U.S. patent application number 13/697565 was filed with the patent office on 2013-06-06 for lubricating composition containing a dispersant.
This patent application is currently assigned to THE LUBRIZOL CORPORATION. The applicant listed for this patent is William Ellyatt, Renee A. Eveland, Matthew D. Gieselman, Joanne L. Jones, Patrick E. Mosier. Invention is credited to William Ellyatt, Renee A. Eveland, Matthew D. Gieselman, Joanne L. Jones, Patrick E. Mosier.
Application Number | 20130143780 13/697565 |
Document ID | / |
Family ID | 44121288 |
Filed Date | 2013-06-06 |
United States Patent
Application |
20130143780 |
Kind Code |
A1 |
Gieselman; Matthew D. ; et
al. |
June 6, 2013 |
Lubricating Composition Containing a Dispersant
Abstract
The invention provides a lubricating composition containing a
compound comprising the reaction product of a polyolefin, an
ethylenically unsaturated aromatic acylating agent (or carboxylic
reactant), and an amine, and an oil of lubricating viscosity. The
invention further relates to the use of the lubricating composition
in an internal combustion engine.
Inventors: |
Gieselman; Matthew D.;
(Wickliffe, OH) ; Jones; Joanne L.; (Nottingham,
GB) ; Eveland; Renee A.; (Concord Township, OH)
; Mosier; Patrick E.; (Bay Village, OH) ; Ellyatt;
William; (Belper, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Gieselman; Matthew D.
Jones; Joanne L.
Eveland; Renee A.
Mosier; Patrick E.
Ellyatt; William |
Wickliffe
Nottingham
Concord Township
Bay Village
Belper |
OH
OH
OH |
US
GB
US
US
GB |
|
|
Assignee: |
THE LUBRIZOL CORPORATION
Wickliffe
OH
|
Family ID: |
44121288 |
Appl. No.: |
13/697565 |
Filed: |
May 17, 2011 |
PCT Filed: |
May 17, 2011 |
PCT NO: |
PCT/US11/36787 |
371 Date: |
January 30, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61346499 |
May 20, 2010 |
|
|
|
Current U.S.
Class: |
508/296 ;
508/510; 508/518; 508/526; 508/549; 508/558; 508/563 |
Current CPC
Class: |
C10N 2030/04 20130101;
C10N 2040/251 20200501; C10M 2223/045 20130101; C10M 2215/28
20130101; C10N 2010/02 20130101; C10M 133/56 20130101; C10N 2040/25
20130101; C10M 163/00 20130101; C10M 2207/262 20130101; C10M 161/00
20130101; C10M 2205/022 20130101; C10M 2219/106 20130101; C10M
2207/028 20130101; C10N 2030/52 20200501; C10M 2215/223 20130101;
C10M 2217/06 20130101; C10N 2040/26 20130101; C10M 2207/023
20130101; C10N 2030/45 20200501; C10M 2215/064 20130101; C10N
2040/255 20200501; C10M 159/12 20130101; C10N 2030/02 20130101;
C10M 133/12 20130101; C10M 2219/046 20130101; C10N 2010/04
20130101; C10M 133/44 20130101; C10N 2030/40 20200501; C10N
2040/252 20200501; C10N 2040/253 20200501; C10M 149/02 20130101;
C10M 159/02 20130101; C10M 2205/022 20130101; C10M 2205/024
20130101; C10M 2209/084 20130101; C10N 2060/09 20200501; C10M
2207/028 20130101; C10N 2010/04 20130101; C10M 2207/028 20130101;
C10N 2010/04 20130101; C10N 2060/10 20130101; C10M 2215/28
20130101; C10M 2215/28 20130101; C10M 2219/046 20130101; C10N
2010/04 20130101; C10M 2223/045 20130101; C10N 2010/04 20130101;
C10M 2207/028 20130101; C10N 2010/04 20130101; C10M 2219/046
20130101; C10N 2010/04 20130101; C10M 2223/045 20130101; C10N
2010/04 20130101; C10M 2207/028 20130101; C10N 2010/04 20130101;
C10N 2060/10 20130101; C10M 2205/022 20130101; C10M 2205/024
20130101; C10M 2209/084 20130101; C10N 2060/09 20200501 |
Class at
Publication: |
508/296 ;
508/558; 508/526; 508/510; 508/518; 508/563; 508/549 |
International
Class: |
C10M 133/12 20060101
C10M133/12 |
Claims
1.-20. (canceled)
21. A lubricating composition comprising an oil of lubricating
viscosity and 0.1 wt % to 15 wt % of a compound comprising the
reaction product of a polyolefin, an ethylenically unsaturated
aromatic acylating agent, and an amine, wherein the amine is an
acyclic polyamine, wherein the polyolefin is a polybutene, and
wherein the lubricating composition has a sulphated ash content of
0.3 wt % to 1.2 wt % of the lubricating composition.
22. The lubricating composition of claim 21, wherein the amine is
an ethylenepolyamine.
23. The lubricating composition of claim 22, wherein the
ethylenepolyamine is selected from the group consisting of
ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, polyamine still
bottoms, and mixtures thereof.
24. The lubricating composition of claim 21, wherein the polyolefin
is derivable from an olefin with 2 to 4 carbon atoms.
25. The lubricating composition of claim 21, wherein the polyolefin
is a polyisobutylene.
26. The lubricating composition of claim 21, wherein the polyolefin
is a copolymer, wherein the polyolefin is a butene and isoprene
copolymer, or an ethylene-.alpha.-olefin copolymer.
27. The lubricating composition of claim 26, wherein the
ethylene-.alpha.-olefin copolymer is an ethylene-propylene
copolymer.
28. The lubricating composition of claim 21, wherein the
ethylenically unsaturated aromatic acylating agent is cis-cinnamic
acid, trans-cinnamic acid, or mixtures thereof.
29. The lubricating composition of claim 21, wherein the compound
is obtained by a process comprising: (1) reacting the polyolefin
with the ethylenically unsaturated aromatic acylating agent; and
(2) reacting the product of step (1) with the amine.
30. The lubricating composition of claim 21, wherein the compound
is non-borated.
31. The lubricating composition of claim 21, wherein the compound
is present at 2 wt % to 12 wt %, of the lubricating
composition.
32. The lubricating composition of claim 21, wherein the
lubricating composition has a sulphated ash content of 0.5 wt % to
1.1 wt % of the lubricating composition.
33. The lubricating composition of claim 21 further comprising an
overbased metal-containing detergent, wherein the overbased
metal-containing detergent is selected from the group consisting of
non-sulphur containing phenates, sulphur containing phenates,
sulphonates, salixarates, salicylates, and mixtures thereof.
34. A method of lubricating an internal combustion engine
comprising supplying to the internal combustion engine a
lubricating composition comprising the lubricating composition of
claim 21.
35. A lubricating composition comprising an oil of lubricating
viscosity and 0.1 wt % to 15 wt % of a compound comprising the
reaction product of a polyolefin, an ethylenically unsaturated
aromatic acylating agent (or carboxylic reactant), and an amine,
wherein the aromatic amine is selected from the group consisting of
aniline, nitroaniline, aminocarbazole, 4-aminodiphenylamine (ADPA),
and coupling products of ADPA.
36. The lubricating composition of claim 35, wherein the aromatic
amine is 4-aminodiphenylamine or coupling products of
4-aminodiphenylamine.
37. The lubricating composition of claim 34, wherein the polyolefin
is a polyisobutylene.
38. The lubricating composition of claim 34, wherein the polyolefin
is a copolymer, wherein the polyolefin is a butene and isoprene
copolymer, or an ethylene-.alpha.-olefin copolymer.
39. The lubricating composition of claim 34, wherein the
lubricating composition has a sulphated ash content of 0.5 wt % to
1.1 wt % of the lubricating composition.
40. A method of lubricating an internal combustion engine
comprising supplying to the internal combustion engine a
lubricating composition comprising the lubricating composition of
claim 34.
Description
FIELD OF INVENTION
[0001] The invention provides a lubricating composition containing
a dispersant and an oil of lubricating viscosity. The invention
further relates to the use of the lubricating composition in an
internal combustion engine.
BACKGROUND OF THE INVENTION
[0002] Engine manufacturers have focused on improving engine design
in order to minimise emissions of particulates and pollutants, and
improve cleanliness and fuel economy. One of the improvements in
engine design is the use of exhaust gas recirculation (EGR)
engines. Heavy duty diesel vehicles may use exhaust gas
recirculation (EGR) engines in efforts to reduce environmental
emissions. Whilst improvements in engine design and operation have
contributed to reducing emissions, some engine design advances are
believed to have generated other challenges for the lubricant. For
example, EGR is believed to have led to increased formation and/or
accumulation of soot and sludge. Among the consequences of
recirculating the exhaust gas through the engine are different soot
structures and increased viscosity of the oil at lower soot levels,
compared with engines without EGR.
[0003] Increased soot-mediated oil thickening is common in heavy
duty diesel engines. Some diesel engines employ EGR. The soot
formed in an EGR engine has different structures and causes
increased viscosity of engine lubricant at lower soot levels than
formation of soot in the engine without an EGR.
[0004] Viscosity improvers are often used to reduce the extent of
the decrease in viscosity as the temperature is raised or to reduce
the extent of the increase in viscosity as the temperature is
lowered, or both. Thus, a viscosity improver ameliorates the change
of viscosity of an oil containing it with changes in
temperature.
[0005] Dispersant viscosity modifiers (DVMs) made from
ethylene-propylene copolymers that have been radically grafted with
maleic anhydride and reacted with various amines have shown
desirable performance to prevent oil thickening in diesel engines.
Aromatic amines are said to show good performance in this regard.
DVMs of this type are disclosed in, for instance, U.S. Pat. Nos.
4,863,623, 5,264,139, 5,264,140, 5,620,486, 6,107,257, 6,107,258,
and 6,117,825.
[0006] U.S. Pat. No. 5,409,623 discloses functionalized graft
copolymers as viscosity index improvers, comprising an ethylene
alpha-monoolefin copolymer grafted with an ethylenically
unsaturated carboxylic acid material and derivatized with an
azo-containing aromatic amine compound.
[0007] U.S. Pat. Nos. 5,264,139 and 5,264,140 disclose polymers
derivatized with a sulphonyl-containing aromatic amine and an
amide-containing aromatic amine material respectively.
[0008] Other dispersant viscosity modifiers have been contemplated
in a variety of applications including U.S. patent application Ser.
Nos. 11/568,051, and 61/118,012; and International Application WO
publication WO 2010/014655 A1.
[0009] U.S. patent application Ser. No. 11/568,051 discloses soot
dispersants derived from esterified maleic anhydride-styrene
interpolymers functionalized with nitrogen-containing moieties.
[0010] International Application WO publication WO2010014655 A1
discloses alpha olefin maleic anhydride (AOMA) interpolymers which
may be esterified and further functionalized with amines having at
least one condensable N--H group.
[0011] U.S. application 61/118,012 (also relating to International
Patent Application WO2010/062842) discloses olefin polymers
functionalized by grafting with an unsaturated carboxylic acid
material and derivatized with aromatic amines having three or more
non-contiguous aromatic groups.
[0012] Other publications disclose the possibility of dispersants
with aromatic groups.
[0013] U.S. Pat. No. 5,182,041 discloses polyolefin based
dispersants functionalized with an ethylenically unsaturated
acylating agent and reacted with an amino-aromatic polyamine to
produce antioxidant dispersants.
[0014] U.S. Pat. No. 6,051,537 discloses hydrocarbyl dispersants
made from polyolefins functionalized with monounsaturated mono acid
materials selected from acrylic acid, methacrylic acid and cinnamic
acid reacted with amines, alcohols and/or aminoalcohols. These
polyolefins have number average molecular weight in the range 1500
to 5000.
SUMMARY OF THE INVENTION
[0015] An objective of the present invention is to provide a
lubricating composition capable of providing at least one of (i) a
lubricating composition capable of reducing viscosity increase
(often having a viscosity of less than 12 mm.sup.2/sec (cSt) at
100.degree. C. at a soot loading of 6 weight % or more), and/or
(ii) a lubricating oil composition that maintains a relatively
stable viscosity over a wide range of temperatures. This could be
desirable because viscosity index improvers or DVMs may be employed
to control viscosity over a wide temperature range and to control
soot. It may also be desirable if a viscosity index improver were
capable of achieving (i) and (ii).
[0016] Unless otherwise indicated, each chemical or composition
referred to herein should be interpreted as being a commercial
grade material which may contain the isomers, by-products,
derivatives, and other such materials which are normally understood
to be present in the commercial grade. However, the amount of each
chemical component is presented exclusive of any solvent or diluent
oil, which may be customarily present in the commercial material,
unless otherwise indicated.
[0017] In one embodiment the present invention provides a
lubricating composition comprising an oil of lubricating viscosity
and a compound comprising the reaction product of a polyolefin, an
ethylenically unsaturated aromatic acylating agent (or carboxylic
reactant), and an amine.
[0018] In one embodiment the present invention provides a
lubricating composition comprising an oil of lubricating viscosity
and a compound comprising the reaction product of a polyolefin, an
ethylenically unsaturated aromatic acylating agent (or carboxylic
reactant), and an aromatic amine (typically wherein the aromatic
amine is not a heterocycle).
[0019] In one embodiment the present invention provides a
lubricating composition comprising (i) an oil of lubricating
viscosity, (ii) a compound comprising the reaction product of a
polyolefin, an ethylenically unsaturated aromatic acylating agent
(or carboxylic reactant), and an amine, and (iii) an overbased
metal-containing detergent.
[0020] In one embodiment the lubricating composition disclosed
herein has a sulphated ash content of 0.3 wt % to 1.2 wt %, or 0.5
wt % to 1.1 wt % of the lubricating composition. The sulphated ash
content may be determined by ASTM D-874.
[0021] The compound disclosed herein may be borated, or
non-borated, typically non-borated.
[0022] In one embodiment the invention provides a lubricating
composition wherein the compound disclosed herein may be present at
0.1 wt % to 15 wt %, or 1 wt % to 14 wt %, or 2 wt % to 12 wt %, or
4 wt % to 9 wt % of the lubricating composition. Typically the
compound is present at an actives level of about 50 wt % of the
ranges quoted. In other words, on an actives basis the compound may
be present at 0.05 to 7.5 wt %, or 0.5 wt % to 7 wt %, or 1 wt % to
6 wt %, or 2 wt % to 4.5 wt % of the lubricating composition.
[0023] In one embodiment the invention provides a lubricating
composition comprising the compound disclosed herein and an
alkylated diarylamine (such as an alkylated diphenylamine, or an
alkylated phenylnapthylamine). The alkylated diphenylamine may
include di-nonylated diphenyl amine, nonyl diphenyl amine, octyl
diphenylamine, di-octylated diphenylamine, di-decylated
diphenylamine, decyl diphenylamine and mixtures thereof. In one
embodiment the diphenylamine may include nonyl, diphenylamine,
dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine,
or mixtures thereof. In one embodiment the diphenylamine may
include nonyl, diphenylamine, or dinonyl diphenylamine. The
alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl,
decyl or di-decyl phenylnapthylamines.
[0024] When present, the alkylated diarylamine may be present at
0.01 wt % to 5 wt %, or 0.05 wt % to 3 wt %, or 0.1 wt % to 1 wt %
of the lubricating composition.
[0025] In one embodiment the invention provides a lubricating
composition wherein the compound as disclosed herein may be present
at 2 wt % to 12 wt % (or typically 4 wt % to 9 wt %) and the
alkylated diphenylamine may be present at 0.05 wt % to 3 wt % (or
typically 0.1 wt % to 1 wt %) of the lubricating composition.
[0026] In one embodiment the invention provides a method of
lubricating an internal combustion engine comprising supplying to
the internal combustion engine a lubricating composition as
disclosed herein.
[0027] In one embodiment the invention provides for the use of the
compound described herein in a lubricant as a dispersant or
dispersant viscosity modifier.
[0028] In one embodiment the invention provides for the use of the
compound disclosed herein in a lubricant as a dispersant or
dispersant viscosity modifier in an internal combustion engine
lubricant. Typically the dispersant or dispersant viscosity
modifier is useful to mitigate soot thickening in an engine
lubricant.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The present invention provides a lubricating composition, a
method for lubricating an engine as disclosed above, and a use of
the compound as disclosed above.
Polyolefin
[0030] The polyolefin may be a homopolymer or a copolymer. The
polyolefin may be derivable (or derived) from an olefin with 2 to
20, or 2 to 10, or 2 to 4 carbon atoms. The polyolefin is known in
the state of the art.
[0031] In one embodiment, the polyolefin may be a polybutene,
typically a polyisobutylene. Typically the polyisobutylene has a
number average molecular weight of 350 to 5000, or 550 to 3000 or
750 to 2500. Typically, when the reaction product of the invention
is a homopolymer (such as polybutene) the homopolymer may be part
of a dispersant.
[0032] When in the form of a copolymer, the polyolefin may be a
copolymer of butene and isoprene, or an ethylene-.alpha.-olefin
copolymer. In one embodiment the polyolefin may be a copolymer of
an ethylene and propylene copolymer. Typically, when the reaction
product of the invention is a copolymer the copolymer may be a
dispersant viscosity modifier.
[0033] The number average molecular weight of a copolymer derivable
from a butene and isoprene copolymer, or an ethylene-.alpha.-olefin
copolymer may be 500 to 200,000, 5000 to 200,000, 5,000 to 100,000,
or 5,000 to 75,000.
Ethylenically Unsaturated Aromatic Acylating Agent (or Carboxylic
Reactant)
[0034] The ethylenically unsaturated aromatic acylating agent (or
carboxylic reactant) may include cis-cinnamic acid, trans-cinnamic
acid, phenylpropiolic acid, phenyl maleic anhydride, or mixtures
thereof, or derivatives thereof (such esters, partial esters,
amides, or partial amides (typically esters, or partial esters)).
In one embodiment the ethylenically unsaturated aromatic acylating
agent (or carboxylic reactant) may include cis-cinnamic acid,
trans-cinnamic acid, phenylpropiolic acid, or mixtures thereof. In
one embodiment the ethylenically unsaturated aromatic acylating
agent (or carboxylic reactant) may include trans-cinnamic acid, or
mixtures of cis and trans cinnamic acid.
[0035] In one embodiment the ethylenically unsaturated acylating
agent may also include a derivative of cinnamic acid that may be
represented by the formula:
##STR00001##
wherein
X may be --O--, >NR'',
[0036] R' and R'' may independently be hydrogen or a hydrocarbyl
group (typically containing 1 to 50, or 1 to 20 carbon atoms, and R
may independently be hydrogen, --OH, --OR, NR'R'', or hydrocarbyl,
and any two R groups together with other atoms may form 5 or 6
membered rings that may be saturated or unsaturated.
[0037] Examples of a derivative of cinnamic acid include
3,4-(methylenedioxy)cinnamic acid, 3,4,5-trimethoxy-trans-cinnamic
acid, 4-(dimethylamine)cinnamic acid, sinapic acid,
2-hydroxycinnamic acid, 3,4-dimethoxycinnamic acid,
3-hydroxy-4-methoxycinnamic acid, 4-methoxycinnamic acid,
.alpha.-methylcinnamic acid, caffeic acid, coumarin,
trans-3-hydroxycinnamic acid, 4-hydroxy-3-phenyl-2(5H)-furanone,
(E)-3-(naphthalene-2-yl)acrylic acid,
trans-3-(4-methoxybenzoyl)acrylic acid, 3-indoleacrylic acid,
2,3-diphenyl-acrylic acid, or 3-(1-naphthyl)acrylic acid.
Amine
[0038] The amine may be a monoamine or a polyamine. The amine may
be a linear or branched, cyclic or acyclic amine, or combinations
thereof. When the amine is cyclic, the amine may be either an
aromatic amine or a non-aromatic amine.
[0039] In one embodiment the amine may be acyclic, typically an
acyclic polyamine. The polyamine may be an aliphatic polyamine such
as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine,
or mixtures thereof. In one embodiment the polyamine may be an
ethylenepolyamine. In one embodiment the aliphatic polyamine may be
selected from the group consisting of ethylenediamine,
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyamine still bottoms, and mixtures
thereof.
[0040] In one embodiment the amine may be an aromatic amine
(typically wherein the aromatic amine is not a heterocycle). The
aromatic amine includes aniline, nitroaniline, aminocarbazole,
4-aminodiphenylamine (ADPA), and coupling products (also referred
to as coupled products) of ADPA. In one embodiment the amine may be
4-aminodiphenylamine (ADPA), or coupling products of ADPA.
[0041] Counted products of ADPA may be represented by the formula
(1):
##STR00002##
wherein independently each variable, R.sup.1 may be hydrogen or a
C.sub.1-5 alkyl group (typically hydrogen); R.sup.2 may be hydrogen
or a C.sub.1-5 alkyl group (typically hydrogen); U may be an
aliphatic, alicyclic or aromatic group, with the proviso that when
U is aliphatic, the aliphatic group may be linear or branched
alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w may
be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).
[0042] In one embodiment the coupled ADPA of Formula (1) may be
represented by Formula (1a):
##STR00003##
wherein independently each variable, R.sup.1 may be hydrogen or a
C.sub.1-5 alkyl group (typically hydrogen); R.sup.2 may be hydrogen
or a C.sub.1-5 alkyl group (typically hydrogen); U may be an
aliphatic, alicyclic or aromatic group, with the proviso that when
U is aliphatic, the aliphatic group may be linear or branched
alkylene group containing 1 to 5, or 1 to 2 carbon atoms; and w may
be 1 to 10, or 1 to 4, or Ito 2 (typically 1).
[0043] Alternatively, the compound of Formula (1a) may also be
represented by:
##STR00004##
wherein each variable U, R.sup.1, and R.sup.2 are the same as
described above and w is 0 to 9 or 0 to 3 or 0 to 1 (typically
0).
[0044] In one embodiment the aromatic amine may have at least 3 or
aromatic groups. Examples of an amine having at least 3 aromatic
groups may be represented by any of the following Formulae (2)
and/or (3):
##STR00005##
[0045] A coupled aromatic amine can be made by the reaction of an
aromatic amine with an aldehyde (such as formaldehyde). A person
skilled in the art will appreciate that compounds of Formulae (2)
and (3) may also react with the aldehyde described below to form
acridine derivatives. Acridine derivatives that may be formed
include compounds represented by Formula (2a) or (3a) below. In
addition to these compounds representing these formulae, a person
skilled in the art will also appreciate that other acridine
structures may be possible where the aldehyde reacts with other
benzyl groups bridged with the >NH group.
[0046] Examples of acridine structures include those represented by
Formulae (2a) and (3a):
##STR00006##
[0047] Any or all of the N-bridged aromatic rings are capable of
such further condensation and perhaps aromatisation. One other of
many possible structures is shown in Formula (3b).
##STR00007##
[0048] Examples of the coupled ADPA include
bis[p-(p-aminoanilino)phenyl]-methane,
2-(7-amino-acridin-2-ylmethyl)-N-4-{4-[4-(4-amino-phenylamino)-benzyl]-ph-
enyl}-benzene-1,4-diamine,
N.sup.4-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-2-[4-(4-amino-phenyla-
mino)-cyclohexa-1,5-dienylmethyl]-benzene-1,4-diamine,
N-[4-(7-amino-acridin-2-ylmethyl)-phenyl]-benzene-1,4-diamine, or
mixtures thereof.
[0049] The coupled ADPA may be prepared by a process comprising
reacting the aromatic amine with an aldehyde. The aldehyde may be
aliphatic, alicyclic or aromatic. The aliphatic aldehyde may be
linear or branched. Examples of a suitable aromatic aldehyde
include benzaldehyde or o-vanillin. Examples of an aliphatic
aldehyde include formaldehyde (or a reactive equivalent thereof
such as formalin or paraformaldehyde), ethanal or propanal.
Typically the aldehyde may be formaldehyde or benzaldehyde.
[0050] The process may be carried out at a reaction temperature in
the range of 40.degree. C. to 180.degree. C., or 50.degree. C. to
170.degree. C.
[0051] The reaction may or may not be carried out in the presence
of a solvent. Examples of a suitable solvent include diluent oil,
benzene, t-butyl benzene, toluene, xylene, chlorobenzene, hexane,
tetrahydrofuran, water, or mixtures thereof.
[0052] The reaction may be performed in either air or an inert
atmosphere. Examples of suitable inert atmosphere include nitrogen
or argon, typically nitrogen.
[0053] Alternatively, the coupled ADPA may also be prepared by the
methodology described in Berichte der Deutschen Chemischen
Gesellschaft (1910), 43, 728-39.
[0054] The compound of the invention may be obtained/obtainable by
a process comprising: [0055] Step (1) reacting a polyolefin
(typically a polybutene such as polyisobutylene) with an
ethylenically unsaturated aromatic acylating agent (or carboxylic
reactant); and [0056] Step (2) reacting the product of step (1)
with an amine.
[0057] The polybutene may be reacted with chlorine to provide a
substance capable of undergoing a Diels-Alder reaction with the
ethylenically unsaturated acylating agent. Alternatively, the
polybutene and/or the ethylene alpha olefin may be reacted with the
ethylenically unsaturated acylating agent in the presence of a
radical initiator.
[0058] The mole ratio of polyolefin to ethylenically unsaturated
aromatic acylating agent (or carboxylic reactant) may range from
5:1 to 1:5, or 3:1 to 1:3, or 2:1 to 1:2, or 1:1. When the mole
ratio is about 1:1 the product of step (1) is typically
mono-substituted.
[0059] Step (2) of the process reacts an amine with the product of
step (1) by processes known to a person skilled in the art. The
mole ratio of the amine to the product of step (1) may vary from
0.3:1 or 0.5:1 or 1:1 or 2:1, to 3:1 or to 2:1, e.g., 0.5:1 to 2:1.
In certain embodiments, the relative amounts may be expressed in
terms of the ratio of nitrogen atoms to carbonyl groups, and
typical N:CO ratios may include 0.5:1 to 5:1. Typically the product
of step (2) is in the form an amide.
[0060] When the polyolefin is a polyisobutylene, the ethylenically
unsaturated acylating agent is trans-cinnamic acid, and any amine
disclosed herein are reacted, the product formed may be represented
by formulae:
##STR00008##
wherein w may be 1 to 5, or 1 to 3 (depending on the mole ratio of
the product of the amine to the product of step (1) or step (i)); Q
may be the residue of polybutene; Ph may be phenyl group derivable
from trans-cinnamic acid; and Am may be the residue of the amine
reacted.
[0061] The compound of the invention may be obtained/obtainable by
a process comprising (i) reacting a polyolefin copolymer (typically
an ethylene-.alpha.-olefin copolymer) with an ethylenically
unsaturated aromatic acylating agent (or carboxylic reactant); and
(ii) reacting the product of (i) with an amine.
[0062] The ethylenically unsaturated aromatic acylating agent (or
carboxylic reactant) may be grafted onto the polyolefin copolymer
(typically an ethylene/propylene copolymer) in a number of ways. It
may be grafted onto the polymer in solution or in molten form using
a radical initiator. The free-radical induced grafting of
ethylenically unsaturated carboxylic acid materials may also be
conducted in solvents, such as hexane or mineral oil. It may be
carried out at an elevated temperature in the range of 100.degree.
C. to 250.degree. such as 120.degree. C. to 190.degree. C. or
150.degree. C. to 180.degree. C. If grafting is conducted in a
solvent such as a mineral lubricating oil solution, the solution
may contain 1 wt % to 50 wt %, or 5 wt % to 30 wt % based on the
initial total oil solution, of the polyolefin copolymer, typically
under an inert environment.
[0063] The free-radical initiators which may be used include
peroxides, hydroperoxides, and azo compounds, typically those which
have a boiling point greater than about 100.degree. C. and which
decompose thermally within the grafting temperature range to
provide free radicals. Representative of these free-radical
initiators include azobisisobutyronitrile and
2,5-dimethyl-hex-3-yne-2,5-bis-tertiary-butyl peroxide. The
initiator is typically used in an amount of 0.005 wt % to 1 wt %
based on the weight of the reaction mixture solution. The grafting
is typically carried out in an inert atmosphere, such as under
nitrogen blanketing. The resulting polymer intermediate is
characterized by having the aromatic acylating functions within its
structure.
[0064] In a melt process for forming a graft polymer, the
ethylenically unsaturated aromatic acylating agent (or carboxylic
reactant), with the optional use of a radical initiator, is grafted
onto molten rubber using rubber masticating or shearing equipment.
The temperature of the molten material in this process may be
70.degree. C. to 250.degree. C. Optionally, as a part of this
process or separate from this process, mechanical shear and
elevated temperatures can be used to reduce the molecular weight of
the copolymer to a value that will eventually provide the desired
level of shear stability for the lubricant application. In one
embodiment, such mastication can be done in a twin screw extruder
properly configured to provide high shear zones, capable of
breaking down the polymer to the desired molecular weight. Shear
degradation can be done before or after grafting with the maleic
anhydride. It can be done in the absence or presence of oxygen. The
shearing and grafting steps can be done in the same extruder or in
separate extruders, in any order.
[0065] In an alternative embodiment, the ethylenically unsaturated
aromatic acylating agent (or carboxylic reactant), may be first
condensed with an amine (as described herein) and the condensation
product itself then grafted onto the polymer backbone in analogous
fashion to that described above.
[0066] The amount of the ethylenically unsaturated aromatic
acylating agent (or carboxylic reactant) on the polymer chain, and
in particular the amount of grafted carboxylic acid on the chain is
typically 1 wt % to 5 wt % based on the weight of the polyolefin
backbone, and in an alternative embodiments 1.5 wt % to 4 wt 5, or
1.5 wt % to 3.5 wt %. These numbers represent the amount of
ethylenically unsaturated aromatic acylating agent (or carboxylic
reactant) monomer and may be adjusted to account for acid monomers
having higher or lower molecular weights or greater or lesser
amounts of acid functionality per molecule, as will be apparent to
the person skilled in the art.
[0067] The product of step (i) may then be functionalised by the
amine in step (2). This reaction step is similar to that described
above for polybutene.
[0068] The product of step (ii) may in some instances be a
dispersant viscosity modifier (DVM).
Oils of Lubricating Viscosity
[0069] The lubricating composition comprises an oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil
derived from hydrocracking, hydrogenation, and hydrofinishing,
unrefined, refined, re-refined oils or mixtures thereof. A more
detailed description of unrefined, refined and re-refined oils is
provided in International Publication WO2008/147704, paragraphs
[0054] to [0056] and in the corresponding paragraphs of
US-2010-0197536. A more detailed description of natural and
synthetic lubricating oils is described in paragraphs [0058] to
[0059] respectively of WO2008/147704. Synthetic oils may also be
produced by Fischer-Tropsch reactions and typically may be
hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one
embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid
synthetic procedure as well as other gas-to-liquid oils.
[0070] Oils of lubricating viscosity may also be defined as
specified in April 2008 version of "Appendix E--API Base Oil
Interchangeability Guidelines for Passenger Car Motor Oils and
Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock
Categories". In one embodiment the oil of lubricating viscosity may
be an API Group II or Group III oil.
[0071] The amount of the oil of lubricating viscosity present is
typically the balance remaining after subtracting from 100 wt % the
sum of the amount of the compound of the invention and the other
performance additives.
[0072] The lubricating composition may be in the form of a
concentrate and/or a fully formulated lubricant. If the lubricating
composition of the invention (comprising the additives disclosed
herein) is in the form of a concentrate which may be combined with
additional oil to form, in whole or in part, a finished lubricant),
the ratio of the of these additives to the oil of lubricating
viscosity and/or to diluent oil include the ranges of 1:99 to 99:1
by weight, or 80:20 to 10:90 by weight.
[0073] A lubricating composition may be prepared by adding the
product of the process described herein to an oil of lubricating
viscosity, optionally in the presence of other performance
additives (as described herein below).
Other Performance Additives
[0074] The composition optionally comprises other performance
additives. The other performance additives include at least one of
metal deactivators, viscosity modifiers, detergents, friction
modifiers, antiwear agents, corrosion inhibitors, dispersants
(other than the compound of the invention), dispersant viscosity
modifiers (other than the compound of the invention), extreme
pressure agents, antioxidants, foam inhibitors, demulsifiers, pour
point depressants, seal swelling agents and mixtures thereof.
Typically, fully-formulated lubricating oil will contain one or
more of these performance additives.
[0075] In one embodiment the lubricating composition further
includes other additives. In one embodiment the invention provides
a lubricating composition further comprising at least one of a
dispersant (other than the compound of the invention), an antiwear
agent, a dispersant viscosity modifier (other than the compound of
the invention), a friction modifier, a viscosity modifier, an
antioxidant, an overbased detergent, or mixtures thereof. In one
embodiment the invention provides a lubricating composition further
comprising at least one of a polyisobutylene succinimide
dispersant, an antiwear agent, a dispersant viscosity modifier, a
friction modifier, a viscosity modifier (typically an olefin
copolymer such as an ethylene-propylene copolymer), an antioxidant
(including phenolic and aminic antioxidants), an overbased
detergent (including overbased sulphonates and phenates), or
mixtures thereof.
[0076] The dispersant may be a succinimide dispersant, or mixtures
thereof. In one embodiment the dispersant may be present as a
single dispersant. In one embodiment the dispersant may be present
as a mixture of two or three different dispersants, wherein at
least one may be a succinimide dispersant.
[0077] The succinimide dispersant may be derived from an aliphatic
polyamine, or mixtures thereof. The aliphatic polyamine may be
aliphatic polyamine such as an ethylenepolyamine, a
propylenepolyamine, a butylenepolyamine, or mixtures thereof. In
one embodiment the aliphatic polyamine may be ethylenepolyamine. In
one embodiment the aliphatic polyamine may be selected from the
group consisting of ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
pentaethylenehexamine, polyamine still bottoms, and mixtures
thereof.
[0078] The dispersant may be an N-substituted long chain alkenyl
succinimide. An example of an N-substituted long chain alkenyl
succinimide is polyisobutylene succinimide. Typically the
polyisobutylene from which polyisobutylene succinic anhydride is
derived has a number average molecular weight of 350 to 5000, or
550 to 3000 or 750 to 2500. Succinimide dispersants and their
preparation are disclosed, for instance in U.S. Pat. Nos.
3,172,892, 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022,
3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743,
3,632,511, 4,234,435, Re 26,433, and 6,165,235, 7,238,650 and EP
Patent Application 0 355 895 A.
[0079] The dispersant may also be post-treated by conventional
methods by a reaction with any of a variety of agents. Among these
are boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon
disulphide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, maleic anhydride,
nitriles, epoxides, and phosphorus compounds.
[0080] The dispersant may be present at 0.01 wt % to 20 wt %, or
0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %,
or 1 to 3 wt % of the lubricating composition.
[0081] In one embodiment the lubricating composition of the
invention further comprises a dispersant viscosity modifier. The
dispersant viscosity modifier may be present at 0 wt % to 5 wt %,
or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt %, or 0.2 wt % to 1.2 wt
% of the lubricating composition.
[0082] The dispersant viscosity modifier may include functionalised
polyolefins, for example, ethylene-propylene copolymers that have
been functionalized with an acylating agent such as maleic
anhydride and an amine; polymethacrylates functionalised with an
amine, or styrene-maleic anhydride copolymers reacted with an
amine. More detailed descriptions of dispersant viscosity modifiers
are disclosed in International Publication WO2006/015130 or U.S.
Pat. Nos. 4,863,623; 6,107,257; 6,107,258; and 6,117,825. In one
embodiment the dispersant viscosity modifier may include those
described in U.S. Pat. No. 4,863,623 (see column 2, line 15 to
column 3, line 52) or in International Publication WO2006/015130
(see page 2, paragraph [0008], and preparative examples are
described paragraphs [0065] to [0073]).
[0083] In one embodiment the invention provides a lubricating
composition which further includes a phosphorus-containing antiwear
agent. Typically the phosphorus-containing antiwear agent may be a
zinc dialkyldithiophosphate, a phosphite, phosphate, phosphonate,
ammonium phosphate salt, or mixtures thereof. Zinc
dialkyldithiophosphates are known in the art. The antiwear agent
may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5
wt % to 0.9 wt % of the lubricating composition.
[0084] In one embodiment the invention provides a lubricating
composition further comprising a molybdenum compound. The
molybdenum compound may be selected from the group consisting of
molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates,
amine salts of molybdenum compounds, and mixtures thereof. The
molybdenum compound may provide the lubricating composition with 0
to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm,
or 20 ppm to 250 ppm of molybdenum.
[0085] In one embodiment the invention provides a lubricating
composition further comprising an overbased metal-containing
detergent. The metal of the metal-containing detergent may be zinc,
sodium, calcium or magnesium.
[0086] The overbased metal-containing detergent may be selected
from the group consisting of non-sulphur containing phenates,
sulphur containing phenates, sulphonates, salixarates, salicylates,
and mixtures thereof.
[0087] The overbased metal-containing detergent may also include
"hybrid" detergents formed with mixed surfactant systems including
phenate and/or sulphonate components, e.g. phenate/salicylates,
sulphonate/phenates, sulphonate/salicylates,
sulphonates/phenates/salicylates, as described; for example, in
U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179.
Where, for example, a hybrid sulphonate/phenate detergent is
employed, the hybrid detergent would be considered equivalent to
amounts of distinct phenate and sulphonate detergents introducing
like amounts of phenate and sulphonate soaps, respectively.
[0088] Typically an overbased metal-containing detergent may be a
zinc, sodium, calcium or magnesium salt of a phenate, sulphur
containing phenate, sulphonate, salixarate or salicylate. Overbased
salixarates, phenates and salicylates typically have a total base
number of 180 to 450 TBN. Overbased sulphonates typically have a
total base number of 250 to 600, or 300 to 500. Overbased
detergents are known in the art. In one embodiment the sulphonate
detergent may be a predominantly linear alkylbenzene sulphonate
detergent having a metal ratio of at least 8 as is described in
paragraphs [0026] to [0037] of US Patent Application 2005065045
(and granted as U.S. Pat. No. 7,407,919). The predominantly linear
alkylbenzene sulphonate detergent may be particularly useful for
assisting in improving fuel economy.
[0089] Typically the overbased metal-containing detergent may be a
calcium or magnesium overbased detergent.
[0090] Overbased detergents are known in the art. Overbased
materials, otherwise referred to as overbased or superbased salts,
are generally single phase, homogeneous Newtonian systems
characterized by a metal content in excess of that which would be
present for neutralization according to the stoichiometry of the
metal and the particular acidic organic compound reacted with the
metal. The overbased materials are prepared by reacting an acidic
material (typically an inorganic acid or lower carboxylic acid,
preferably carbon dioxide) with a mixture comprising an acidic
organic compound, a reaction medium comprising at least one inert,
organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for
said acidic organic material, a stoichiometric excess of a metal
base, and a promoter such as a phenol or alcohol. The acidic
organic material will normally have a sufficient number of carbon
atoms to provide a degree of solubility in oil. The amount of
excess metal is commonly expressed in terms of metal ratio. The
term "metal ratio" is the ratio of the total equivalents of the
metal to the equivalents of the acidic organic compound. A neutral
metal salt has a metal ratio of one. A salt having 4.5 times as
much metal as present in a normal salt will have metal excess of
3.5 equivalents, or a ratio of 4.5. The term metal ratio is also
explained in standard textbook entitled "Chemistry and Technology
of Lubricants", Second Edition, Edited by R. M. Mortier and S. T.
Orszulik, Copyright 1997. In one embodiment, the lubricant
composition comprises at least one overbased detergent with a metal
ratio of at least 3, or at least 8, or at least 15.
[0091] The overbased detergent may be present at 0 wt % to 15 wt %,
or 0.1 wt % to 10 wt %, or 0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt
%. For example, in a heavy duty diesel engine the detergent may be
present at 2 wt % to 3 wt % of the lubricating composition.
Similarly, for example, in a passenger car engine the detergent may
be present at 0.2 wt % to 1 wt % of the lubricating
composition.
[0092] In one embodiment the lubricating composition includes an
antioxidant, or mixtures thereof. The antioxidant may be present at
0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt %,
or 0.5 wt % to 3 wt % of the lubricating composition.
[0093] Antioxidants include sulphurised olefins, alkylated
diphenylamines (as described previously), hindered phenols,
molybdenum compounds (such as molybdenum dithiocarbamates), or
mixtures thereof.
[0094] The hindered phenol antioxidant often contains a secondary
butyl and/or a tertiary butyl group as a sterically hindering
group. The phenol group may be further substituted with a
hydrocarbyl group (typically linear or branched alkyl) and/or a
bridging group linking to a second aromatic group. Examples of
suitable hindered phenol antioxidants include
2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,
4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol
or 4-butyl-2,6-di-tert-butylphenol, or
4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered
phenol antioxidant may be an ester and may include, e.g.,
Irganox.TM. L-135 from Ciba. A more detailed description of
suitable ester-containing hindered phenol antioxidant chemistry is
found in U.S. Pat. No. 6,559,105.
[0095] In one embodiment the friction modifier may be selected from
the group consisting of long chain fatty acid derivatives of
amines, long chain fatty esters, or derivatives of a long chain
fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric
acids; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty
alkyl tartramides. The friction modifier may be present at 0 wt %
to 6 wt %, or 0.05 wt % to 4 wt %, or 0.1 wt % to 2 wt % of the
lubricating composition.
[0096] As used herein the term "fatty" or "fatty alkyl" means a
carbon chain having 10 to 22 carbon atoms, typically a straight
carbon chain.
[0097] Examples of suitable friction modifiers include long chain
fatty acid derivatives of amines, fatty esters, or fatty epoxides;
fatty imidazolines such as condensation products of carboxylic
acids and polyalkylene-polyamines; amine salts of alkylphosphoric
acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty
alkyl tartramides.
[0098] Friction modifiers may also encompass materials such as
sulphurised fatty compounds and olefins, molybdenum
dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil
or soybean oil monoester of a polyol and an aliphatic carboxylic
acid.
[0099] In one embodiment the friction modifier may be a long chain
fatty acid ester. In another embodiment the long chain fatty acid
ester may be a mono-ester and in another embodiment the long chain
fatty acid ester may be a triglyceride.
[0100] Other performance additives such as corrosion inhibitors
include those described in paragraphs 5 to 8 of WO2006/047486,
octylamine octanoate, condensation products of dodecenyl succinic
acid or anhydride and a fatty acid such as oleic acid with a
polyamine. In one embodiment the corrosion inhibitors include the
Synalox.RTM. corrosion inhibitor. The Synalox.RTM. corrosion
inhibitor may be a homopolymer or copolymer of propylene oxide. The
Synalox.RTM. corrosion inhibitor is described in more detail in a
product brochure with Form No. 118-01453-0702 AMS, published by The
Dow Chemical Company. The product brochure is entitled "SYNALOX
Lubricants, High-Performance Polyglycols for Demanding
Applications."
[0101] Metal deactivators including derivatives of benzotriazoles
(typically tolyltriazole), dimercaptothiadiazole derivatives,
1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or
2-alkyldithiobenzothiazoles; foam inhibitors including copolymers
of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl
acetate; demulsifiers including trialkyl phosphates, polyethylene
glycols, polyethylene oxides, polypropylene oxides and (ethylene
oxide-propylene oxide) polymers; pour point depressants including
esters of maleic anhydride-styrene, polymethacrylates,
polyacrylates or polyacrylamides may be useful. Foam inhibitors
that may be useful in the compositions of the invention include
silicones such as polysiloxanes, copolymers of ethyl acrylate and
2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers
including trialkyl phosphates, polyethylene glycols, polyethylene
oxides, polypropylene oxides and (ethylene oxide-propylene oxide)
polymers.
[0102] Pour point depressants that may be useful in the
compositions of the invention include polyalphaolefins, esters of
maleic anhydride-styrene, poly(meth)acrylates, polyacrylates or
polyacrylamides.
[0103] In different embodiments the lubricating composition may
have a composition as described in the following table:
TABLE-US-00001 Embodiments (wt %) Additive A B C Compound of the
Invention 0.1 to 15 1 to 14 4 to 9 Dispersant 0 to 12 0 to 8 0.5 to
6 Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to 2 Overbased
Detergent 0 to 15 0.1 to 10 0.2 to 8 Antioxidant 0 to 13 0.1 to 10
0.5 to 5 Antiwear Agent 0 to 15 0.1 to 10 0.3 to 5 Friction
Modifier 0 to 6 0.05 to 4 0.1 to 2 Viscosity Modifier 0 to 10 0.5
to 8 1 to 6 Any Other Performance Additive 0 to 10 0 to 8 0 to 6
Oil of Lubricating Viscosity Balance to Balance to Balance to 100%
100% 100%
INDUSTRIAL APPLICATION
[0104] The lubricating composition may be utilised in an internal
combustion engine. The engine components may have a surface of
steel or aluminium (typically a surface of steel).
[0105] An aluminium surface may be derived from an aluminium alloy
that may be a eutectic or a hyper-eutectic aluminium alloy (such as
those derived from aluminium silicates, aluminium oxides, or other
ceramic materials). The aluminium surface may be present on a
cylinder bore, cylinder block, or piston ring having an aluminium
alloy, or aluminium composite.
[0106] The internal combustion engine may or may not have an
Exhaust Gas Recirculation system. The internal combustion engine
may be fitted with an emission control system or a turbocharger.
Examples of the emission control system include diesel particulate
filters (DPF), or systems employing selective catalytic reduction
(SCR).
[0107] In one embodiment the internal combustion engine may be a
diesel fuelled engine (typically a heavy duty diesel engine), a
gasoline fuelled engine, a natural gas fuelled engine or a mixed
gasoline/alcohol fuelled engine. In one embodiment the internal
combustion engine may be a diesel fuelled engine and in another
embodiment a gasoline fuelled engine. In one embodiment the
internal combustion engine may be a heavy duty diesel engine. In
one embodiment the internal combustion engine may be a heavy duty
diesel engine equipped with exhaust gas recirculation.
[0108] The internal combustion engine may be a 2-stroke or 4-stroke
engine. Suitable internal combustion engines include marine diesel
engines, aviation piston engines, low-load diesel engines, and
automobile and truck engines.
[0109] The lubricant composition for an internal combustion engine
may be suitable for any engine lubricant irrespective of the
sulphur, phosphorus or sulphated ash (ASTM D-874) content. The
sulphur content of the engine oil lubricant may be 1 wt % or less,
or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In
one embodiment the sulphur content may be in the range of 0.001 wt
% to 0.5 wt %, or 0.01 wt % to 0.3 wt %. The phosphorus content may
be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or
0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or
less, 0.055 wt % or less, or 0.05 wt % or less. In one embodiment
the phosphorus content may be 0.4 wt % to 0.12 wt %. In one
embodiment the phosphorus content may be 100 ppm to 1000 ppm, or
200 ppm to 600 ppm. The total sulphated ash content may be 0.3 wt %
to 1.2 wt %, or 0.5 wt % to 1.1 wt % of the lubricating
composition. In one embodiment the sulphated ash content may be 0.5
wt % to 1.1 wt % of the lubricating composition.
[0110] In one embodiment the lubricating composition may be an
engine oil, wherein the lubricating composition may be
characterised as having at least one of (i) a sulphur content of
0.5 wt % or less, (ii) a phosphorus content of 0.12 wt % or less,
and (iii) a sulphated ash content of 0.5 wt % to 1.1 wt % of the
lubricating composition.
[0111] The following examples provide illustrations of the
invention. These examples are non-exhaustive and are not intended
to limit the scope of the invention.
EXAMPLES
Preparative Example 1 (EX1)
[0112] A 5 L 5 neck flask is charged with 1326.8 g of
polyisobutylene (vinylidene content of 5-8 mol %, and number
average molecular weight of about 2050) and 1044 g of hexane. A
thermocouple, water condenser and two subsurface gas inlet tubes
are connected to the flask. Prior to the gas inlet, two sinter gas
filters, air trap and flow meter are connected. Prior to the flow
meter an air trap is connected. After the condenser, a dry-ice tap,
air trap, o-toluidine trap, water trap (500 mL) and caustic trap
are connected. The contents of the flask are stirred for 2 hours.
The flask is then heated to 65.degree. C. and 58 g of chlorine is
added over a period of 4 hours. The reaction is blown with nitrogen
gas for 30 minutes, before cooling to ambient temperature. The
flask is then heated to 130.degree. C. over 4 hours to remove
hexane under vacuum. The reaction yields 1293.5 g of product.
Preparative Example 2 (EX2)
[0113] 979.4 g of the product of EX1 and 982.4 g of dodecane are
charged into a 500 ml flask. The flask has a Friedrichs condenser
attached and Tygon.TM. tubing from the condenser outlet to a
caustic trap. The thermocouple is placed in a pocket to prevent
corrosion and a PTFE stirrer is used. The contents of the flask are
stirred for 30 minutes at 50.degree. C. Trans-cinnamic acid (146.5
g) is then added at room temperature via a powder funnel. The
resulting mixture is stirred (250 rpm) and heated to 90.degree. C.
under nitrogen. The mixture is then heated to 180.degree. C. over 1
hour and held at 180.degree. C. for 18 hours. The reaction is then
vacuum stripped over 7 hours while increasing the temperature from
150.degree. C. to 200.degree. C., before cooling to ambient
temperature.
Preparative Example 3 (EX3)
[0114] 292.7 g of the product of EX1 and 250 g of dodecane are
charged into a 1 L flask. The flask has a Friedrichs condenser
attached and Tygon.TM. tubing from the condenser outlet to a
caustic trap. The thermocouple is placed in a pocket to prevent
corrosion and a PTFE stirrer is used. The contents of the flask are
stirred for 30 minutes at 50.degree. C. before cooling to ambient
temperature. 32.5 g of phenylpropiolic acid is added in one
portion. The resulting mixture is stirred (250 rpm) and heated to
90.degree. C. under nitrogen. The mixture is then heated to
180.degree. C. over 1.5 hour and held at 180.degree. C. for 18
hours. The reaction is then vacuum stripped over 10 hours while
increasing the temperature from 150.degree. C. to 200.degree. C.,
before cooling to ambient temperature.
Preparative Example 4 (EX4)
[0115] 230.3 g of the product of EX2 and 235.4 g of diluent oil are
placed in a 1 L flask and heated to 110.degree. C. under a nitrogen
atmosphere. The contents of the flask are stirred at 200 rpm. 6.6 g
of triethylenetetramine is added dropwise (subsurface) over a
period of 10 minutes. The temperature is increased to 155.degree.
C. over a period of 15 minutes. The flask is held at 155.degree. C.
for 4 hours.
Preparative Example 5 (EX5)
[0116] 254.3 g of the product of EX2, 275.2 g of diluent oil are
placed in a 1 L flask and heated to 110.degree. C. under a nitrogen
atmosphere. The contents of the flask are stirred at 200 rpm. 21.7
g of 4-aminodiphenylamine is added portionwise via a powder funnel
over 5 minutes. The temperature is increased to 155.degree. C. and
held for 12 hours and then raised to at 180.degree. C. and held for
5 hours. The flask is cooled to 100.degree. C. and filtered over a
period of 1 hour. The flask is then cooled to ambient
temperature.
Preparative Example 6 (EX6)
[0117] A 2-L four neck flask equipped with an overhead stirrer,
thermowell, subsurface nitrogen feed topped with addition funnel,
and condenser is charged with 8000 Mn olefin copolymer (derived
from ethylene and propylene) (500.0 g), trans-cinnamic acid (10.0
g) and t-butyl benzene (1000 mL) and heated to 150.degree. C. A
solution of t-butyl peroxide (4.9 g) in t-butyl benzene (100 mL) is
charged to the addition funnel and added to the flask subsurface
over 60 min. The reaction is stirred at 150.degree. C. for an
additional 5 hours, then vacuum stripped at reduced pressure. A
viscous product is obtained (510.0 g).
Preparative Example 7 (EX7)
[0118] A 3-L, 4-neck flask equipped with an overhead stirrer,
thermowell, subsurface inlet with nitrogen line, and Dean-Stark
trap with condenser is charged with the product of EX6 (510.0 g)
and diluent oil (1107.3 g) and heated to 110.degree. C.
Dimethylaminopropylamine (6.8 g) is added in one portion,
subsurface. The temperature is then raised to 160.degree. C. and
held at that temperature for 10 hours. The resultant product is a
dark viscous oil (1628.4 g).
[0119] A series of SAE 15W-40 heavy duty diesel engine lubricants
(IVL1 to IVL3) are prepared containing antioxidants (mixture
hindered phenols and alkylated diphenylamines), 1.09 wt % of zinc
dialkyldithiophosphate, a mixture of detergents (including calcium
sulphonate and calcium phenate), 0.2 wt % of
2-tert-nonyldithio-5-mercapto-1,3,4-thiadiazole and further
containing 2 wt % of a dispersant viscosity modifier as described
in International Publication WO2006/015130 (see preparative
examples described in paragraphs [0065] to [0073]). IVL1, IVL2 and
IVL3 contain 4.1 wt % of EX4, EX5 and EX7 respectively.
[0120] Comparative Example 1 (CE1) is a SAE 15W-40 engine lubricant
similar to IVL1, except it replaces the reaction product of the
present invention with 4.1 wt % of a succinimide dispersant.
[0121] IVL1 to IVL2 and CE1 are evaluated for performance for soot
dispersancy. The lubricants are stressed by addition of 1 vol % of
a 17.4 M mixture of sulphuric and nitric acid (10:1) (amount of
acid calculated to reduce TBN by 11). The acid stressed samples are
top treated with 6 wt % carbon black (soot model) and 5 wt % diesel
fuel. The lubricant mixture is the homogenised in a tissumizer to
make a slurry. The slurry is then sonicated to completely disperse
the carbon black. The dispersed sample is stored at 90.degree. C.
for 7 days while blowing 0.5 cc min.sup.-1 of 0.27% nitrous oxide
in air through the sample. 25 microliter aliquots of sample are
blotted onto chromatography paper once daily. After curing the
filter paper for 2 hours at 90.degree. C., the ratio of the
diameter of the internal carbon black containing spot to the
external oil spot (.times.100) is measured, averaged over 7 days
and reported in the table as soot ratio. Higher soot ratio
indicates improved soot dispersion. The results obtained are as
follows:
TABLE-US-00002 CE1 IVL1 IVL2 IVL3 Soot Ratio 43 70 72 N.M.
Footnote: N.M. indicates not measured.
[0122] The results indicate that high soot ratio correlates to
better soot dispersion.
[0123] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. The products formed thereby, including the products formed
upon employing lubricant composition of the present invention in
its intended use, may not be susceptible of easy description.
Nevertheless, all such modifications and reaction products are
included within the scope of the present invention; the present
invention encompasses lubricant composition prepared by admixing
the components described above.
[0124] Each of the documents referred to above is incorporated
herein by reference. Except in the Examples, or where otherwise
explicitly indicated, all numerical quantities in this description
specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood
as modified by the word "about." It is to be understood that the
upper and lower amount, range, and ratio limits set forth herein
may be independently combined. Similarly, the ranges and amounts
for each element of the invention may be used together with ranges
or amounts for any of the other elements.
[0125] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: hydrocarbon substituents,
including aliphatic, alicyclic, and aromatic substituents;
substituted hydrocarbon substituents, that is, substituents
containing non-hydrocarbon groups which, in the context of this
invention, do not alter the predominantly hydrocarbon nature of the
substituent; and hetero substituents, that is, substituents which
similarly have a predominantly hydrocarbon character but contain
other than carbon in a ring or chain. A more detailed definition of
the term "hydrocarbyl substituent" or "hydrocarbyl group" is
described in paragraphs [0118] to [0119] of International
Publication WO2008147704 and paragraphs [0137] to [0141] of
published application US 2010-0197536.
[0126] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *