FRICTION MODIFIER FOR HYDROCARBON FUELS

MODIFICATEUR DE COEFFICIENT DE FROTTEMENT POUR COMBUSTIBLES HYDROCARBONES

English Abstract

There is provided a friction modifier of the formula R1~-L-N(R2~)(R3~) wherein
R1~ is a hydrocarbyl group that has a number average molecular weight (Mn) of
from 500 to 5000; L is an optional linker group; and R2~ and R3~ are
independently selected from H, a hydrocarbyl group and a bond to optional
group L, wherein at least one of R2~ and R3~ is H or a hydrocarbyl group, with
the proviso that if one of R2~ and R3~ is a hydrocarbyl group and the other of
R2~ and R3~ is H, the hydrocarbyl group does not contain a terminal amine.

French Abstract

L'invention concerne un modificateur de coefficient de frottement repr~sent~ par la formule g~n~rale R?1´-L-N(R?2´)(R?3´), dans laquelle R?1´ d~signe un groupe hydrocarbyle ayant un poids mol~culaire moyen en nombre (Mn) compris entre 500 et 5000, L d~signe un groupe de liaison facultatif et R?2´ et R?3´ d~signent chacun un ~l~ment s~lectionn~ ind~pendamment dans l'ensemble comprenant H, un groupe hydrocarbyle et une liaison vers le groupe de liaison facultatif L. Dans cette formule, R?2´ et/ou R?3´ d~signent H ou un groupe hydrocarbyle. Toutefois, si R?2´ ou R?3´ d~signe un groupe hydrocarbyle et que l'autre R?2´ ou R?3´ d~signe H, le groupe hydrocarbyle ne contient pas d'amine terminale.

Claims

25
CLAIMS
1. A friction modifier of the formula
R1-L-N(R2)(R3)
wherein
R1 is a hydrocarbyl group and has a number average molecular weight (Mn) of
from 500
to 5000;
L is an optional linker group; and
R2 and R3 are independently selected from H, a hydrocarbyl group and a bond to
optional group L, wherein at least one of R2 and R3 is H or a hydrocarbyl
group,
with the proviso that if one of R2 and R3 is a hydrocarbyl group and the other
of R2 and
R3 is H, the hydrocarbyl group does not contain a terminal amine.
2. A friction modifier according to claim 1 wherein R1 is a hydrocarbon group.
3. A friction modifier according to claim 1 or 2 wherein R1 is a branched or
straight
chain alkyl group.
4. A friction modifier according to claim 3 wherein R1 is a branched alkyl
group.
5. A friction modifier according to claim 2, 3 or 4 wherein R1 is
polyisobutene.
6. A friction modifier according to any one of the preceding claims wherein R1
has a
molecular weight of from 800 to 1300.
7. A friction modifier according to claim 5 wherein R1 is polyisobutene having
a
molecular weight of from 800 to 1300.
8. A friction modifier according to any one of the preceding claims wherein
group R1
has from 10 to 200 carbons.
9. A friction modifier according to any one of the preceding claims wherein
group R1
has from 10 to 100 carbons.
10. A friction modifier according to any one of the preceding claims which
comprises

26
linker L.
11. A friction modifier according to any one of the preceding claims wherein L
when
bonded to N(R2)(R3) provides a cyclic group of formula:
<IMG>
wherein e and f are independently an integer of from 0 to 6.
12. A friction modifier according to any one of claims 1 to 10 wherein both R2
and R3
are H.
13. A friction modifier according to any one of claims 1 to 11 wherein at
least one of
R2 and R3 is a hydrocarbyl group.
14. A friction modifier according to claim 13 wherein at least one of R2 and
R3 is a
hydrocarbyl group terminated with a moiety selected from -CH3, =CH2, -OH, -
C(O)OH,
and derivatives thereof.
15. A friction modifier according to claim 13 or 14 wherein at least one of R2
and R3 is
a hydrocarbyl group of the formula
-[R4NH]p R5X
wherein R4 is an alkylene group having from 1 to 10 carbons
wherein R5 is an alkylene group having from 1 to 10 carbons
wherein p is an integer from 0 to 10;
wherein X is selected from -CH3, -CH2=CH2, -OH, and -C(O)OH.
16. A friction modifier according to claim 15 wherein R4 is an alkylene group
having
from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons.
17. A friction modifier according to claim 15 or 16 wherein R5 is an alkylene
group
having from 1 to 5, preferably 1 to 3 carbons, preferably 2 carbons.

27
18. A friction modifier according to claim 15 wherein at least one of R2 and
R3 is a
hydrocarbyl group of the formula
-[(CH2)q NH]p(CH2)r X
wherein p is an integer from 0 to 10;
wherein q is an integer from 1 to 10;
wherein r is an integer from 1 to 10; and
wherein X is selected from -CH3, -CH2=CH2, -OH, and -C(O)OH.
19. A friction modifier according to claim 18 wherein p is an integer from 1
to 10,
preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
20. A friction modifier according to claim 18 or 19 wherein q is an integer
from 1 to 10,
preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
21. A friction modifier according to claim 18, 19 or 20 wherein r is an
integer from 1 to
10, preferably from 1 to 5, preferably from 1 to 3, preferably 1 or 2.
22. A friction modifier according to any one of claims 15 to 21 wherein X is
selected
from -CH3, and ~OH.
23. A friction modifier according to any one of claims 15 to 22 wherein at
least one of
R2 and R3 is a group of the formula ~(CH2)3CH3.
24. A friction modifier according to claim 23 wherein one of R2 and R3 is a
group of
the formula ~(CH2)3CH3, and the other of R2 and R3 is H.
25. A friction modifier according to any one of claims 15 to 22 wherein at
least one of
R2 and R3 is a group of the formula ~(CH2)2NH(CH2)2OH.
26. A friction modifier according to claim 25 wherein one of R2 and R3 is a
group of
the formula ~(CH2)2NH(CH2)2OH, and the other of R2 and R3 is H.
27. A friction modifier according to any one of the preceding claims which is
a
polyisobutenyl succinimide.

28
28. A friction modifying composition comprising:
(i) a friction modifier according to any one of claims 1 to 27;
(ii) a carrier oil comprising an optionally esterified polyether.
29. A friction modifying composition according to claim 28 wherein the
polyether
carrier oil has a molecular weight in the range 500 to 5000.
30. A friction modifying composition according to claim 28 or 29 wherein the
polyether carrier oil is a mono end-capped polypropylene glycol.
31. A friction modifying composition according to claim 30 wherein the end cap
is a
group consisting of or containing a hydrocarbyl group having up to 30 carbon
atoms.
32. A friction modifying composition according to claim 31 wherein the end cap
is or
comprises an alkyl group having from 4 to 20 carbon atoms.
33. A friction modifying composition according to claim 30 wherein the carrier
oil is a
polypropyleneglycol monoether of the formula:
<IMG>
where R6 is straight chain C12-C18 alkyl; and n is an integer of from 10 to
30.
34. A friction modifying composition according to any one of claims 28 to 33
wherein
the friction modifier is present in an amount of from 10 to 60% by weight,
preferably 30 to
60% by weight, based on the total composition.
35. A friction modifying composition according to any one of claims 28 to 34
wherein
the carrier oil is present in an amount of from 10 to 40% by weight, based on
the total
composition.
36. A friction modifying composition according to any one of claims 28 to 35
wherein
the weight ratio of friction modifier to carrier oil is from 0.2:1 to 5:1.
37. A friction modifying composition according to any one of claims 28 to 36
further

29
comprising a solvent.
38. A friction modifying composition according to claim 37 wherein the solvent
is a
hydrocarbon solvent having a boiling point in the range 66 to 320°C.
39. A fuel additive composition comprising:
(i) a friction modifier as defined in any one of claims 1 to 27; and
(ii) a carrier, diluent or solvent;
which is substantially free of any detergent and/or friction modifier other
than the friction
modifier as defined in any one of claims 1 to 27.
40. A fuel additive composition according to claim 39 which is substantially
free of
any detergent and any friction modifier other than the friction modifier as
defined in any
one of claims 1 to 27.
41. A fuel additive composition according to claim 39 or 40 wherein the
carrier,
diluent or solvent is a carrier oil comprising an optionally esterified
polyether.
42. A fuel additive composition according to any one of claims 39 to
41.wherein the
carrier, diluent or solvent is a polyether carrier oil as defined in any one
of claims 29 to
33.
43. A fuel composition comprising
(i) a fuel; and
(ii) a friction modifier according to any one of claims 1 to 27.
44. A fuel composition comprising
(i) a fuel; and
(ii) a friction modifying composition according to any one of claims 28 to 38.
45. A fuel composition comprising
(i) a fuel; and
(ii) a fuel additive composition according to any one of claims 39 to 42.
46. A fuel composition according to claim 43, 44 or 45 wherein the friction
modifier is

30
present in an amount, on a weight basis, of 50 to 500ppm.
47. A fuel composition according to claim 44 wherein the friction modifying
composition is present in an amount to provide on a weight basis, from 50 to
500 ppm
friction modifier and 30 to 500 ppm carrier oil.
48. A fuel composition according to any one of claims 43 to 47 wherein the
fuel is a
gasoline.
49. A process for the reduction of friction in a combustion engine comprising
the
steps of:
(i) dosing a fuel with a friction modifier as defined in any one of claims 1
to 27, or a
friction modifying composition as defined in any one of claims 28 to 38, or a
fuel additive
composition as defined in any one of claims 39 to 42, to provide a fuel
composition;
(ii)combusting the fuel composition in a combustion engine.
50. A process according to claim 49 wherein the fuel composition is
substantially free
of any detergent other than the friction modifier as defined in any one of
claims 1 to 27.
51. A process according to claim 49 or 50 wherein the fuel composition is
substantially free of any friction modifier other than the friction modifier
as defined in any
one of claims 1 to 27.
52. Use of a friction modifier as defined in any one of claims 1 to 27, or a
friction
modifying composition as defined in any one of claims 28 to 38, or a fuel
additive
composition as defined in any one of claims 39 to 42, for reducing friction
and/or
improving detergency in a combustion engine.
53. Use of a friction modifier as defined in any one of claims 1 to 27, or a
friction
modifying composition as defined in any one of claims 28 to 38, or a fuel
additive
composition as defined in any one of claims 39 to 42, for reducing friction
and improving
detergency in a combustion engine.
54. A friction modifier as substantially herein before described with
reference to any
one of the Examples.

31
55. A friction modifying composition as substantially herein before described
with
reference to any one of the Examples.
56. A fuel additive composition as substantially herein before described with
reference to any one of the Examples.
57. A fuel composition as substantially herein before described with reference
to any
one of the Examples.
58. A process for the reduction of friction in a combustion engine as
substantially
herein before described with reference to any one of the Examples.
59. A use as substantially herein before described with reference to any one
of the
Examples.

Description

CA 02475601 2004-08-09
WO 03/070860 PCT/GB03/00643
FRICTION MODIFIER FOR HYDROCARBON FUELS
This invention relates to multi-functional friction modifiers and friction .
modifying
compositions for hydrocarbon fuels, especially gasoline. In particular, the
invention
s relates to alkenylsuccinimide-based friction modifiers and friction
modifying compositions
for hydrocarbon fuels and especially gasoline.
It has been of major concern in this field to find methods of reducing engine
friction and
fuel consumption in internal combustion engines. It is believed that by
reducing engine
io friction, increased power and fuel economy may be obtained. One method of
reducing
engine friction is to use fuel which has been dosed with an additive having
friction
reducing properties.
Additive compositions for gasoline have to satisfy a large number of criteria,
amongst the
is most important.of which are:
i) reduction of engine friction to increase fuel economy;
ii) good lubrication to reduce wear;
iii) elimination of carburettor and injector fouling;
iv) good detergency in the intake port and intake valve regions of the engine;
2o v) elimination of valve stick, a problem often associated with the use of
high molecular
weight detergents;
vi) corrosion protection;
vii) good demulsifying characteristics.
2s In order to meet these criteria, it has been necessary until now to provide
additive
packages comprising a separate friction modifier and detergent/deposit
inhibiting
compound. For example, WO-A-98/11175 discloses an additive package comprising
an
ashless friction modifier, a deposit inhibitor and a carrier fluid. As
discussed in WO-A-
98/11175, current practice in the supply of gasoline is generally to pre-mix
the fuel
3o additives into a concentrate in a hydrocarbon solvent base, and then inject
the
concentrate into gasoline pipelines used to fill tankers prior to delivery to
the customers.
Under present operating conditions, the maximum amount of concentrate that can
be
incorporated into a tanker of gasoline is typically about 2000ppm based on the
weight of
the gasoline. It would appear that in order to avoid exceeding this maximum
amount of
3s additive, the provision of multi-functional fuel additives would be
advantageous.

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2
WO-A-93/20170 discloses a composition comprising succinimide detergents and
mono
end-capped polypropylene glycol. Each of the spec~cally disclosed detergents
is
derived from a polyalkylene polyamine comprising two primary amine groups. The
resultant succinimide detergent comprises a terminal amine group.
Some aspects of the present invention are defined in the appended claims.
In a first aspect the present invention provides a friction modifier of the
formula R'-L-
N(R2)(R3) wherein R' is a hydrocarbyl group and has a number average molecular
weight
to (Mn) of from 500 to 5000; L is an optional linker group; R2 and R3 are
independently
selected from H, a hydrocarbyl group and a bond to optional group L, wherein
at least
one of R2 and R3 is H or a hydrocarbyl group, with the proviso that if one of
RZ and R3 is
a hydrocarbyl group and the other of R2 and R3 is H, the hydrocarbyl group
does not
contain a terminal amine.
In a second aspect the present invention provides a friction modifying
composition
comprising a friction modifier as herein defined and a carrier oil comprising
an optionally
esterified polyether.
2o It has surprisingly been found that these new friction mod~ers and fiction
modifying
compositions are mufti-functional and exhibit, in addition to their friction
modifying
characteristic, good intake valve detergency, good valve stick performance and
good
padcagability. The mufti-functional nature of the friction modfiers and
friction modifying
compositions according to the present invention enables them to be used in the
substantial
absence of any additional friction modfier or detergent. This is advantageous,
for example,
because of the need to conform to limits on the amount of fuel additive
incorporated into
fuel.
Use of these new friction modifiers and friction ~ modifying compositions in
fuel in a
combustion engine, may result in a considerable reduction in friction and
wear, in particular
a reduction in wear in the fuel pump and around the piston walls of the
combustion engine.
The reduction in friction should result in improved fuel economy. Wear of
components of a
combustion engine limits the useful life of these components and may be costly
given that
the engine components are expensive to produce. Additionally, wear of
components of a
3s combustion engine may result in down time for equipment, reduced safety and
a decrease

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3
in reliability. Use of the friction modfiers or friction modifying
compositions according to the
present invention may reduce wear increasing the lifetime of the combustion
engine
components and thus avoiding the problems associated with wear. These friction
mod~ers
and friction modifying compositions may also be of benefit in gasoline direct
injection
engines (GDI).
In the present application by the term "friction modifier" it is meant a
substance capable of
modifying friction. In particular, by the term "friction mod~er" it is meant a
substance
capable of reducing fiction. In particular, the term "friction modifier"
refers to a substance
1o which is capable of reducing friction, when dosed into a fuel which is
subsequently
combusted in a combustion engine.
In one aspect, the term "friction mod~er" refers to a substance which, at a
treat rate of
120mg11 in unleaded gasoline generates a Wear Scar Diameter in the High
Frequency
Reciprocating Rig test at 20°C of less than 500 miaons, preferably less
than 450 microns,
more preferably less than 400 microns.
In the present specification by the term "hydrocarbyl group" it is meant a
group comprising
at least C and H and may optionally comprise one or more other suitable
substituents.
2o Examples of such substituents may include alkoxy-, nitro-, a hydrocarbon
group, an N-
acyl group, a cyclic group etc. In addition to the possibility of the
substituents being a
cyclic group, a combination of substituents may form a cyclic group. If the
hydrocarbyl
group comprises more than one C then those carbons need not necessarily be
linked to
each other. For example, at least two of the carbons may be linked via a
suitable
2s element or group. Thus, the hydrocarbyl group may contain hetero atoms.
Suitable
hetero atoms will be apparent to those skilled in the art and include, for
instance,
nitrogen and oxygen.
FRICTION MODIFIER - R'
Preferably R' is a hydrocarbon group. By the term "hydrocarbon group" it is
meant a
group comprising only C and H. The hydrocarbon group may be saturated or
unsaturated. The hydrocarbon group may be straight chained or branched.
Preferably R' is a branched or straight chain alkyl group. More preferably R'
is a

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4
branched alkyl group.
In a particularly preferred embodiment R' is polyisobutene.
Conventional and so called high reactivity polyisobutenes are suitable for use
in the
invention. High reactivity is defined as a polyisobutene wherein at least 50%,
preferably
70% or more of the terminal olefinic double bonds are of the vinylidene type.
The preparation of polyisobutenyl substituted succinic anhydrides (PIBSA) is
1o documented. in the art. Suitable processes include thermally reacting
polyisobutenes
with malefic anhydride (see for example US-A-3,361,673 and US-A-3,018,250),
and
reacting a halogenated, in particular a chlorinated, polyisobutene (PIB) with
malefic
anhydride (see for example US-A-3,172,892). Alternatively, the polyisobutenyl
succinic
anhydride can be prepared by mixing the polyolefin with malefic anhydride and
passing
chlorine through the mixture (see for example GB-A-949,981 ).
The reaction product of these processes will be a complex mixture of unreacted
polymer
as well as the product polyisobutenyl succinic acid anhydride, the
polyisobutenyl
substituent being connected to either one or both of the alpha carbon atoms of
the
2o succinic acid group.
R' may have a molecular weight selected to provide the required properties of
the
detergent compound. In a preferred aspect R' has a molecular weight of from
800 to
1300. In a particularly preferred aspect R' is polyisobutene having a
molecular weight of
from 800 to 1300. The-molecular weights are as determined by vapour phase
osmometry
or by gel permeation chromatography, on the originating polymer.
In one aspect R' may have from 10 to 200 carbons or from 10 to 100 carbons.
3o FRICTION MODIFIER - LINKER
The friction modifier of the formula R'-L-N(R2)(R3) may or may not comprise
optional linker
L. If L is present it may be any suitable group. Suitable groups include
~ C,.~ hydrocarbyl groups optionally including one or more, preferably two,
carbonyl
groups,

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~ C~~ hydrocarbon groups optionally including one or more, preferably two,
carbonyl
groups,
C~,Zdiacyl groups which when bonded to N(R2)(R3) provides a cyclic group of
formula:
O
'e I
NCR
f II
s 0
wherein a and f are independently an integer of from 0 to 6.
~ diacyl groups derived from succinic anhydride which when bonded to N(RZ)(R3)
provides a cyclic group of formula:
N~~
1o wherein a is 0 and f is 1.
FRICTION MODIFIER - N(R~(R3)
The friction modifier of the present invention contains a nitrogen moiety
N(RZ)(R3)
attached to the hydrocarbyl group R' via optional linker. L. The groups and R2
and R3 of
the nitrogen moiety are independently H or a hydrocarbyl group. Thus
~ both R2 and R3 may be H
~ one of R2 and R3 may be H and the other of R2 and R3 may be hydrocarbyl
~ both of R2 and R3 may be hydrocarbyl.
R2 and R3 are independently selected from H, a hydrocarbyl group and a bond to
optional group L, wherein at least one of RZ and R3 is H or a hydrocarbyl
group. When
one of RZ and R3 is a bond to optional group L, the nitrogen may contain
either a double
bond to a single atom of the group L or may be bonded to two different
moieties of group
L to form a cyclic group. Clearly if optional group L is not present these
explanations
equally apply to the connection between R' and N(R2)(R3).
It is requirement that when one of RZ and R3 is a hydrocarbyl group and the
other of ft2

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6
and R3 is H, the hydrocarbyl group does not contain a terminal amine. In other
words
when one of RZ and R3 is a hydrocarbyl group and the other of R2 and R3 is H,
if the
hydrocarbyl group is an amine or polyamine the amine or amine units are
selected from
secondary and tertiary amines.
Suitable terminal groups include -CH3, =CHZ, -OH, -C(O)OH and derivatives
thereof.
Suitable derivatives include esters and ethers.
Preferably the hydrocarbyl group RZ and/or R3 does not contain a terminal
amine. In
other words if R2 and/or R3 is a hydrocarbyl group selected from an amine or
polyamine,
the amine or amine units are selected from secondary and tertiary amines.
A preferred hydrocarbyl group for each of R2 and R3 is a group of the formula
-[R4N H]PR5X
wherein R4 is an alkylene group having from 1 to 10 carbons, preferably from 1
to 5,
preferably 1 to 3 carbons, preferably 2 carbons;
wherein RS is an alkylene group having from 1 to 10 carbons, preferably from 1
to 5,
preferably 1 to 3 carbons, preferably 2 carbons;
wherein p is an integer from 0 to 10;
2o wherein X is selected from -CH3, -CH2=CH2, -OH, and -C(O)OH.
A preferred hydrocarbyl group for each of R2 and R3 is a group of the formula
-[(CH2)qNH]P(CH2)~X
wherein p is an integer from 0 to 10, preferably 1 to 10, preferably from 1 to
5, preferably
from 1 to 3, preferably 1 or 2;
wherein q is an integer from 1 to 10, preferably from 1 to 5, preferably from
1 to 3,
preferably 1 or 2;
wherein r is an integer from 1 to 10, preferably from 1 to 5, preferably from
1 to 3,
preferably 1 or 2; and
3o wherein X is selected from -CH3, -CH2=CH2, -OH, and -C(O)OH.
Preferably X is -CH3, or -0H.
The friction modifiers of the present invention may be derived from a wide
range of
precursors. Embodiments of the present invention include compounds derived
from

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7
amines selected from ammonia, butylamine, aminoethylethanolamine, aminopropan-
2-ol,
5-aminopentan-1-ol, 2-(2-aminoethoxy)ethanol, monoethanolamine, 3-aminopropan-
1-ol,
2-((3-aminopropyl)amino)ethanol, dimethylaminopropylamine, and N-(alkoxyalkyl)-
alkanediamines including N-(octyloxyethyl)-1,2-diaminoethane and N-
(decyloxypropyl)-
N-methyl-1,3-diaminopropane.
The features described above may provide particularly preferred compounds in
accordance with the present invention. These include compounds wherein
~ at least one of R2 and R3 is a group of the formula -(CHZ)3CH3;
~ one of RZ and R3 is a group of the formula -(CH2)3CH3, and the other of R2
and R3 is
H;
~ at least one of R2 and R3 is a group of the formula -(CH2)2NH(CH2)ZOH;
~ one of R2 and R3 is a group of the formula -(CH2)2NH(CH2)20H, and the other
of R2
and R3 is H; and
~ the friction modfier is a polyisobutenyl succinimide.
In one preferred aspect the friction modifier of formula R'-L-N(R2)(R3)
comprises the
optional linker L, and L, when bonded to N(R2)(R3), provides a cyclic group of
formula:
2o wherein a and f are independently and integer from 0 to 6. In this aspect,
R3 is preferably
a hydrocarbyl group.
In one aspect R3 is a hydrocarbyl group of formula:
-[R4NHJPR5-N(R2~)-L'-R'.
wherein R'~ is a hydrocarbyl group and has a number average molecular weight
(Mn) of
from 500 to 5000;
wherein L' is an optional linker group;
wherein Rr is independently selected from H, a hydrocarbyl group and a bond to
optional
group L';
3o wherein R4 is an alkylene group having from 1 to 10 carbons, preferably
from 1 to 5,
preferably 1 to 3 carbons, preferably 2 carbons;

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8
wherein R5 is an alkylene group having from 1 to 10 carbons, preferably from 1
to 5,
preferably 1 to 3 carbons, preferably 2 carbons; and
wherein p is an integer from 0 to 10.
In a preferu ed aspect R3 is a hydrocarbyl group of formula:
-[(CH2)qNH)P(CH2)~ N(R2~)-L'-R'
wherein R'~ is a hydrocarbyl group and has a number average molecular weight
(Mn) of
from 500 to 5000;
wherein L' is an optional linker group;
1o wherein Rr is independently selected from H, a hydrocarbyl group and a bond
to optional
group L';
wherein p is an integer from 0 to 10, preferably 1 to 10, preferably from 1 to
5, preferably
from 1 to 3, preferably 1 or 2;
wherein q is an integer from 1 to 10, preferably from 1 to 5, preferably from
1 to 3,
preferably 1 or 2; and
wherein r is an integer from 1 to 10, preferably from 1 to 5, preferably from
1 to 3,
preferably 1 or 2.
Preferably R'~ is a hydrocarbon group. Preferably R'~ is a branched or
straight chain alkyl
2o group. More preferably R'~ is a branched alkyl group. In a particularly
preferred
embodiment R'~ is polyisobutene.
R'~ may have a molecular weight selected to provide the required properties of
the friction
modifier. In a preferred aspect R'~ has a molecular weight of from 800 to
1300. In a
particularly preferred aspect R'~ is polyisobutene having a molecular weight
of from 800 to
1300. The molecular weights are as determined by vapour phase osmometry or by
gel
permeation chromatography, on the originating polymer.
In one aspect R'~ may have from 10 to 200 carbons or from 10 to 100 carbons.
If L' is present it may be any suitable group. Suitable groups include
~ C,~ hydrocarbyl groups optionally including one or more, preferably two,
carbonyl
groups,
~ C,~ hydrocarbon groups optionally including one or more, preferably two,
carbonyl
groups,

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9
~ C~,2 diacyl groups which, when R2~ is a bond to group L', provide a cyclic
group of
formula:
wherein e' and f are independently an integer of from 0 to 6.
~ diacyl groups derived from succinic anhydride which, when Rz is a bond to
group L',
provide a cyclic group of formula:
wherein e' is 0 and f is 1.
io FRICTION MODIFYING COMPOSITION - CARRIER OIL
As previously mentioned, in one aspect the present invention provides a
friction
modifying composition comprising a friction modifier as herein defined and a
carrier oil
comprising an optionally ester~ed polyether.
The carrier oil may have any suitable molecular weight. A preferred molecular
weight is
in the range 500 to 5000.
In a prefer-ed aspect the polyether carrier oil is a mono end-capped
polypropylene
2o glycol. Preferably the end cap is a group consisting of or containing a
hydrocarbyl group
having up to 30 carbon atoms. More preferably the end cap is or comprises an
alkyl
group having from 4 to 20 carbon atoms or from 12 to 18 carbon atoms.
The alkyl group may be branched or straight chain. Preferably it is a straight
chain
group.
Further hydrocarbyl end capping groups include alkyl-substituted phenyl,
especially

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where the alkyl substituent(s) is or are alkyl groups of 4 to 20 carbon atoms,
preferably 8
to 12, preferably straight chain.
The hydrocarbyl end capping group may be attached to the polyether via a
linker group.
5 Suitable end cap linker groups include an ether oxygen atom (-O-), an amine
group (-
NH-), an amide group (-CONH-), or a carbonyl group -(C=O)-.
In a preferred embodiment the carrier oil is a polypropyleneglycol monoether
of the
formula:
CH3
R60-(-H-H-O-~-H
l0
where Re is straight chain C~-C~ alkyl, preferably C4-C~ alkyl, preferably
C~rC,B alkyl;
and n is an integer of from 10 to 50, preferably 10 to 30, more preferably 12
to 20.
Such alkyl polypropyleneglycol monoethers are obtainable by the polymerisation
of
propylene oxide using an aliphatic alcohol, preferably a straight chain
primary alcohol of
to 20 carbon atoms, as an initiator. If desired a proportion of the
propyleneoxy units may
be replaced by units derived from other CrCe alkylene oxides, e.g. ethylene
oxide or
isobutylene oxide, and are to be included within the term
"polypropyleneglycol". The
initiator may also be a phenol or alkyl phenol of the formula R'OH, a
hydrocarbyl amine
or amide of the formula R'NH2 or R'CONH, respectively, where R' is C,-C~
hydrocarbyl
group, preferably a saturated aliphatic or aromatic hydrocarbyl group such as
alkyl,
phenyl or phenalkyl etc. Preferred initiators include long chain alkanols
giving rise to the
long chain polypropyleneglycol monoalkyl ethers.
2s In a further aspect the polypropyleneglycol may be an ester (RsC00) group
where RB is
defined above. In this aspect the carrier oil may be a polypropyleneglycol
monoester of
the formula
3
s C-CH O-Rs
R O--~-H2 H O
where Rg and n are as defined above and R8 is a C,-C~ hydrocarbyl group,
preferably
3o an aliphatic hydrocarbyl group, and more preferably C,-C,a alkyl.

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11
FRICTION MODIFYING COMPOSITION - COMPOSITION
The friction modifier may be present in the friction modifying composition in
an amount to
provide the necessary and/or required handling and/or functional properties.
Typically
the friction mod~er (including solvent of production) is present in an amount
of from 10 to
60% by weight, preferably 30 to 60% by weight, based on the total composition.
Typically the friction modifier (excluding solvent of production) is present
in an amount of
from 6 to 36% by weight, preferably 18 to 36% by weight, based on the total
composition.
to The carrier oil may be present in an amount of from 10 to 40% by weight,
based on the
total composition.
The weight ratio of active friction modifier to carrier oil in the friction
modifying
composition may be from 0.2:1 to 5:1.
Preferably the weight ratio of active friction modifier to carrier oil in the
friction modifying
composition will be in the range 0.2:1 to 5:1, or 0.6:1 to 5:1, typically
about 5:1, 2:1, 1:1,
0.9:1, 0.8:1, or 0.6:1.
2o Preferably the weight ratio of active friction modifier to carrier oil in
the friction modifying
composition will be in the range 1:0.2 to 1:1.8, or 1:0.3 to 1:1.7, or 1:0.4
to 1:1.6, or 1:0.5
to 1:1.5, or 1:0.6 to 1:1.4, or 1:0.7 to 1:1.3, or 1:0.8 to 1:1.2 or 1:0.9 to
1:1.1, typically
approximately 1:0.2, 1:0.5, 1:0.7, 1:1, 1:1.1, 1:1.2 or 1:1.6, such as 1:1.
In a preferred aspect the friction modifying composition of the present
invention further
comprises a solvent. The solvent may be a hydrocarbon solvent having a boiling
point in
the range 66 to 320°C. Suitable solvents include xylene, toluene, white
spirit, mixtures of
aromatic solvents boiling in the range 180°C to 270°C (including
aromatic solvent
mixtures sold under the trade marks Shellsol AB, Shellsol R, Solvesso 150,
Aromatic
150), and environmentally friendly solvents such as the low aromatic content
solvents of
the FINALAN range.
If present the amount of solvent to be incorporated will depend upon the
desired final
viscosity of the friction modifying composition. Typically the solvent will be
present in an
amount of from 20 to 70% of the final composition on a weight basis.

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12
In a preferred aspect the friction modifying composition of the present
invention
comprises a solvent and a co-solvent. The co-solvent may be typically present
in an
amount of 1-2 wt.%. Suitable co-solvents include aliphatic alcohols (such as
CAS no
66455-17-2)
The friction modifying compositions of the present invention may contain a
number of
minor ingredients, often added to meet specific customer requirements.
Included
amongst these are dehazers, usually an alkoxylated phenol formaldehyde resin,
added
1o to minimise water adsorption and to prevent a hazy or cloudy appearance,
and a
corrosion inhibitor, usually of the type comprising a blend of one or more
fatty acids and
amines. Either or both may be present in the compositions of the present
invention in
amounts ranging from 1 to 5%, or 1 to 3% each, based on the total weight of
the
composition.
Other minor ingredients which may be added include anti-oxidants, anti-icing
agents,
metal deactivators, dehazers, corrosion inhibitors, dyes, lubricity additives,
additional
friction modifiers, and the like. These may be added in amounts ranging from a
few parts
per million, up to 2 or 3% by weight, according to conventional practice.
In one preferred aspect, no lubricity additives or friction modfiers other
than the friction
modifier as herein defined are added to the friction modifying composition.
In general terms the total amount of such . minor functional ingredients in
the friction
modifying composition will not exceed about 10% by weight, more usually not
exceeding
about 5% by weight.
FUEL ADDITIVE COMPOSITION
3o In one aspect the present invention provides a fuel additive composition
comprising a
friction mod~er as herein defined and a carrier, diluent or solvent, wherein
the fuel
additive composition is substantially free of any detergent and/or friction
modifier other
than the friction modifier as herein defined.

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13
The term °fuel additive composition" as used herein refers to a
composition which will
undergo no modification before it is dosed into a fuel. In particular the term
refers to a
composition to which no further components are added before it is dosed into a
fuel.
s The term °substantially free° of a given substance, as used
herein in relation to a fuel
additive composition, means that the substance is present in the fuel additive
composition in an amount of less than 1% by weight of the composition,
preferably less
than 0.5%, preferably less than 0.1 %, preferably less than 0.05%.
to Preferably the fuel additive composition is substantially free of any
detergent other than
the friction modifier as herein defined.
Preferably the fuel additive composition is substantially free of any friction
mod~er other
than the friction mod~er as herein defined.
Preferably the fuel additive composition is substantially free of any
detergent and any
friction modifier other than the friction modifier as herein defined.
In a preferred aspect, the carrier, diluent or solvent is a carrier oil
comprising an
2o optionally esterified polyether.
Preferably the carrier, diluent or solvent is a polyether carrier oil as
herein defined.
Preferably the carrier, diluent or solvent of the fuel additive composition is
a
polypropyleneglycol monoether of the formula:
CH3
R60-~-H-H-O-~-H
z
where Re is straight chain C,rC,B alkyl; and n is an integer of from 10 to 30.
FUEL COMPOSITIONS
The friction modifier of the present invention may be incorporated in fuel to
provide a fuel
composition. Thus in a further aspect the present invention provides a fuel
composition
comprising a fuel and a friction mod~er as herein defined.

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14
The friction modifying composition of the present invention may be
incorporated in fuel to
provide a fuel composition. Thus in a further aspect the present invention
provides a fuel
composition comprising a fuel and a friction modifying composition as herein
defined.
The fuel additive composition of the present invention may be incorporated in
fuel to
provide a fuel composition. Thus in a further aspect the present invention
provides a fuel
composition comprising a fuel and a fuel additive composition as herein
defined.
to Preferably the friction modifier is present in the fuel in an amount to
provide on a weight
basis, from 50 to 500 ppm.
Preferably the friction modifying composition is present in the fuel in an
amount to
provide on a weight basis, from 50 to 500 ppm friction modifier and 30 to 500
ppm carrier
oil.
Preferably the fuel composition is substantially free of any detergent other
than the
friction modifier as herein defined.
2o Preferably the fuel composition is substantially free of any friction
modifier other than the
friction modifier as herein defined.
Preferably the fuel composition is substantially free of any detergent other
than the
friction mod~er as herein defined and substantially free of any friction
modifier other than
the friction modifier as herein defined.
The term °substantially free" of a given substance, as used herein in
relation to a fuel
composition, means that the substance is present in the fuel composition in an
amount of
less than 10 ppm, preferably less than 5 ppm, preferably less than 1 ppm.
Preferably the fuel is a gasoline.
By the term "gasoline", it is meant a liquid fuel for use with spark ignition
engines
(typically or preferably containing primarily or only C4-C12 hydrocarbons) and
satisfying
international gasoline specifications, such as ASTM D-439 and EN228. The term

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includes blends of distillate hydrocarbon fuels with oxygenated components
such as
ethanol, as well as the distillate fuels themselves. The fuels may contain, in
addition to
the additive composition of the invention, any of the other additives
conventionally added
to gasoline as, for example, antiknock additives, anti-icing additives, octane
requirement
5 additives, lubricity additives etc."
It is known that prior to combustion certain fuel additives can reach the thin
film of
lubricant that coats the cylinder wall and can, over time, accumulate in
engine oil. It is
therefore envisaged that in one aspect the friction modifier or friction
modifying
1o composition accumulates in engine oil. In one embodiment, the present
invention
provides an oil composition comprising an engine oil and a friction modifier
or friction
modifying composition as herein defined. In one aspect the present invention
provides
an oil composition comprising (i) an oil, preferably an engine oil and (ii) a
friction modifier
of the formula R'-L-N(R2)(R3) wherein R' is a hydrocarbyl group and has a
number
15 average molecular weight (Mn) of from 500 to 5000; L is an optional linker
group; RZ and
R3 are independently selected from H, a hydrocarbyl group and a bond to
optional group
L, wherein at least one of R2 and R3 is H or a hydrocarbyl group, with the
proviso that if
one of R2 and R3 is a hydrocarbyl group and the other of R2 and R3 is H, the
hydrocarbyl
group does not contain a terminal amine.
PROCESS
In one aspect the present invention provides a process for the reduction of
friction in a
combustion engine comprising the steps of (i) dosing a fuel with a friction
modifier as
herein defined, or a friction modifying composition as herein defined, or a
fuel additive
composition as herein defined, to provide a fuel composition; (ii) combusting
the fuel
composition in a combustion engine.
USE
In one aspect the present invention provides use of a friction modifier as
herein defined
for reducing friction and/or improving detergency in a combustion engine. In
one
preferred aspect the present invention provides use of a friction mod~er as
herein
defined for reducing friction in a combustion engine. In one highly preferred
aspect the
present invention provides use of a friction modifier as herein defined for
reducing friction

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16
and improving detergency in a combustion engine.
In one aspect the present invention provides use of a friction modifying
composition as
herein defined for reducing friction and/or improving detergency in a
combustion engine.
In one preferred aspect the present invention provides use of a friction
modifying
composition as herein defined for reducing friction in a combustion engine. In
one highly
preferred aspect the present invention provides use of a friction modifying
composition
as herein defined for reducing friction and improving detergency in a
combustion engine.
to In one aspect the present invention provides use of a fuel additive
composition as herein
defined for reducing friction and/or improving detergency in a combustion
'engine. In one
preferred aspect the present invention provides use of a fuel additive
composition as
herein defined for reducing friction in a combustion engine. In one highly
preferred
aspect the present invention provides use of a fuel additive composition as
herein
defined for reducing friction and improving detergency in a combustion engine.
The present invention will now be described in further detail by way of
Example only.
EXAMPLES
SYNTHESIS OF FRICTION MODIFIERS
Amine used to Produce Friction Modifier
Friction Modifier
Ammonia PIBSI
0
PIB \NH
O
Butylamine ButA PIBSI
0
PIB- N
O

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17
Amine used to Produce Friction Modifier
Friction Modifier
Aminoethylethanolamine AEEA PIBSI
(AEEA) off
0
~NH
PIB ~N
O
Tetraethylenepentamine bis TEPA PIBSI
(TEPA) o 0
H H
PIB H H ~ PIB
N
H
O O
Example 1 - 1000 mwt PIBSA & Butylamine
1000 mwt high reactive PIB derived PIBSA (467.6g) was stirred with Shellsol AB
(311.8g) in a 11 oil jacketed reactor equipped with an ovefiead stir-er,
thermometer and
Dean 8 Stark trap. Whilst still at room temperature butylamine (31.5g) was
added in one
aliquot with continued stirring. An immediate exotherm was noted. The reaction
mix was
heated to 150°C for three hours whilst removing water. 720g of product
was isolated..
to
Analysis of the product showed it to contain 40%m/m solvent, 0.81 %mlm
nitrogen.
Example 2 - 1000 mwt PIBSA & Aminoethylethanolamine
1000 mwt high reactive PIB derived PIBSA (633.2g) was stirred with Shellsol AB
(421g)
in a 11 oil jacketed reactor equipped with an overhead stir-er, thermometer
and Dean &
Stark trap. Whilst still at room temperature aminoethylethanolamine (60.6g)
was added
in one aliquot with continued stirring. An immediate exotherm was noted. The
reaction
mix was heated to 130-150°C for three hours whilst removing water.
1058g of product
2o was isolated.
Analysis of the product showed it to contain 39%m/m solvent, 1.47%m/m
nitrogen.

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18
Example 3 - 550 mwt PIBSA & Aminoethylethanolamine
550 mwt high reactive PIB derived PIBSA in Shellsol AB (900g, 40% solvent) was
stirred
in a 11 oil jacketed reactor equipped with an overhead stirrer, thermometer
and Dean &
Stark trap. Aminoethylethanolamine (84.2g) was added at room temperature
whilst
stirring. An exotherm was noted. The reaction mix was heated to 140°C
for four hours
whilst removing water. 926g of product was isolated.
Analysis of the product showed it to contain 38.5 %m/m solvent, 2.33 %m/m
nitrogen.
to
Example 4 - 2300 mwt PIBSA & Butvlamine
2300 mwt high reactive PIB derived PIBSA in Shellsol (495g, 21.6% solvent) was
stirred
with extra Shellsol AB (110g) in a 11 oil jacketed reactor equipped with an
overhead
stirrer, them~ometer and Dean ~ Stark trap. Butylamine (9.37g)was added at
room
temperature whilst stirring. The reaction mix was heated to 130°C for
three hours whilst
removing water. 645g of product was isolated.
Analysis of the product showed it to contain 38 %m/m solvent, 0.35 %m/m
nitrogen.
Example 5 - 2300 mwt PIBSA & Aminoethylethanolamine
2300 mwt high reactive PIB derived PIBSA in Shellsol (5088, 21.6% solvent) was
stirred
with extra Shellsol AB (157g) in a 11 oil jacketed reactor equipped with an
overhead
stirrer, thermometer and Dean & Stark trap. Aminoethylethanolamine (17.65g)
was
added at room temperature whilst stirring. The reaction mix was heated to
140°C for 3.5
hours whilst removing water. 8388 of product was isolated.
3o Analysis of the product showed it to contain 42 %m/m solvent, 0.65 %m/m
nitrogen.
Example 6 -1000 mwt PIBSA & Ammonia
1000 mwt high reactive PIB derived PIBSA (450.15g) was stirred with Shellsol
AB
(298.99g) in a 11 oil jacketed reactor equipped with an overhead stirrer,
thermometer,

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19
Dean & Stark trap and a dip tube through which to add ammonia. The temperature
was
taken up to 138°C and the ammonia gas (5.81g) was added over 3 hours,
whilst
collecting water in the trap. Heating was continued for a further 2 hours. 731
g of product
was isolated.
s
Analysis of the product showed it to contain 40 %rNm solvent, 0.76 %m/m
nitrogen.
TEST DATA
Example 7 - High Freguency Reciprocating! Rig (HFRR) Test
The standard procedure for evaluating diesel fuel lubricity using the High
Frequency
Reciprocating Rig (HFRR) test was modified to evaluate gasoline lubricity. A
temperature of 20°C, which is lower than the standard temperature, was
selected due to
is the higher volatility of gasoline as compared with diesel.
The procedure was as follows. A steel ball was attached to an oscillating arm
assembly
and mated to a steel disk specimen in the HFRR sample cell. The fuel reservoir
contained 6ml of the fuel composition being tested. A load of 200 grams was
applied to
2o the ball/disk interface by dead weights. The ball assembly was oscillated
over a 1000p,
path at a rate of 50 Hertz. After a prescribed period of time, the steel ball
assembly was
removed. Wear, and hence the lubricity of the fuel composition, was assessed
by
measuring the wear scar diameter on the ball resulting from oscillating
contact with the
disk. The lower the value of the wear scar diameter the better the performance
of the
2s additive in the fuel composition. A wear scar diameter of below 500 is
particularly
desirable. The results are set out in the tables below.
Fuel Com osition Total Treat Rate m Wear Scar microns
II
Unleaded asoline 824
basefuel
Unleaded gasoline 200 434
basefuel
+ bis TEPA PIBSI
1000mwt
Unleaded gasoline 200 376
basefuel
+ AEEA PIBSI 1000mwt
Unleaded gasoline 420 321
basefuel
+ AEEA PIBSI (1000mwt)
+ Pol ether

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Fuel Composition Total Treat Rate Active IngredientWear Scar
(mg/l)
Treat Rate microns
m II
Unleaded asoline 0 0 838
basefuel
Unleaded gasoline 200 120 400
basefuel
+ AEEA PIBSI 1000mwt
Unleaded gasoline 156 120 825
basefuel
+ButA PIBamine 1000mwt
Unleaded gasoline 120 120 767
basefuel
+ PIB 1000mwt
The following table shows the results obtained for commercial gasoline
additives and an
example of the present invention in this test. The additives were tested at
equivalent
active treat rates.
5
Fuel com osition Wear Scar microns
Unleaded asoline basefuel 810
Unleaded gasoline basefuel 609
+ commercial Mannich amine
Unleaded gasoline basefuel 699
+ commercial PIBamine 1
Unleaded gasoline basefue 743
+ commercial PIBamine 2
Unleaded gasoline basefuel 674
+ commercial Pol etheramine
Unleaded gasoline basefuel 414
+ AEEA PIBSI
Example 8 - Improved Packagability
Generally friction modifiers such as polyisobutenyl succinimide (PIBSI) and
carrier fluids
l0 are incompatible without the addition of a suitable solvent. Many packages
require
additional solvent above the amount already present due to the manufacture of
the
friction modifier.
A series of packages were produced using a range of carriers and friction
modfiers. The
15 following table shows the total percentage of solvent required to keep a
1:1 ratio of active
friction modifier and can-ier fluid package in one phase at ambient
conditions. The lowest
solvent content possible in this test is 25-26% due to the solvent associated
with the
friction modifier manufacture.

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21
Amine
used
to produce
friction
modifier
AmmoniaButylamineAminoethylethanolamineTetraethylenepentamine
Carrier 26 25 25
A
Carrier 26 25 30
B
Carrier 25 26 25 37
C
Carrier 26 30 40
D
Carrier A is a C,~,S initiated polyether having 12 propylene oxide units
attached
Carrier B is a C,~,S initiated polyether having 14 propylene oxide units
attached
Carrier C is a C,~,5 initiated polyether having 17 propylene oxide units
attached
Carrier D is a nonylphenol initiated polyether having 17 propylene oxide units
attached
Further storage stability testing has been carried out at -10°C,
ambient and +40°C over
5-7days. This showed that the amount of additional solvent required to keep a
package,
to showing similar IVD performance, in one phase could be reduced by up to 60%
by using
the present invention.
Example 9 - Intake valve deterctency
The intake valve detergency properties exhibited by the friction mod~er and
carrier oil
combinations listed below were measured using industry standard- CEC-F-05-A93
test
procedure on a bench engine. The test engine was a Mercedes-Benz M 102.982
four
cylinder, four stroke 2.3 litre gasoline-injection engine with a standard KE-
Jettonic
injection system. The test carried out involved a cyclic procedure, each cycle
including
2o the following four operating states:
Sta Time min S eed min-1 Tor ues Nm Power kW
a
1 0.5 800 t 50 0 2 0
2 1.0 1,300 50 29.4 t 2
3 2.0 1,850150 32. 6.3
5 2
~~ 1.0 I _ _ 11.0
3,000 t 50 35.0 2 ~
I
The duration of each test was exactly 60 h with the cycle repeated 800 times.
At the
beginning of each test the engine was fitted with new inlet valves which were
weighed
before fitting. At the end of each test, and before the visual assessment and
before
weighing the used inlet valves, residues were cleaned carefully from the valve
surface

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22
facing the combustion space. The valves were then immersed in n-heptane for 10
seconds and swung dry. After drying for 10 minutes, the valves were weighed
and the
increase in valve weight caused by deposits was measured in mg. During the
dismantling of the valves the sticky or non-sticky appearance of the deposits
formed on
the valve tulip and valve stem was also evaluated. The tendency to form
deposits of
sticky appearance could indicate, ultimately, a tendency to the appearance of
the valve
stick phenomenon which is desirable to avoid.
The fuel employed in the test procedure was an unleaded gasoline meeting EN228
1o specification. The test compositions were added to the fuel so as to obtain
a
concentration of active substance (friction mod~er and carrier oil) in the
fuel in the
amounts indicated.
Using Carrier D as carrier, at 1:1.6 ratio of friction modifiercarrier
Active Friction Modifier ND
treat
150 m 1000 mwt bis TEPA PIBSIIVD = 82:1 m valve
150 m I 1000 mwt mono Bu amine IVD = 87.6 m alve
PIBSI
Using Carrier A as canier, at 1:1 ratio of friction mod~er:carrier
Active Friction Modifier ND
treat
245 m /I 1000 mwt bis TEPA PIBSI IVD = 82 m /valve
245 m 1000 mwt AEEA PIBSI IVD = 37 m valve
Using Carrier C at 1:1 ratio of friction mod~er:carrier in a fuel of low
sulphur content
Active Friction Modifier IVD
treat
254 m 1000 mwt AEEA PIBSI IVD = 33.2 m
/I valve
350 m 1000 mwt AEEA PIBSI IVD = 15.5 m
/I /valve
Example 10 - Valve stick performance
A series of tests was also carried out to evaluate the actual valve stick
properties of
various formulations. Test running was carried out on a single roll distance
accumulation
dynamometer manufactured by Labeco. The test engine is a regular Volkswagen
Transporter 1.9-liter, 44 kW water-cooled-boxer Otto engine type 2 series with
hydraulic
valve filter. It is a flat four cylinder engine mounted at the rear, with a
three-speed
automatic transmission. The cylinder heads are dismantled after each test (one
test=3
runs on the same fuel) and are cleaned with a suitable cleansing agent until
metallically
clean. The valve guides and valve stems are measured before each test.

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23
The fuel used in these tests is an unleaded gasoline meeting EN228
specification.
The procedure described by DKA (Deutscher Koordinierungs Ausschuess) CEC F-16-
T-
96 was followed. Each cycle included the following operating states:
Drive 130 km at level road load as follows:
5 km at 50 km/h
5 km at 60 km/h
Sto en ine - ause 10 minutes
Cany out a total of 13 times to occupy 4 hours
33 minutes
Switch off engine and soak to temperature for
15h
Cany out three cycles with a soak
tem erature of +5°C
At the end of each engine soak phase, an engine compression test is carried
out to
highlight any valve which is not functioning correctly. If compression at one
or more of
the cylinders is less than 8 bar then the inlet valve is deemed to have been
sticking in the
valve guide. For the final result, with a pass at -18°C, the same cycle
is used except the
soak temperature is -18°C rather than 5°C.
The test compositions are added to the fuel so as to obtain a concentration of
active
substarice in the fuel containing additives which is specked for each example
in the
Table below, which gives the results obtained.
Friction CarrierTotal activeActive Friction Temp.Passlfail
Modifier m II Modifierl
Carrier ratio
1000/b/TEPAD 141 1:1.6 +5C Fail
1000/ButAA 317 1:1.6 +5C Pass
1000/AEEAA 317 1:1.6 +5C Pass
1000/AEEAA 317 1:0.9 -18C Pass
1000/AEEAC 317 1:1 -18C Pass
10001AEEAC 350 1:1 -18C Pass
Example 11 - Intake valve deteraency
The intake valve detergency properties exhibited by the friction mod~er and
carrier oil
combinations listed have been measured using the CEC F-20-A-98 test procedure
on a
bench engine. The test engine is a Mercedes Benz M111 four cylinder, four-
stroke 2.0
litre gasoline-injection engine with four valves per cylinder and an
electronically

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24
controlled ignition and fuel injection system. The test carried out involves a
cyclic
procedure, each cycle including the following four operating states:
Stage Time (min)Speed (min-Torque (Nm)
1
1 0.5 750 t 50 Closed throttle
2 1.0 1500 t 40 t 2
25
3 2.0 2500 t 40 t 2
25
4 1.0 3500 t 40 t 2
25
The duration of each test is 60 hours. At the beginning of each test, the
engine is fitted
with new inlet valves, which are weighed before fitting. At the end of each
test, and
before weighing of the used inlet valves, residues are cleaned carefully from
the valve
surface facing the combustion space. The valves are then immersed in n-heptane
for 10
seconds and air dried for at least 10 minutes and a maximum of 2 hours. Each
valve is
1o then weighed on a precision scale to an accuracy of at least one milligram,
to determine
the total weight of the valve and all its deposits.
The inlet valve deposit weight is determined by subtracting the weight of the
clean intake
valve that was determined before commencement of test and expressed in
mg/valve.
The fuel employed was an unleaded gasoline meeting EN228 specification.
Using Carrier C as carrier, at a 1:1 ratio of friction modifier:carrier:
Active Treat Friction Modifier IVD m Ivalve
m /I
188 1000mwt AEEA PIBSI 106.2
254 1000mwt AEEA PIBSI 63.6
306 1000mwt AEEA PIBSI 27.3
All publications mentioned in the above specification are herein incorporated
by
reference. Various modifications and variations of the described methods and
system of
the invention will be apparent to those skilled in the art without departing
from the scope
and spirit of the invention. Although the invention has been described in
connection with
specific preferred embodiments, it should be understood that the invention as
claimed
should not be unduly limited to such specific embodiments. Indeed, various
modifications of the described modes for canying out the invention which are
obvious to
those skilled in chemistry or related fields are intended to be within the
scope of the
following claims.