol. 234.degree. C. Point at 40% vol. 250.degree. C. Point
at 50% vol. 263.degree. C. Point at 60% vol. 276.degree. C. Point
at 70% vol. 290.degree. C. Point at 80% vol. 307.degree. C. Point
at 90% vol. 327.degree. C. Point at 95% vol. 346.degree. C. Final
point 363.degree. C.
[0140] was added with various ingredients.
[0141] In particular, two compositions G1 and G2 were prepared.
[0142] The composition G1 comprises: [0143] the additive MDFI A;
[0144] the additive WASA 1.
[0145] The composition G2 comprises: [0146] the additive MDFI A;
[0147] the additive WASA 2.
[0148] The compositions of the additives are reported in table III
below, the concentrations indicated being in percentage by weight
relative to the total weight of the additive:
TABLE-US-00003 TABLE III Additive MDFI A WASA 1 WASA 2 Solvesso 150
solvent 28 28 28 Ethylene/vinyl acetate 61 20 20 copolymer
Ethylene/vinyl acetate/2- 10 -- -- ethylhexyl acrylate terpolymer
Homopolymer as defined in -- 10 -- example 1 statistical copolymer
1 -- -- 10 alkylphenol resin grafted with -- 32 32 a tallow
triamine alpha-olefin/stearyl acrylate/ -- 10 10 maleic anhydride
amidified with a tallow amine terpolymer
[0149] Thus, the composition G1 comprises a comparative composition
of additives. The composition G1 is thus a comparative composition.
The composition G2 comprises a composition of additives according
to the invention. The composition G2 is thus a composition
according to the invention.
[0150] For the composition G1, 170 ppm of WASA 1 additive were
added. Two concentrations of MDFI A additive were tested at 100 and
150 ppm.
[0151] For the composition G2, 170 ppm of WASA 2 additive were
added. Two concentrations of MDFI A additive were tested at 100 and
150 ppm.
[0152] The performance of the compositions of additives was tested,
by evaluating their aptitude to lower the cold filter plugging
point (CFPP) of the additive-containing compositions of diesel fuel
G1 and G2.
[0153] The results obtained are presented in the single drawing.
The CFPPs of the compositions G1 and G2 were measured in accordance
with the standard EN 116.
[0154] The drawing presents the CFPP results obtained by adding
each of the additives defined above, according to the concentration
of MDFI A additive, the concentration of WASA 1, WASA 2 additive,
respectively, being constant (170 ppm).
[0155] The curve A corresponds to the results relating to the
comparative composition G1. The curve B corresponds to the results
relating to the composition G2 according to the invention.
[0156] The CFPP target to be reached is set to -28.degree. C., as
has been shown in the single drawing (dotted line).
[0157] The drawing thus shows that the composition of additives
according to the invention allows to reach the CFPP target of
-28.degree. C. with a concentration of MDFI A additive of only 100
ppm. This same CFPP of -28.degree. C. is reached with the
comparative composition of additives with a concentration greater
by 50%, i.e. 150 ppm.
[0158] Thus, the use of the composition of additives according to
the invention allows to reduce by 33% the treatment concentration,
with respect to the comparative composition. Moreover, with an
identical treatment concentration, the composition of additives
according to the invention allows to obtain better cold resistance
performance.
Example 3: Evaluation of the Cold Resistance Performance
[0159] A composition G' of fuel of the type diesel fuel that is
particularly difficult to process, and the characteristics of which
are described in detail in table IV below:
TABLE-US-00004 TABLE IV Characteristic Method Value Density at
15.degree. C. ISO 12185 831.1 kg/m.sup.3 Cloud point (CP).degree.
EN 23015 -6.degree. C. ? Cold filter plugging point (CFPP) EN 116
-6.degree. C. Pour point (PP) ASTM D 7346 -12.degree. C.
Concentration of paraffins 13% by weight Concentration of C16+
n-paraffins 6% by weight D86 Distillation profile ISO 3405 Point
initial 167.degree. C. Point at 5% vol. 192.degree. C. Point at 10%
vol. 205.degree. C. Point at 20% vol. 225.degree. C. Point at 30%
vol. 243.degree. C. Point at 40% vol. 260.degree. C. Point at 50%
vol. 276.degree. C. Point at 60% vol. 291.degree. C. Point at 70%
vol. 305.degree. C. Point at 80% vol. 319.degree. C. Point at 90%
vol. 335.degree. C. Point at 95% vol. 349.degree. C. Final point
355.degree. C.
[0160] was added with various ingredients.
[0161] In particular, three compositions G'1, G'2 and G'3 were
prepared.
[0162] The composition G'1 comprises:
the additive MDFI B, in Solvesso 150 solvent (28% by weight
relative to the weight of the additive), marketed by the company
Total Additifs Carburants Speciaux, which comprises 65% by weight
of an ethylene/vinyl acetate copolymer (EVA), and 7% by weight of
an alpha-olefin/stearyl acrylate/maleic anhydride amidified with a
tallow amine terpolymer.
[0163] The composition G'2 comprises: [0164] the additive MDFI B as
described above; [0165] the additive WASA 1 as described in example
2.
[0166] The composition G'3 comprises: [0167] the additive MDFI B as
described above; [0168] the additive WASA 2 as described in example
2.
[0169] Thus, the compositions G'1 and G'2 comprise a comparative
composition of additives. The compositions G'1 and G'2 are thus
comparative compositions. The composition G'3 comprises a
composition of additives according to the invention. The
composition G'3 is thus a composition according to the
invention.
[0170] For each of the compositions G'1, G'2 and G'3, two
concentrations of MDFI B additive were tested: 400 and 600 ppm.
[0171] For the composition G'2, 200 ppm of WASA 1 additive were
added.
[0172] For the composition G'3, 200 ppm of WASA 2 additive were
added.
[0173] The performance of the compositions of additives was tested,
by evaluating their aptitude to lower the cold filter plugging
point (CFPP) of the additive-containing compositions of diesel fuel
G'1, G'2 and G'3. The CFPPs of the compositions G'1, G'2 and G'3
were measured in accordance with the standard EN 116.
[0174] The results obtained are presented in table V below:
TABLE-US-00005 TABLE V CFPP (.degree. C.) CFPP (.degree. C.) CFPP
(.degree. C.) Compositions G'1 G'2 G'3 G'1 MDFI B 400 ppm
-18.degree. C. -- -- G'1 MDFI B 600 ppm -25.degree. C. -- -- G'2
MDFI B 400 ppm -- -20.degree. C. -- G'2 MDFI B 600 ppm --
-23.degree. C. -- G'3 MDFI B 400 ppm -- -- -24.degree. C. G'3 MDFI
B 600 ppm -- -- -27.degree. C.
[0175] The results clearly show that the composition of additives
according to the invention leads to a significant lowering of the
CFPP.
* * * * *