U.S. patent application number 13/818923 was filed with the patent office on 2013-08-01 for engine lubricant.
The applicant listed for this patent is Nguyen Truong-Dinh. Invention is credited to Nguyen Truong-Dinh.
Application Number | 20130196888 13/818923 |
Document ID | / |
Family ID | 43127271 |
Filed Date | 2013-08-01 |
United States Patent
Application |
20130196888 |
Kind Code |
A1 |
Truong-Dinh; Nguyen |
August 1, 2013 |
ENGINE LUBRICANT
Abstract
A lubricant composition includes: (a) one or more base oils, (b)
at least one comb polymer formed by a polyalkyl(meth)acrylate main
chain, and hydrocarbon side chains including at least 50 carbon
atoms, (c) at least one nitrogen-containing organic friction
modifier chosen from the optionally alkoxylated fatty amines, fatty
amides or imides obtained by the condensation of fatty amines and
carboxylic acids, alone or in a mixture, (d) optionally, one or
more organometallic organomolybdenum-type friction modifiers. This
is used for the lubrication of 4-stroke gasoline or diesel engines
of light vehicles, preferentially of hybrid vehicles.
Inventors: |
Truong-Dinh; Nguyen; (Rueil
Malmaison, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Truong-Dinh; Nguyen |
Rueil Malmaison |
|
FR |
|
|
Family ID: |
43127271 |
Appl. No.: |
13/818923 |
Filed: |
August 25, 2011 |
PCT Filed: |
August 25, 2011 |
PCT NO: |
PCT/IB2011/053738 |
371 Date: |
February 25, 2013 |
Current U.S.
Class: |
508/364 ;
508/469; 508/472; 508/473; 508/474 |
Current CPC
Class: |
C10M 161/00 20130101;
C10M 2205/02 20130101; C10N 2040/253 20200501; C10M 2223/065
20130101; C10M 2205/173 20130101; C10M 2227/066 20130101; C10M
2205/06 20130101; C10M 169/044 20130101; C10N 2030/54 20200501;
C10M 2215/08 20130101; C10N 2040/255 20200501; C10M 2203/1025
20130101; C10M 141/06 20130101; C10M 2209/084 20130101; C10M
2219/068 20130101; C10M 2215/04 20130101; C10M 2205/04 20130101;
C10M 2215/042 20130101; C10M 2223/045 20130101; C10M 2215/086
20130101; C10M 2203/1025 20130101; C10N 2020/02 20130101; C10M
2205/02 20130101; C10M 2209/084 20130101; C10M 2205/04 20130101;
C10M 2209/084 20130101; C10M 2205/06 20130101; C10M 2209/084
20130101; C10M 2219/068 20130101; C10N 2010/12 20130101; C10M
2223/045 20130101; C10N 2010/12 20130101; C10M 2223/065 20130101;
C10N 2010/12 20130101; C10M 2219/068 20130101; C10N 2010/12
20130101; C10M 2223/045 20130101; C10N 2010/12 20130101; C10M
2223/065 20130101; C10N 2010/12 20130101; C10M 2203/1025 20130101;
C10N 2020/02 20130101 |
Class at
Publication: |
508/364 ;
508/473; 508/472; 508/469; 508/474 |
International
Class: |
C10M 141/06 20060101
C10M141/06 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 27, 2010 |
FR |
1056832 |
Claims
1. A lubricant composition comprising: (a) one or more base oils;
(b) at least one comb polymer formed by a polyalkyl(meth)acrylate
main chain, and hydrocarbon side chains comprising at least 50
carbon atoms; and (c) at least one nitrogen-containing organic
friction modifier chosen from fatty amines, alkoxylated fatty
amines, fatty amides or imides obtained by the condensation of
fatty amines and carboxylic acids, alone or in a mixture.
2. The lubricant composition according to claim 1 where the
hydrocarbon side chains of the comb polymers (b) are obtained by
the polymerization or copolymerization of olefins.
3. The lubricant composition according to claim 1 where the comb
polymers (b) are obtained by the copolymerization of macromonomers
of formula (II) ##STR00020## with acrylic or methacrylic monomers
of formula (III): ##STR00021## where: each R' is independently
hydrogen or a methyl, R1 is an alkyl or aryl radical comprising
from 1 to 6 carbon atoms, R2 is an alkyl radical comprising from 1
to 26 carbon atoms, A is formed by the 1,4 addition of butadiene,
optionally substituted by alkyl groups comprising 1 to 6 carbon
atoms, or by the vinyl addition of styrene, optionally substituted
by alkyl groups comprising 1 to 6 carbon atoms, and A' is formed by
the 1,2 addition of butadiene optionally substituted by alkyl
groups comprising 1 to 6 carbon atoms, or by the vinyl addition of
styrene, optionally substituted by alkyl groups comprising 1 to 6
carbon atoms, n and m are integers greater than or equal to zero,
and n+m is an integer between 7 and 3000.
4. The lubricant composition according to claim 1 where the comb
polymers (b) are obtained by the copolymerization of macromonomers
of formula (IV): ##STR00022## with acrylic or methacrylic monomers
of formula (III): ##STR00023## where: each R' is independently
hydrogen or a methyl, R1 is an alkyl or aryl radical comprising
from 1 to 6 carbon atoms, R2 is an alkyl radical comprising from 1
to 26 carbon atoms, X1, X2, X3 are independently either hydrogen,
or alkyl groups comprising from 1 to 18 carbon atoms, and p, q, r
are integers greater than or equal to zero, and p+q+r is an integer
between 7 and 3000.
5. The lubricant composition according to claim 1 where at least
one nitrogen-containing organic friction modifier (c) is chosen
from the fatty amines of formula (V): ##STR00024## where R3, R4, R5
are independently either hydrogen or aliphatic chains comprising
from 1 to 150 carbon atoms, and at least one of the R3, R4, or R5
chains is a fatty aliphatic chain comprising at least 7 carbon
atoms, and n is an integer greater than or equal to 1.
6. The lubricant composition according to claim 1 where at least
one nitrogen-containing organic friction modifier (c) is chosen
from the alkoxylated amines corresponding to formulae (VI) or (VII)
below: ##STR00025## where R6 and R10 are, independently, fatty
aliphatic chains, comprising between 7 and 150, R7 and R8 are,
independently, hydrocarbon radicals comprising from 2 to 6 carbon
atoms, R9 is a hydrocarbon radical comprising from 1 to 6 carbon
atoms, and x, y, p, q and z are integers between 0 and 50,
complying with: 0<x+y<(or equal to) 50 and 0<p+q+z<(or
equal to) 50.
7. The lubricant composition according to claim 6 where at least
one nitrogen-containing organic friction modifier (c) is chosen
from the diethanolamines of formula (VIII): ##STR00026## where R11
is a fatty aliphatic chain comprising from 7 to 150 carbon
atoms.
8. The lubricant composition according to claim 1 where at least
one nitrogen-containing organic friction modifier (c) is chosen
from the fatty amides or imides obtained by the condensation of a
dicarboxylic acid of formula (IX) ##STR00027## where R12 and R13
are independently hydrogen or a hydrocarbon group, or the R12 and
R13 hydrocarbon groups form a ring, with an amine of formula (X)
R14R15NH, and where R14 and R15 represent independently hydrogen or
an aliphatic chain comprising between 1 and 150 carbon atoms and at
least one of the R1 or R2 chains is a fatty aliphatic chain
comprising at least 7 carbon atoms.
9. The lubricant composition according to claim 1 comprising at
least one nitrogen-containing organic friction modifier (c) and at
least one organometallic friction modifier (d).
10. The lubricant composition according to claim 9 where the
organometallic friction modifiers (d) are chosen from molybdenum
dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates,
thioxanthates.
11. The lubricant composition according to claim 10 where the
organometallic friction modifier (d) is a molybdenum
dithiocarbamate of formula (XI): ##STR00028## where R16, R17, R18,
R19 are alkyl chains comprising from 8 to 13 carbon atoms.
12. The lubricant composition according to claim 8 comprising: from
65 to 90% by weight one or more base oils (a); from 2 to 15% by
weight polymer (b); and from 0.01 to 2% by weight friction
modifiers (c).
13. The lubricant composition according to claim 1 comprising at
least one isoparaffinic mineral base oil (a) obtained by
hydro-isomerization of an n-paraffin feedstock originating from
solvent dewaxing or catalytic dewaxing, or at least one
isoparaffinic synthetic base oil (a) obtained by
hydro-isomerization of an n-paraffin feedstock constituted by a
Fischer Tropsch wax.
14. The lubricant composition according to claim 1 which is of
grade 0W20 or 0W30 according to the SAE J300 classification.
15. A method of lubricating a 4-stroke gasoline or diesel engines
of light with a lubricant composition comprising: (a) one or more
base oils; (b) at least one comb polymer formed by a
polyalkyl(meth)acrylate main chain, and hydrocarbon side chains
comprising at least 50 carbon atoms; and (c) at least one
nitrogen-containing organic friction modifier chosen from fatty
amines, alkoxylated fatty amines, fatty amides or imides obtained
by the condensation of fatty amines and carboxylic acids, alone or
in a mixture, (d) one or more organometallic organomolybdenum-type
friction modifiers vehicles.
16. The method according to claim 15 wherein the diesel engine is
lubricated with the lubricant composition.
17. The lubricant composition according to claim 5 wherein the
nitrogen-containing organic friction modifier (c) is chosen from
the fatty amines of formula (V): ##STR00029## where R3, R4, R5 are
independently either hydrogen or aliphatic chains comprising from 1
to 32 carbon atoms and at least one of the R3, R4, or R5 chains is
a fatty aliphatic chain comprising at least 7 carbon atoms, and n
is an integer greater than or equal to 1.
18. The lubricant composition according to claim 6 wherein the
nitrogen-containing organic friction modifier (c) is chosen from
the alkoxylated amines corresponding to formulae (VI) or (VII)
below: ##STR00030## where R6 and R10 are, independently, fatty
aliphatic chains, comprising between 7 and 32, R7 and R8 are,
independently, hydrocarbon radicals comprising from 2 to 6 carbon
atoms, R9 is a hydrocarbon radical comprising from 1 to 6 carbon
atoms, and x, y, p, q and z are integers between 0 and 50,
complying with: 0<x+y<(or equal to) 50 and 0<p+q+z<(or
equal to) 50.
19. The lubricant composition according to claim 7 where at least
one nitrogen-containing organic friction modifier (c) is chosen
from the diethanolamines of formula (VIII): ##STR00031## where R11
is a fatty aliphatic chain comprising from 7 to 32 carbon
atoms.
20. The lubricant composition according to claim 2 wherein the
olefins are selected from the group consisting of the styrenes
comprising from 8 to 17 carbon atoms, the substituted styrenes
comprising from 8 to 17 carbon atoms, 1,4 or 1,2 addition
butadiene, or the monomers of formula (I): ##STR00032## wherein X1
and X2 are independently either hydrogen, or alkyl groups
comprising from 1 to 18 carbon atoms.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Phase Entry of International
Application No. PCT/IB2011/053738, filed on Aug. 25, 2011, which
claims priority to French Patent Application Serial No. 1056832,
filed on Aug. 27, 2010, both of which are incorporated by reference
herein.
TECHNICAL FIELD
[0002] A subject of the present invention is lubricant compositions
for engines of gasoline vehicles or diesel vehicles, allowing a
reduction in the fuel consumption of said vehicles.
BACKGROUND
[0003] Energy efficiency and reducing the fuel consumption of motor
vehicle engines is a growing concern. It is known that the engine
lubricants used in said vehicles play an important role in this
regard. The energy losses due to friction between different engine
components are produced, depending on the engine part, under
regimes of either hydrodynamic and elastohydrodynamic, or limiting
friction.
[0004] The choice of the bases and polymers improving the viscosity
index (VI improver) has an influence on the losses under a
hydrodynamic and elastohydrodynamic regime, while the choice of the
friction modifiers influences the energy losses under limiting
friction conditions. However, the formulation of a fuel-saving
engine lubricant is not limited to the selection of these different
components independently of each other. Account must be taken of
the interactions between the different components, and the other
performances of the lubricant, such as viscosity stability,
corrosion inhibition, dispersing power etc. should not be
changed.
[0005] Examples of engine lubricant formulas combining
organometallic friction modifiers and/or various organic friction
modifiers and VI improver polymers are known. Thus, engine
lubricant compositions making it possible to achieve fuel economies
(so-called "fuel eco" compositions) can be formulated by combining
GTL-type bases with fatty acid ester- and polyol-type organic
friction modifiers and polybutene-type VI improver polymers,
ethylene propylene copolymers, polyacrylates or polymethacrylates,
AB block copolymers obtained by the copolymerization of diene such
as butadiene and isoprenes with vinyl aromatics such as styrene.
Such compositions are for example disclosed in the application WO
2008/124191. Such bases however have the drawback of high cost and
it is desirable to develop the use of additives making it possible
to formulate fuel economy or fuel eco (FE) lubricants with
predominantly conventional bases.
[0006] Organometallic friction modifiers can also be combined. The
application EP 2078745 thus discloses a lubricant composition, for
gasoline and diesel engines, combining molybdenum dithiocarbamates
and zinc dithiophosphates, and making it possible to obtain fuel
economies in the vehicles equipped with these engines. These
formulas however contain high levels of sulphur, metals and
phosphorus which can be prejudicial as regards particle emissions
and post-treatment systems.
[0007] Fuel-eco engine lubricants comprising a mixture of
organomolybdenum-type friction modifiers such as molybdenum
dithiocarbamates, and organic friction modifiers such as fatty acid
monoesters and polyols are described in the application WO
2004/053033. The application WO 93/21288 describes FE engine
lubricants also combining ethoxylated amine-type friction modifiers
with partial esters of fatty acids and polyols, and VI improvers of
polyester, polymethacrylate, polyacrylate, polyolefin type. The
application EP 0955353 also describes fuel-eco engine lubricant
formulas combining organomolybdenum friction modifiers (MoDTC) with
ethoxylated fatty amine-type organic friction modifiers, optionally
in combination with VI improver polymers of polymethacrylate,
polyolefin, styrene diene copolymer type.
[0008] The fuel economies achieved thanks to the engine lubricant
have to be assessed overall, based on an entire standardized engine
cycle representative of average conditions of use. However, a
significant part of the energy losses occurs in the cold phase of
the engine cycle, at start-up. This is particularly true for
vehicles used in an urban setting, and in particular for the new
hybrid vehicles which operate with a stop-start system, where the
heat engine is stopped and restarted a significant number of
times.
[0009] A need therefore exists for engine lubricants making it
possible to achieve fuel economies greater than or equivalent to
the existing formulas, and in particular over the cold phase of the
engine cycle. The lubricant compositions according to the invention
make it possible to achieve significant fuel economies, in
particular in an urban cold cycle, thanks to a combination of VI
improver polymers and specific friction modifiers.
SUMMARY
[0010] A subject of the present invention is a lubricant
composition comprising:
(a) one or more base oils, (b) at least one comb polymer formed by
a main polyalkyl(meth)acrylate chain, and hydrocarbon side chains
comprising at least 50 carbon atoms, (c) at least one
nitrogen-containing organic friction modifier chosen from the
optionally alkoxylated fatty amines, the fatty amides or imides
obtained by the condensation of fatty amines and carboxylic acids,
alone or in a mixture, (d) optionally, one or more organometallic
friction modifiers of the organomolybdenum type.
[0011] Preferentially, the hydrocarbon side chains of the comb
polymers (b) are obtained by the polymerization or copolymerization
of olefins, preferentially chosen from the optionally substituted
styrenes, and comprising from 8 to 17 carbon atoms, 1,4 or 1,2
addition butadiene, or the monomers of formula (I)
##STR00001##
where X1 and X2 are independently either hydrogen, or alkyl groups
comprising from 1 to 18 carbon atoms.
[0012] According to an embodiment, the comb polymers (b) are
obtained by the copolymerization of macromonomers of formula
(II)
##STR00002##
with acrylic or methacrylic monomers of formula (III):
##STR00003##
where: each R' is independently hydrogen or a methyl, R1 is an
alkyl or aryl radical comprising from 1 to 6 carbon atoms, R2 is an
alkyl radical comprising from 1 to 26 carbon atoms, A is formed by
the 1,4 addition of butadiene, optionally substituted by alkyl
groups comprising from 1 to 6 carbon atoms, or by the vinyl
addition of styrene, optionally substituted by alkyl groups
comprising from 1 to 6 carbon atoms, A' is formed by the 1,2
addition of butadiene optionally substituted by alkyl groups
comprising from 1 to 6 carbon atoms, or by the vinyl addition of
styrene, optionally substituted by alkyl groups comprising from 1
to 6 carbon atoms, n and m are integers greater than or equal to
zero, and n+m is an integer between 7 and 3000, preferentially
between 10 and 3000.
[0013] According to another embodiment, the comb polymers (b) are
obtained by the copolymerization of macromonomers of formula
(IV):
##STR00004##
with acrylic or methacrylic monomers of formula (II):
##STR00005##
where: each R' is independently hydrogen or a methyl, R1 is an
alkyl or aryl radical comprising from 1 to 6 carbon atoms, R2 is an
alkyl radical comprising from 1 to 26 carbon atoms, X1, X2, X3 are
independently either hydrogen, or alkyl groups comprising from 1 to
18 carbon atoms, p, q, r are integers greater than or equal to
zero, and p+q+r is an integer between 7 and 3000, preferentially
between 10 and 3000.
[0014] According to an embodiment of the compositions according to
the invention, at least one nitrogen-containing organic friction
modifier (c) is chosen from the fatty amines of formula (V):
##STR00006##
where R3, R4, R5 are independently either hydrogen or aliphatic
chains comprising from 1 to 150 carbon atoms, preferentially from 1
to 32 carbon atoms, and at least one of the R3, R4, or R5 chains is
a fatty aliphatic chain comprising at least 7 carbon atoms, n is an
integer greater than or equal to 1, preferably comprised between 1
and 2.
[0015] According to another embodiment of the compositions
according to the invention, at least one nitrogen-containing
organic friction modifier (c) is chosen from the alkoxylated amines
corresponding to formulae (VI) or (VII) below:
##STR00007##
where R6 and R10 are, independently, fatty aliphatic chains,
comprising between 7 and 150, preferentially between 7 and 32
carbon atoms, preferentially between 12 and 18 carbon atoms, R7 and
R8 are, independently, hydrocarbon radicals comprising from 2 to 6
carbon atoms, preferentially from 2 to 4, preferentially 2 carbon
atoms, R9 is a hydrocarbon radical comprising from 1 to 6 carbon
atoms, x, y, p, q and z are integers between 0 and 50, complying
with: 0<x+y<(or equal to) 50 and 0<p+q+z<(or equal to)
50.
[0016] Preferentially, when at least one nitrogen-containing
organic friction modifier (c) is chosen from the ethoxylated
amines, said friction modifier is chosen from the diethanolamines
of formula (VIII):
##STR00008##
where R11 is a fatty aliphatic chain comprising from 7 to 150
carbon atoms, preferentially from 7 to 32 carbon atoms,
preferentially from 12 to 18 carbon atoms.
[0017] According to yet another embodiment of the compositions
according to the invention, at least one nitrogen-containing
organic friction modifier (c) is chosen from the fatty amides or
imides obtained by the condensation of a dicarboxylic acid of
formula (IX)
##STR00009##
where R12 and R13 are independently hydrogen or a hydrocarbon
group, or the R12 and R13 hydrocarbon groups form a ring, with an
amine of formula (X) R14R15NH, where R14 and R15 represent
independently hydrogen or an aliphatic chain comprising between 1
and 150 carbon atoms, preferentially from 1 to 32 carbon atoms,
preferentially from 1 to 26 carbon atoms, and at least one of the
R1 or R2 chains is a fatty aliphatic chain comprising at least 7
carbon atoms.
[0018] According to a preferred embodiment, the lubricant
compositions according to the invention comprise at least one
nitrogen-containing organic friction modifier (c) as described
above and at least one organometallic friction modifier (d).
Preferentially, in the lubricant compositions according to the
invention containing organometallic friction modifiers (d), the
latter are chosen from molybdenum dithiocarbamates,
dithiophosphates, dithiophosphinates, xanthates and
thioxanthates.
[0019] Preferentially, the organometallic friction modifier (d) is
a molybdenum dithiocarbamate of formula (XI):
##STR00010##
where R16, R17, R18, R19 are alkyl chains comprising from 8 to 13
carbon atoms.
[0020] Preferentially, the lubricant compositions according to the
invention comprise:
[0021] from 65 to 90% by weight of one or more base oils (a),
[0022] from 2 to 15% by weight of polymer (b),
[0023] from 0.01 to 2% by weight of friction modifiers (c).
[0024] In a particularly preferred manner, the lubricant
compositions according to the invention comprise at least one
isoparaffinic mineral base oil (a) obtained by hydro-isomerization
of an n-paraffin feedstock originating from solvent dewaxing or
catalytic dewaxing, or at least one isoparaffin synthetic base oil
(a) obtained by hydro-isomerization of an n-paraffin feedstock
constituted by a Fischer Tropsch wax. According to an embodiment,
the lubricant compositions according to the invention are of 0W20
or 0W30 grade according to the SAE J300 classification. According
to a particularly preferred embodiment, the lubricant compositions
according to the invention are oils for four-stroke gasoline or
diesel engines of motor vehicles, preferentially of light vehicles,
preferentially diesel. The present invention also relates to the
use of lubricant compositions as described above for the
lubrication of the 4-stroke gasoline or diesel engines of light
vehicles, preferentially of hybrid vehicles. According to a
preferred embodiment, this use is carried out in a diesel
engine.
DETAILED DESCRIPTION
[0025] The lubricant compositions according to the invention make
it possible to achieve fuel economies, in particular in a cold
urban cycle, thanks to a specific combination of VI improver
polymers and friction modifiers.
[0026] VI Improver Polymer (b):
[0027] The VI improver polymers are compounds making it possible to
minimize variations in the viscosity range with temperature, i.e.
making it possible to maintain a film of oil sufficient to protect
the parts subject to friction at high temperature, and preventing
too great an increase in viscosity when cold. The known viscosity
index improvers are typically polyalkylmethacrylates (PMAs),
polyacrylates, polyolefins, copolymers of olefins (dienes) with
vinyl aromatics (styrene).
[0028] The U.S. Pat. Nos. 5,565,130 and 5,597,871 and the U.S.
patent publication 2008/0194443 describe, as VI improver polymers,
polymers having a comb structure (comb polymer), formed by the
copolymerization of acrylate or methacrylate macromonomers
comprising a hydrocarbon chain, for example of olefin-type
copolymer, with acrylate or methacrylate monomers. Depending on
whether the monomers are of acrylate or methacrylate type, these
polymers are referred to as comb polyacrylates (comb PAs) or comb
polymethacrylates (comb PMAs), respectively. According to the IUPAC
Compendium of Chemical technology, 2.sup.nd edition, 1997, a comb
polymer is a polymer composed of comb macromolecules, which are
macromolecules constituted by a main chain having multiple
trifunctional branch points, each of which is the starting point
for a linear side chain. This comb structure distinguishes the
polymers of the U.S. Pat. Nos. 5,565,130 and 5,597,871 and U.S.
patent publication 2008/0194443 from the polyacrylates and
polymethacrylates (PMAs) usually utilized as VI improvers in the
lubricant compositions of the prior art, in particular those
described in the applications EP 0955353 and WO 93/21288. The
lubricant compositions according to the invention include as
polymer VI improver such a "comb polymer", or polymer with a comb
structure, as for example described in the U.S. Pat. Nos. 5,565,130
and 5,597,871, and the U.S. patent publication 2008/0194443 of the
present application.
[0029] The lubricant compositions according to the invention
contain therefore, as polymer VI improver, comb polyacrylates (comb
Pas) or comb polymethacrylates (comb PMAs) which are comb polymers
formed by a polyalkyl(meth)acrylate main chain, and long
hydrocarbon side chains comprising at least 50 carbon atoms.
Preferentially, these hydrocarbon side chains comprise between 50
and 25,000 carbon atoms, preferentially between 80 and 20,000
carbon atoms, typically of the order of 10,000 carbon atoms.
[0030] According to a preferred embodiment, the hydrocarbon side
chains are obtained by the polymerization or copolymerization of
olefins, for example styrene-type monomers, optionally substituted,
and comprising from 8 to 17 carbon atoms, 1,4 or 1,2 addition
butadiene, ethylene, propylene, isobutene and more generally
monomers of formula (I):
##STR00011##
where X1 and X2 are independently either hydrogen or alkyl groups
comprising from 1 to 18 carbon atoms.
[0031] According to an embodiment, the compositions according to
the invention contain a comb polymer obtained by the
copolymerization of macromonomers of formula (II)
##STR00012##
[0032] with acrylic or methacrylic monomers of formula (III):
##STR00013##
where: [0033] each R' is independently hydrogen or a methyl, [0034]
R1 is an alkyl or aryl radical comprising from 1 to 6 carbon atoms,
[0035] R2 is an alkyl radical comprising from 1 to 26 carbon atoms,
[0036] A is formed by the 1,4 addition of butadiene, optionally
substituted by alkyl groups comprising 1 to 6 carbon atoms, or by
the vinyl addition of styrene, optionally substituted by alkyl
groups comprising 1 to 6 carbon atoms, [0037] A' is formed by the
1,2 addition of butadiene optionally substituted by alkyl groups
comprising from 1 to 6 carbon atoms, or by the vinyl addition of
styrene, optionally substituted by alkyl groups comprising 1 to 6
carbon atoms, [0038] n and m are integers greater than or equal to
zero, and n+m is an integer between 7 and 3000, preferentially
between 10 and 3000.
[0039] According to another embodiment, the compositions according
to the invention contain a comb polymer obtained by the
copolymerization of macromonomers of formula (IV):
##STR00014##
with acrylic or methacrylic monomers of formula (III):
##STR00015##
where: each R' is independently hydrogen or a methyl, R1 is an
alkyl or aryl radical comprising from 1 to 6 carbon atoms, R2 is an
alkyl radical comprising from 1 to 26 carbon atoms, X1, X2, X3 are
independently either hydrogen, or alkyl groups comprising from 1 to
18 carbon atoms, p, q, r are integers greater than or equal to
zero, and p+q+r is an integer between 7 and 3000, preferentially
between 10 and 3000.
[0040] In the compositions according to the invention, these comb
polymers are advantageously used in combination with other VI
improver polymers well known to a person skilled in the art. These
well-known polymers are for example chosen from the category of the
hydrogenated styrene diene copolymers, for example hydrogenated
styrene butadiene copolymers (HSB) or styrene isoprene, which are
well known to a person skilled in the art, preferentially
hydrogenated styrene butadiene. The latter VI improver polymers,
without influencing the fuel eco performances, however make it
possible to provide the viscosity allowing formulation of grade 30
oils.
[0041] In the compositions according to the invention, the VI
improver polymers (b) are typically present at levels comprised
between 2 and 20% by mass with respect to the total weight of the
composition, or also between 2 and 15%, or also between 5 and 15%
by mass with respect to the total weight of the composition. When
the polymers (b) are used in combination with other VI improver
polymers, the total content of polymer VI improver is situated
within the same ranges (between 2 and 20%, or between 2 and 15%, or
between 5 and 15% by mass of the VI improver polymers with respect
to the total weight of the composition).
[0042] Friction Modifiers:
[0043] Nitrogen-Containing Organic Friction Modifiers (c):
[0044] The nitrogen-containing organic friction modifiers of the
compositions according to the invention are optionally alkoxylated
fatty amines, or fatty amine derivatives of the amide or imide type
obtained by the condensation of fatty amines with (di)carboxylic
acids.
[0045] Fatty Amines:
[0046] The fatty amines used in the lubricants according to the
present invention are primary, secondary or tertiary monoamines, or
polyamines, comprising one or more fatty chains. The term fatty
chain here denotes non-cyclic aliphatic hydrocarbon chains
comprising at least 7 carbon atoms, saturated or unsaturated,
optionally branched. The fatty amines are mainly obtained from the
fatty acids (fatty-chain carboxylic acids), generally originating
from the hydrolysis of the triglycerides present in vegetable and
animal oils, such as copra, palm, olive, peanut, rapeseed,
sunflower, soya, cotton or linseed oil, or beef tallow.
[0047] The fatty acids making it possible to obtain the fatty
amines of the compositions according to the invention generally
comprise from 7 to 32 carbon atoms, preferentially from 8 to 24
carbon atoms, preferentially from 10 to 20, preferentially from 12
to 18 carbon atoms. These are for example the caprylic, pelargonic,
capric, undecylenque, lauric, tridecylenic, myristic, pentadecylic,
palmitic, margaric, stearic, isostearic, nonadecylic, arachic,
heneicosanoic, behenic, tricosanoic, lignoceric, pentacosanoic,
cerotic, heptacosanoic, montanic, nonacosanoic, melissic,
hentriacontanoic, laceroic acids or unsaturated fatty acids such as
palmitoleic, oleic, erucic, nervonic, linoleic, a-linolenic,
c-linolenic, di-homo-c-linolenic, arachidonic, eicosapentaenoic,
docosahexanoic acids. These acids are dehydrated in the presence of
ammonia in order to produce nitriles, which are then subjected to
catalytic hydrogenation in order to produce primary, secondary or
tertiary amines.
[0048] The fatty amines used as compound (c) in the lubricant
compositions according to the invention correspond to general
formula (V):
##STR00016##
where R3, R4, R5 are independently either hydrogen or aliphatic
chains comprising from 1 to 150 carbon atoms, preferentially from 1
to 32 carbon atoms, and at least one of the R3, R4 or R5 chains is
a fatty aliphatic chain comprising at least 7 carbon atoms, n is an
integer greater than or equal to 1, preferably comprised between 1
and 2.
[0049] The fatty amines used in the lubricants according to the
invention are preferentially obtained from natural vegetable or
animal resources. The treatments making it possible to arrive at
fatty amines starting from natural oils can result in mixtures of
primary, secondary and tertiary monoamines and polyamines.
[0050] Ethoxylated Amines:
[0051] As compound (c) in the lubricant compositions according to
the invention, it is possible to use mono- or polyalkoxylated, for
example mono or polyethoxylated, fatty amines obtained from the
fatty amines described above. The alkoxylated amines used in the
lubricant compositions according to the invention correspond for
example to formulae (VI) and (VII) below:
##STR00017##
where R6 and R10 are, independently, fatty aliphatic chains,
comprising between 7 and 150, preferentially between 7 and 32
carbon atoms, preferentially between 12 and 18 carbon atoms, R7 and
R8 are, independently, hydrocarbon radicals comprising from 2 to 6
carbon atoms, preferentially from 2 to 4, preferentially 2 carbon
atoms, R9 is a hydrocarbon radical comprising from 1 to 6 carbon
atoms, x, y, p, q and z are integers between 0 and 50 complying
with: 0<x+y<(or equal to) 50 and 0<p+q+z<(or equal to)
50.
[0052] Preferentially, R5 and R9 are aliphatic fatty chains,
optionally substituted by aryl groups. In a particularly preferred
manner, they comprise between 7 and 30 carbon atoms, preferentially
between 10 and 20, preferentially between 12 and 18 carbon atoms.
Preferentially, R6 and R7 are aliphatic, preferentially alkyl,
chains comprising from 2 to 6 carbon atoms, preferentially from 2
to 4, preferentially 2 carbon atoms. Preferentially, R8 is an
aliphatic, preferentially alkyl, chain comprising from 1 to 6
carbon atoms, preferentially from 2 to 4, preferentially 3 carbon
atoms.
[0053] Particularly preferred compounds are the diethanolamines of
formula (VIII):
##STR00018##
where R11 is an aliphatic chain comprising from 7 to 150 carbon
atoms, preferentially from 7 to 32 carbon atoms, preferentially
from 12 to 18 carbon atoms
[0054] Fatty Amides and Imides:
[0055] The nitrogen-containing organic friction modifiers (c) of
the lubricant compositions according to the invention can be amides
or imides obtained by the condensation of the fatty amines
described above and carboxylic acids, such as for example the
oleylamides, in particular primary oleylamides. According to an
embodiment, the organic friction modifiers (c) are amides or imides
obtained by the condensation of fatty amines and dicarboxylic,
aliphatic or aromatic acids, optionally hydroxylated, such as for
example malonic, succinic, malic, tartaric, phthalic, isophthalic
acids, preferentially tartaric acid.
[0056] According to an embodiment, the organic friction modifiers
(c) are fatty amides or imides obtained by the condensation of a
dicarboxylic acid of formula (IX)
##STR00019##
where R12 and R13 are independently hydrogen or a hydrocarbon
group, or the hydrocarbon groups R12 and R13 form a ring, with an
amine of formula (X) R14R15NH where R14 and R15 represent
independently hydrogen or an aliphatic chain comprising between 1
and 150 carbon atoms, preferentially from 1 to 32 carbon atoms,
preferentially from 1 to 26 carbon atoms, and at least one of the
R1 or R2 chains is a fatty aliphatic chain comprising at least 7
carbon atoms.
[0057] Such friction modifiers are described in the U.S. patent
publication 2006/0079413, paragraphs [0025] to [028].
[0058] Organometallic Friction Modifiers (d):
[0059] Optionally, the lubricant compositions according to the
invention can contain one or more organomolybdenum compounds as
friction modifiers. These compounds are well known to a person
skilled in the art. These are for example compounds also containing
sulphur or phosphorus, such as molybdenum dithiophosphates,
dithiocarbamates, dithiophosphinates, xanthates, thioxanthates.
Organomolybdenum compounds suitable for the lubricant compositions
according to the present invention are for example described in the
application EP 2 078 745, [0036] to [062].
[0060] In the compositions according to the invention, the
nitrogen-containing organic friction modifiers (c) are typically
present at levels comprised between 0.01 and 2% by mass with
respect to the total weight of the composition, or also between 0.1
and 1%, or also between 0.3 and 0.8% by mass with respect to the
total weight of the composition. When the nitrogen-containing
organic friction modifiers (c) are used in combination with other
organometallic friction modifiers, (d), the total content of
friction modifiers is situated in the same ranges (between 0.01 and
2%, or between 0.1 and 1%, or between 0.5 and 0.8% by mass of the
friction modifiers with respect to the total weight of the
composition).
[0061] Base Oils (a):
[0062] The lubricant compositions according to the present
invention include one or more base oils, generally representing at
least 60% by weight of the lubricant compositions, generally at
least 65% by weight, and possibly ranging up to 90% and more. The
base oil or oils used in the compositions according to the present
invention can be oils of mineral or synthetic origin of groups I to
V according to the classes defined in the API classification (or
their equivalents according to the ATIEL classification) as
summarized below, alone or in a mixture.
TABLE-US-00001 Saturates content Sulphur content Viscosity index
Group I mineral oils <90% >0.03% 80 .ltoreq. VI < 120
Group II hydrocracked oils .gtoreq.90% .ltoreq.0.03% 80 .ltoreq. VI
< 120 Group III .gtoreq.90% .ltoreq.0.03% .gtoreq.120
hydrocracked or hydro- isomerized oils Group IV PAO
Polyalphaolefins Group V Esters and other bases not included in
bases of groups I to IV
[0063] These oils can be oils of vegetable, animal, or mineral
origin. The mineral base oils according to the invention include
all types of bases obtained by atmospheric and vacuum distillation
of crude oil, followed by refining operations such as solvent
extraction, deasphalting, solvent dewaxing, hydrotreatment,
hydrocracking and hydroisomerization, hydrofinishing.
[0064] The base oils of the compositions according to the present
invention can also be synthetic oils, such as certain esters of
carboxylic acids and alcohols, or polyalphaolefins. The
polyalphaolefins used as base oils are for example obtained from
monomers having 4 to 32 carbon atoms (for example octene, decene),
and have a viscosity at 100.degree. C. comprised between 1.5 and 15
Cst. Their weight-average molecular mass is typically comprised
between 250 and 3000.
[0065] Mixtures of synthetic and mineral oils can also be used.
Preferentially, the lubricant compositions according to the
invention are formulated with bases of group III and/or IV.
[0066] According to a preferred embodiment, the lubricant
compositions according to the invention include at least one
isoparaffinic mineral base oil, obtained by hydro-isomerization of
an n-paraffin feedstock, originating from solvent dewaxing or
catalytic dewaxing operations. Such bases are mineral bases of
group III referred to as group III+ bases. According to another
preferred embodiment, the lubricant compositions according to the
invention include at least one synthetic isoparaffinic base oil,
obtained by the hydro-isomerization of an n-paraffin feedstock such
as a Fischer Tropsch wax. According to a particularly preferred
embodiment, the lubricant compositions according to the invention
contain 65 to 90% by weight of such isoparaffinic bases. According
to an embodiment, the lubricant compositions according to the
invention contain exclusively so-called group III+ mineral bases or
bases obtained by the hydro-isomerization of a Fischer Tropsch wax
as base oil, in a proportion comprised between 65 and 90% by
mass.
[0067] Preferably, the compositions according to the present
invention have a kinematic viscosity at 100.degree. C. comprised
between 5.6 and 16.3 Cst measured by the standard ASTM D445, (SAE
grade 20, 30 and 40), preferentially comprised between 9.3 and 12.5
Cst (grade 30). According to a particularly preferred embodiment,
the compositions according to the present invention are multigrade
oils of grade 0W30 or 0W20 according to the SAE J300
classification. The compositions according to the present invention
also preferably have a viscosity index VI greater than 130,
preferentially greater than 150, preferentially greater than 160.
Preferentially, the lubricant compositions according to the
invention are engine oils for gasoline or diesel vehicles,
preferentially for diesel vehicles, preferentially according to the
specifications ACEA C2 or JASO DL1 well known to a person skilled
in the art.
[0068] Other Additives:
[0069] The lubricant compositions according to the invention can
also contain all types of additives suited to their use. These
additives can be added individually, or in the form of packages of
additives, guaranteeing a certain level of performance to the
lubricant compositions, as required, for example for an ACEA
(European Automobile Manufacturers Association) or JASO (Japan
Automobile Standards Organization) diesel lubricant. These are
given by way of example and non-limitatively:
[0070] Dispersants, generally representing between 5 and 8% by
weight of the lubricant compositions. The dispersants such as for
examples succinimides, PIB (polyisobutene) succinimides, Mannich
bases ensure that the insoluble solid contaminants constituted by
the secondary oxidation products formed when the engine oil is in
service are maintained in suspension and removed.
[0071] Antioxidants, generally representing between 0.5 and 2% by
weight of the lubricant compositions. The antioxidants slow down
the degradation of the oils in service, a degradation which can
result in the formation of deposits, the presence of sludge, or an
increase in the viscosity of the oil. They act as radical
inhibitors or hydroperoxide destroyers. Among the antioxidants
commonly used are found the phenolic type antioxidants and
sterically hindered amines. Another class of antioxidants is that
of the oil-soluble copper compounds, for examples copper thio- or
dithiophosphates, salts of copper and carboxylic acids, copper
dithiocarbamates, sulphonates, phenates, acetylacetonates. Copper I
and II salts of succinic acid or anhydride are used.
[0072] Anti-wear additives, generally representing between 1 and 2%
by weight of the lubricant compositions. The anti-wear additives
protect the friction surfaces by the formation of a protective film
adsorbed on these surfaces. The most commonly used is zinc
dithiophosphate or DTPZn. Also found in this category are various
phosphorus-, sulphur-, nitrogen-, chlorine- and boron-containing
compounds.
[0073] Detergents, generally representing between 2 and 4% by
weight of the lubricant compositions. The detergents are typically
alkali or alkaline-earth metal salts of carboxylic acids,
sulphonates, salicylates, naphthenates, as well as phenate salts.
They typically have a BN according to ASTM D2896 greater than 40 or
80 mg KOH/gram of detergent, and are most often overbased, with BN
values typically of the order of 150 and more, or even 250 or 400
or more (expressed in mg of KOH per gram of detergent).
[0074] And also antifoaming agents, pour point depressants,
corrosion inhibitors, etc.
EXAMPLES
[0075] Preparation of the Oils:
[0076] Several oils for diesel engine vehicles, of grade 0W30, were
prepared from a package of performance additives for diesel engine
oils making it possible to meet the ACEA C2/JASO DL1
specifications, and comprising antioxidants, corrosion inhibitors,
dispersants, detergents, anti-wear agents, pour point depressants
and corrosion inhibitors.
[0077] The compositions (in % by mass) of these oils are given in
Table 1 below:
TABLE-US-00002 TABLE 1 compositions by mass of the engine oils of
grade 0W30 A B C D E F Group III+ 79.2 73.0 72.7 -- -- 79.9 base
Synthetic base -- -- -- 72.8 72.3 -- Additives 11.9 12.2 12.2 12.2
12.2 12.4 package Pour point -- -- -- 0.2 0.2 -- depressant SBH 2.6
14.3 14.3 13.5 14.8 -- Comb PMA 5.8 -- -- -- -- -- PMA 6.7 Fatty
amides 0.5 0.5 0.5 0.5 0.5 1 and imides of tartaric acid MoDTC --
0.3 0.3 -- -- (Mo ppm) (300 ppm) (300 ppm) Total 100.0 100.0 100.0
100.00 100.00 100.00
[0078] Fuel Consumption Measurement:
[0079] Engine tests have made it possible to evaluate the fuel
economies achieved on a diesel engine vehicle, the engine of which
is lubricated with these different oils. 5W30 oil, comprising an
additives package with a performance level ACEA Cl/ASO DL1, a VI
improver polymer of hydrogenated polyisoprene type and formulated
from group III base oils, serves as a reference for the test.
[0080] Principle of the Test:
[0081] A Toyota Corolla Verso D4D Clean Power vehicle, equipped
with a Common Rail injection 2AD engine, a DPNR (Diesel
Particulate-Nox reduction) post-treatment system with a 5.sup.th
injector regeneration trap, placed in a B7 environment, is
subjected to an NEDC standardized driving cycle (New European
Driving Cycle), also called an MVEG (Motor Vehicle Emissions group)
cycle. This cycle is designed to reproducibly imitate the
conditions encountered on European roads and is widely used to
measure the vehicles' fuel consumption and pollutant emissions. The
characteristics of this cycle (speed as a function of time) are
given in FIG. 1. It comprises a cold phase or cold urban phase
(from 0 to 200 seconds), an intermediate phase or hot urban phase
(from 200 to 725 seconds), a hot phase or extra urban phase (from
725 to 1200 seconds).
[0082] Implementation:
[0083] The vehicle is placed on a double roller dynamometer meeting
E4 standards making it possible to reproducibly simulate the
on-road resistance encountered due to the aerodynamic drag and mass
of the vehicle. The tests are carried out at an ambient air
temperature of 20.degree. C., 50% humidity and pressure of 1000
mbar. The consumption is calculated on the basis of carbon
accounting after analysis of the exhaust gas. The fuel used for all
the tests is an EN590-B7 gasoil.
[0084] Results:
[0085] The absolute fuel consumptions are measured (in litres/100
km), over the whole cycle and by phase. The differences in
consumption (in %) relative to the reference taken immediately
before the oil sample to be analyzed are also calculated. The
results are given in Table 2.
[0086] Oil A is in accordance with the invention. It contains as
friction modifier a mixture of fatty amides and imides of tartaric
acid. It contains as VI improver comb polymer PMA, and a smaller
quantity of SBH, intended to provide the viscosity necessary in
order to obtain a grade 30 oil.
[0087] Oils B to F contain friction modifiers identical to the oils
according to the invention, at comparable levels, but are
formulated without comb polymer. The quantities of VI improver
polymer are adjusted in order to obtain the desired viscosimetric
grade.
[0088] Oil A according to the invention makes it possible to
achieve fuel economies relative to oils B, C, D, E, F, throughout
the engine cycle and in particular in the cold phase and the
intermediate phase.
TABLE-US-00003 TABLE 2 fuel consumptions Cold phase Intermediate
phase Previous Difference/ Previous Difference/ reference previous
reference previous consumption consumption reference consumption
consumption reference A 261 B 9.08 9.74 6.77% 7.97 8.25 3.39% B 53
C 9.62 9.74 1.23% 8.21 8.25 0.48% C 53 D 9.39 9.71 3.29% 8.01 8.14
1.59% D 130 mix 9.49 9.73 2.46% 8.18 8.38 2.38% E 130 9.43 9.71
2.88% 8.17 8.32 1.80% F G09- 9.36 9.71 3.60% 8.25 8.32 0.84% 0052C
Hot phase Complete cycle Previous Difference/ Previous Difference/
reference previous reference previous consumption consumption
reference consumption consumption reference A 261 B 5.74 5.81 1.20%
6.67 6.86 2.77% B 53 C 5.94 5.81 -2.23% 6.92 6.86 -0.87% C 53 D
5.73 5.84 1.88% 6.71 6.85 2.04% D 130 mix 5.75 5.81 1.03% 6.78 6.90
1.74% E 130 5.76 5.78 0.34% 6.78 6.86 1.16% F G09- 5.78 5.78 0.00%
6.81 6.86 0.73% 0052C
* * * * *