Canadian Patents Database / Patent 2833977 Summary

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(12) Patent Application: (11) CA 2833977
(54) English Title: MARINE ENGINE LUBRICATING OIL COMPOSITION COMPRISING AN OIL-SOLUBLE ESTER BASESTOCK AND AN OIL-SOLUBLE POLYALKENYL-SUBSTITUTED CARBOXYLIC ACID ANHYDRIDE
(54) French Title: COMPOSITION D'HUILE LUBRIFIANTE DE MOTEUR MARIN RENFERMANT UNE MATIERE DE BASE D'ESTER SOLUBLE A L'HUILE ET UN ANHYDRE D'ACIDE CARBOXYLIQUE SUBSTITUE PAR UN POLYALKENYL
(51) International Patent Classification (IPC):
  • C10M 169/04 (2006.01)
  • C10M 105/38 (2006.01)
  • C10M 129/34 (2006.01)
  • C10M 159/22 (2006.01)
(72) Inventors :
  • BRADLEY-SHAW, JOSHUA (United Kingdom)
  • DODD, JAMES CHRISTIAN (United Kingdom)
(73) Owners :
  • INFINEUM INTERNATIONAL LIMITED (Not Available)
(71) Applicants :
  • INFINEUM INTERNATIONAL LIMITED (United Kingdom)
(74) Agent: BORDEN LADNER GERVAIS LLP
(74) Associate agent:
(45) Issued:
(22) Filed Date: 2013-11-21
(41) Open to Public Inspection: 2014-05-21
Examination requested: 2018-05-30
(30) Availability of licence: N/A
(30) Language of filing: English

(30) Application Priority Data:
Application No. Country/Territory Date
12193607.4 European Patent Office (EPO) 2012-11-21

English Abstract


Trunk piston marine engine lubrication comprising a major amount of (A) an oil
of
lubricating viscosity that comprises an oil-soluble ester basestock, or that
comprises greater than
0.1 to less than 90 mass % of an oil-soluble ester basestock and, as 50 mass %
or more of the
remainder of the oil of lubricating viscosity, a high saturates basestock; (B)
a minor amount of a
metal alkyl salicylate detergent; and (C) greater than 0.1 to less than 10
mass %, of an oil-soluble
polyalkenyl-substituted carboxylic acid anhydride, wherein the or at least one
polyalkenyl group
is derived from a polyalkene having a number average molecular weight of from
200 to 3,000.
Asphaltene precipitation in the lubricant composition, caused by the presence
of contaminant
heavy fuel oil, is prevented or inhibited.


Note: Claims are shown in the official language in which they were submitted.

CLAIMS:
1. A trunk piston marine engine lubricating oil composition for improving
asphaltene
handling in use thereof, in operation of the engine when fuelled by a heavy
fuel oil, which
composition comprises or is made by admixing
(A) an oil of lubricating viscosity, in a major amount, which is either an
oil-soluble
ester basestock (A1); or comprises greater than 0.1 to less than 90 mass %,
preferably 1 to 85 mass %, of an oil-soluble ester basestock (A1) and, as 50
mass % or more of the remainder of the oil of lubricating viscosity, a
basestock
containing greater than or equal to 90% saturates and less than or equal to
0.03 %
sulphur or a mixture thereof (A2);
(B) an oil-soluble metal detergent, in a minor amount; and
(C) an oil-soluble polyalkenyl-substituted carboxylic acid anhydride, in a
minor
amount of from greater than 0.1 to less than 10 mass %, preferably greater
than
0.5 to less than 8 mass %, the, or at least one, polyalkenyl group being
derived
from polyalkene having a number average molecular weight of from 200 to 3000.
2. The lubricating oil of claim 1 where, in the oil of lubricating
viscosity, the basestock (A2),
when present, contains more than 60 mass %, preferably more than 70 mass %,
even
more preferably more than 80 mass %, and most preferably more than 90 mass %,
of the
basestock containing greater than or equal to 90% saturates and less than or
equal to
0.03% sulphur or a mixture thereof.
3. The lubricating oil of claim 1 or 2 where the basestock (A2), when
present, is a Group II,
Group III or Group IV basestock; preferably a Group II basestock.

26

4. The lubricating oil of any of claims 1 to 3 where the metal detergent
(B) is a metal
hydrocarbyl-substituted hydroxybenzoate detergent.
5. The lubricating oil of claim 4 where the metal detergent (B) is a
calcium alkyl salicylate
detergent.
6. The lubricating oil of claim 4 or 5 where the metal detergent (B) is C9
to C30 alkyl-
substituted .
7. The lubricating oil of claim 4 or 5 where the metal detergent (B) is C20
or higher alkyl-
substituted.
8. The lubricating oil of any of claims 1 to 7 where the polyalkenyl
substituent in the
anhydride (C) has from 8 to 400, such as 12 to 100, especially 16 to 64,
carbon atoms.
9. The lubricating oil of any of claims 1 to 8 where the polyalkenyl
substituent in the
anhydride (C) has a number average molecular weight of from 350 to 1000, such
as from
500 to 1000.
10. The lubricating oil of any of claims 1 to 9 where the polyalkenyl-
substituted carboxylic
acid anhydride (C) is a succinic anhydride.
11. The lubricating oil of claim 10 where the succinic anhydride (C) is a
polybutene succinic
anhydride.
12. The lubricating oil of any of claims 1 to 11 where the ester basestock
(A1) is present in
an amount of 10 to 90, such as 20 to 90, such as 30 to 90, mass %.
13. The lubricating oil of any of claims 1 to 12 where the ester basestock
(A1) has a
kinematic viscosity of 2 to 10 mm2s-1 at 100°C.

27

14. The lubricating oil of any of claims 1 to 13 where the ester basestock
(A1) is a polyol
ester basestock.
15. The lubricating oil composition of any of claims 1 to 14 further
including a heavy fuel oil
content.
16. A method of operating a trunk piston medium-speed compression-ignited
marine engine
comprising
fuelling the engine with a heavy fuel oil; and
(iii) lubricating the crankcase of the engine with a composition as
claimed in any of
claims 1 to 15.
17. A method of dispersing asphaltenes in a trunk piston marine lubricating
oil composition
during its lubrication of surfaces of the combustion chamber of a medium-speed

compression-ignited marine engine and operation of the engine, which method
comprises:
providing a composition as claimed in any of claims 1 to 15;
(ii) providing the composition in the combustion chamber;
(iii) providing heavy fuel oil in the combustion chamber; and
(iv) combusting the heavy fuel oil in the combustion chamber.
18. The method of claim 17, wherein the dispersion of asphaltenese is
measured using the
Focussed Beam Reflectance Method ('FBRM').

28

19. The use of detergent (B) in combination with component (C), as defined
in and in the
amounts stated in any of claims 1 to 15 in a trunk piston marine lubricating
oil
composition for a medium-speed compression-ignited marine engine, which
composition
comprises an oil of lubricating viscosity (A) in a major amount as defined in
claim 1, to
provide comparable or improved asphaltene handling during operation of the
engine,
fuelled by a heavy fuel oil, and its lubrication by the composition, in
comparison with
that of a comparable oil where the basestock (A2) is a Group I basestock.
20. The use of claim 19, wherein asphaltene handling during operation of
the engine is
measured using the Focussed Beam Reflectance Method ('FBRM').

29

Note: Descriptions are shown in the official language in which they were submitted.

CA 02833977 2013-11-21
MARINE ENGINE LUBRICATION
FIELD OF THE INVENTION
This invention relates to a trunk piston marine engine lubricating composition
for
a medium-speed four-stroke compression-ignited (diesel) marine engine and
lubrication of such
an engine.
BACKGROUND OF THE INVENTION
Marine trunk piston engines generally use Heavy Fuel Oil ('HF0') for offshore
running. Heavy Fuel Oil is the heaviest fraction of petroleum distillate and
comprises a complex
mixture of molecules including up to 15% of asphaltenes, defined as the
fraction of petroleum
distillate that is insoluble in an excess of aliphatic hydrocarbon (e.g.
heptane) but that is soluble
in aromatic solvents (e.g. toluene). Asphaltenes can enter the engine
lubricant as contaminants
either via the cylinder or the fuel pumps and injectors, and asphaltene
precipitation can then
occur, manifested in 'black paint' or 'black sludge' in the engine. The
presence of such
carbonaceous deposits on a piston surface can act as an insulating layer that
can result in the
formation of cracks that then propagate through the piston. If a crack travels
through the piston,
hot combustion gases can enter the crankcase, possibly resulting in a
crankcase explosion.
It is therefore highly desirable that trunk piston engine oils (`TPEO's)
prevent or inhibit
asphaltene precipitation. TPEO's using Group 1 basestocks may have the ability
to solubilise
asphaltenes. However, TPEO's using high saturate basestocks (e.g. Group II or
III) require a
booster to achieve similar performance levels in this respect.
WO 2010/115594 ("594") and WO 2010/115595 ("595") describe the use, in trunk
piston
marine engine lubricating oil compositions that contain 50 mass % or more of a
Group II
basestock, of respective minor amounts of a calcium salicylate detergent and
of a polyalkenyl-

CA 02833977 2013-11-21
. .
substituted carboxylic and anhydride. The data in "594" and "595" show that
the combination
gives rise to improved asphaltene dispersancy.
US 2011/0319304 Al (`304) describes the use of ester basestock in a high
saturates
basestock TPEO to improve asphaltene dispersancy.
A problem in the art is to improve still further the asphaltene dispersancy
performance of
TPEO' s that employ high saturate basestocks.
SUMMARY OF THE INVENTION
The invention meets the above problem by employing an anhydride and an ester
in a
TPEO: a synergistic effect is observed as demonstrated in the data herein.
A first aspect of the invention is a trunk piston marine engine lubricating
oil composition
for improving asphaltene handling in use thereof in operation of the engine
when fuelled by a
heavy fuel oil, which composition comprises or is made by admixing
(A) an oil of lubricating viscosity, in a major amount, which is either an oil-
soluble
ester basestock (Al); or comprises greater than 0.1 to less than 90 mass %,
preferably greater than 1 to less than 80 mass%, of an oil-soluble ester
basestock
(Al) and, as 50 mass % or more of the remainder of the oil of lubricating
viscosity,
a basestock containing greater than or equal to 90% saturates and less than or
equal
to 0.03 % sulphur or a mixture thereof (A2);
(B) an oil-soluble metal detergent, in a minor amount; and
(C) an oil-soluble polyalkenyl-substituted carboxylic acid anhydride, in a
minor amount
of from greater than 0.1 to less than 10 mass %, preferably greater than 1 to
less than
2

CA 02833977 2013-11-21
8 mass%, the, or at least one, polyalkenyl group being derived from polyalkene

having a number average molecular weight of from 200 to 3000.
A second aspect of the invention is a method of operating a trunk piston
medium-speed
compression-ignited marine engine comprising
(i) fuelling the engine with a heavy fuel oil; and
(ii) lubricating the crankcase of the engine with a composition according
to the first
aspect of the invention.
A third aspect of the invention is a method of dispersing asphaltenes in a
trunk piston
marine lubricating oil composition during its lubrication of surfaces of the
combustion chamber
of a medium-speed compression-ignited marine engine and operation of the
engine, which
method comprises:
(i) providing a composition according to the first aspect of the invention;
(ii) providing the composition in the combustion chamber;
(iii) providing heavy fuel oil in the combustion chamber; and
(iv) combusting the heavy fuel oil in the combustion chamber.
A fourth aspect of the invention is the use of detergent (B) in combination
with
component (C) as defined in and in the amounts stated in the first aspect of
the invention in a
trunk piston marine lubricating oil composition for a medium-speed compression-
ignited marine
engine, which composition comprises an oil of lubricating viscosity (A) in a
major amount as
defined in the first aspect of the invention, to provide comparable or
improved asphaltene
handling during operation of the engine, fuelled by a heavy fuel oil, and its
lubrication by the
3

CA 02833977 2013-11-21
composition, in comparison with that of a comparable oil where the basestock
is a Group I
basestock.
In this specification, the following words and expressions, if and when used,
have the
meanings ascribed below:
"active ingredients" or "(a.i.)" refers to additive material that is not
diluent or solvent;
"comprising" or any cognate word specifies the presence of stated features,
steps, or
integers or components, but does not preclude the presence or addition of one
or more
other features, steps, integers, components or groups thereof; the expressions
"consists
of' or "consists essentially of' or cognates may be embraced within
"comprises" or
cognates, wherein "consists essentially of' permits inclusion of substances
not materially
affecting the characteristics of the composition to which it applies;
"major amount" means 50 mass % or more, preferably 60 mass % or more, more
preferably 70 mass % or more, even more preferably 80 mass % or more, of a
composition;
"minor amount" means less than 50 mass %, preferably less than 40 mass %, more

preferably less than 30 mass %, and even more preferably less than 20 mass %,
of a
composition;
"TBN" means total base number as measured by ASTM D2896.
Furthermore in this specification, if and when used:
"calcium content" is as measured by ASTM 4951;
"phosphorus content" is as measured by ASTM D5185;
4

CA 02833977 2013-11-21
. .
"sulphated ash content" is as measured by ASTM D874;
"sulphur content" is as measured by ASTM D2622;
"KV100" means kinematic viscosity at 100 C as measured by ASTM D445.
Also, it will be understood that various components used, essential as well as
optimal and
customary, may react under conditions of formulation, storage or use and that
the invention also
provides the product obtainable or obtained as a result of any such reaction.
Further, it is understood that any upper and lower quantity, range and ratio
limits set forth
herein may be independently combined.
DETAILED DESCRIPTION OF THE INVENTION
The features of the invention will now be discussed in more detail below.
OIL OF LUBRICATING VISCOSITY (A)
ESTER BASESTOCKS (Al)
These are organic ester basestocks that include but are not limited to
monoesters , diesters
and polyolesters, and also polymer esters. They are generally considered to be
Group V
basestocks and are typically derived from animal or vegetable sources.
Naturally-occurring
organic esters can be found in animal fats or in vegetable oils. Organic
esters can be synthesised
by reacting organic acids with alcohols.
Monesters may be prepared by reacting monohydric alcohols with monobasic fatty
acids
to create a molecule with a single ester linkage and linear or branched alkyl
groups.

CA 02833977 2013-11-21
Diesters may be prepared by reacting monohydric alcohols (e.g., butyl alcohol,

hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol,
diethylene glycol
monoether, propylene glycol) with dibasic acids (e.g., phthalic acid, succinic
acid, alkyl succinic
acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid,
sebacic acid, fumaric
acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids,
alkenyl malonic acids) to
create a molecule which may be linear, branched or aromatic with two ester
groups. Specific
examples of such esters includes dibutyl adipate, di(2-ethylhexyl) sebacate,
di-n-hexyl fumarate,
dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,
didecyl phthalate,
dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the
complex ester formed
by reacting one mole of sebacic acid with two moles of tetraethylene glycol
and two moles of 2-
ethylhexanoic acid.
Polyol esters may be prepared by esterifying one or more polyols such as
neopentyl
glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and
tripentaerythritol with one or
more organic acids such as C5 to C12 monocarboxylic acids. See, for example,
US-A-6,462,001.
Examples of polyol esters include trimethylolpropane (TMP) esters.
Tricarboxylic acid esters are also preferred. The tricarboxylic acid ester is
preferably a
benzene tricarboxylic acid.
A preferred benzene tricarboxylic acid ester is 1,2,4-
benzenetricarboxylic acid having alkyl chain lengths ranging from 5 to 10,
preferably from 7 to 9.
A preferred 1,2,4-benzenetricarboxylic acid is trioctyl trimellitate.
Examples of ester basestocks for use in the present invention are those having
a
kinematic viscosity of 2 to 10 mm2s-I at 100 C or those having a kinematic
viscosity of greater
than 10 to 100 mm2s-1 at 100 C. A specific example of suitable polyol ester is
Priolube
(Registered Trade Mark) 3970, which is an ester of a neopentyl polyol,
suitably TMP, with at
least one aliphatic, saturated monocarboxylic acid and having 6 to 12 carbon
atoms and a
kinematic viscosity of 4.4 mm2s-I at 100 C.
6

CA 02833977 2013-11-21
The ester basestock may be present in an amount in the range of 2 to 85,
preferably 5 to
50, more preferably 8 to 40 mass %.
BASESTOCKS (A2)
These may range in viscosity from light distillate mineral oil to heavy
lubricating oil.
Generally, the viscosity of the oil ranges from 2 to 40 mm2s-1, as measured at
100 C.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard
oil); liquid
petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils
of the paraffinic,
naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating
viscosity derived from
coal or shale also serve as useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted
hydrocarbon oils
such as polymerized and interpolymerized olefins (e.g., polybutylenes,
polypropylenes,
propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes),
poly(1-octenes),
poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes,
di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated
polyphenols); and
alkylated diphenyl ethers and alkylated diphenyl sulphides and derivative,
analogues and
homologues thereof.
Unrefined, refined and re-refined oils can be used in lubricants of the
present invention.
Unrefined oils are those obtained directly from a natural or synthetic source
without further
purification treatment. For example, a shale oil obtained directly from
retorting operations; and
petroleum oil obtained directly from distillation are unrefined oils. Refined
oils are similar to
unrefined oils except that the oil is further treated in one or more
purification steps to improve
one or more properties. Many such purification techniques, such as
distillation, solvent
extraction, acid or base extraction, filtration and percolation, are known to
those skilled in the art.
Re-refined oils are obtained by processes similar to those used to provide
refined oils but begin
7

CA 02833977 2013-11-21
with oil that has already been used in service. Such re-refined oils are also
known as reclaimed
or reprocessed oils and are often subjected to additional processing using
techniques for
removing spent additives and oil breakdown products.
The American Petroleum Institute (API) publication "Engine Oil Licensing and
Certification System", Industry Services Department, Fourteenth Edition,
December 1996,
Addendum 1, December 1998 categorizes base stocks as follows:
Group I base stocks contain less than 90 percent saturates and/or greater than
0.03 percent
sulphur and have a viscosity index greater than or equal to 80 and less than
120 using the test
methods specified in Table E-1.
Group II base stocks contain greater than or equal to 90 percent saturates and
less than or
equal to 0.03 percent sulphur and have a viscosity index greater than or equal
to 80 and less than
120 using the test methods specified in Table E-1.
Group III base stocks contain greater than or equal to 90 percent saturates
and less than or
equal to 0.03 percent sulphur and have a viscosity index greater than or equal
to 120 using the
test methods specified in Table E-1.
Group IV base stocks are polyalphaolefins (PAO).
Group V base stocks include all other base stocks not included in Group I, II,
III, or IV.
Analytical Methods for Base Stock are tabulated below:
8

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(TABLE E-1)
PROPERTY TEST METHOD
Saturates ASTM D 2007
Viscosity Index ASTM D 2270
Sulphur ASTM D 2622
ASTM D 4294
ASTM D 4927
ASTM D 3120
By way of example, the basestocks (A2) embraces Group II, Group III and Group
IV
basestocks and also basestocks derived from hydrocarbons synthesised by the
Fischer-Tropsch
process. In the Fischer-Tropsch process, synthesis gas containing carbon
monoxide and
hydrogen (or `syngas') is first generated and then converted to hydrocarbons
using a Fischer-
Tropsch catalyst. These hydrocarbons typically require further processing in
order to be useful as
a base oil. For example, they may, by methods known in the art, be
hydroisomerized;
hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed. The
syngas
may, for example, be made from gas such as natural gas or other gaseous
hydrocarbons by steam
reforming, when the basestock may be referred to as gas-to-liquid ("GTL") base
oil; or from
gasification of biomass, when the basestock may be referred to as biomass-to-
liquid ("BTU or
"BMTL") base oil; or from gasification of coal, when the basestock may be
referred to as coal-
to-liquid ("CTL") base oil.
As stated, the basestock (A2), when used in this invention, contains 50 mass %
or more
of the defined basestock or a mixture thereof. Preferably, it contains 60,
such as 70, 80 or 90,
mass % or more of the defined basestock or a mixture thereof (A2) may comprise
substantially
all the defined basestock or a mixture thereof.
9

CA 02833977 2013-11-21
OVERBASED METAL DETERGENT (B)
A metal detergent is an additive based on so-called metal "soaps", that is
metal salts of
acidic organic compounds, sometimes referred to as surfactants. They generally
comprise a
polar head with a long hydrophobic tail. Overbased metal detergents, which
comprise
neutralized metal detergents as the outer layer of a metal base (e.g.
carbonate) micelle, may be
provided by including large amounts of metal base by reacting an excess of a
metal base, such as
an oxide or hydroxide, with an acidic gas such as carbon dioxide. Examples of
detergents
include metal salicylates, phenates and salicylates and combinations thereof.
In the present invention, overbased metal detergents (B) are preferably
overbased
metal hydrocarbyl-substituted hydroxybenzoate, more preferably hydrocarbyl-
substituted
salicylate, detergents. The metal may be an alkali metal (e.g. Li, Na, K) or
an alkaline earth
metal (e.g. Mg, Ca).
"Hydrocarbyl" means a group or radical that contains carbon and hydrogen atoms
and
that is bonded to the remainder of the molecule via a carbon atom. It may
contain hetero atoms,
i.e. atoms other than carbon and hydrogen, provided they do not alter the
essentially hydrocarbon
nature and characteristics of the group. As examples of hydrocarbyl, there may
be mentioned
alkyl and alkenyl. A preferred overbased metal hydrocarbyl-substituted
hydroxybenzoate is a
calcium alkyl-substituted salicylate and has the structure shown:
OH
I- C Calf
wherein R is a linear alkyl group. There may be more than one R group attached
to the benzene
ring. The COO- group can be in the ortho, meta or para position with respect
to the hydroxyl

CA 02833977 2013-11-21
group; the ortho position is preferred. The R group can be in the ortho, meta
or para position
with respect to the hydroxyl group.
Salicylic acids are typically prepared by the carboxylation, by the Kolbe-
Schmitt process,
of phenoxides, and in that case will generally be obtained (normally in a
diluent) in admixture
with tmcarboxylated phenol. Salicylic acids may be non-sulphurized or
sulphurized, and may be
chemically modified and/or contain additional substituents. Processes for
sulphurizing an alkyl
salicylic acid are well known to those skilled in the art, and are described
in, for example, US
2007/0027057.
The alkyl groups advantageously contain 5 to 100, preferably 9 to 30,
especially 14 to 24,
carbon atoms.
The term "overbased" is generally used to describe metal detergents in which
the ratio of
the number of equivalents of the metal moiety to the number of equivalents of
the acid moiety is
greater than one. The term 'low-based' is used to describe metal detergents in
which the
equivalent ratio of metal moiety to acid moiety is greater than 1, and up to
about 2.
By an "overbased calcium salt of surfactants" is meant an overbased detergent
in which
the metal cations of the oil-insoluble metal salt are essentially calcium
cations. Small amounts of
other cations may be present in the oil-insoluble metal salt, but typically at
least 80, more
typically at least 90, for example at least 95, mole % of the cations in the
oil-insoluble metal salt,
are calcium ions. Cations other than calcium may be derived, for example, from
the use in the
manufacture of the overbased detergent of a surfactant salt in which the
cation is a metal other
than calcium. Preferably, the metal salt of the surfactant is also calcium.
Carbonated overbased metal detergents typically comprise amorphous
nanoparticles.
Additionally, the art discloses nanoparticulate materials comprising carbonate
in the crystalline
calcite and vaterite forms.
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CA 02833977 2013-11-21
. .
The basicity of the detergents may be expressed as a total base number (TBN),
sometimes referred to as base number (BN). A total base number is the amount
of acid needed
to neutralize all of the basicity of the overbased material. The TBN may be
measured using
ASTM standard D2896 or an equivalent procedure. The detergent may have a low
TBN (i.e. a
TBN of less than 50), a medium TBN (i.e. a TBN of 50 to 150) or a high TBN
(i.e. a TBN of
greater than 150, such as 150-500). The bascicity may also be expressed as
basicity index (BI),
which is the molar ratio of total base to total soap in the overbased
detergent.
POLYALKENYL-SUBSTITUTED CARBOXYLIC ACID ANHYDRIDE (C)
The anhydride may constitute at least 1 to 7, preferably 2 to 6 mass % of the
lubricating
oil composition. Preferably it constitutes 3 to 5, even more preferably 4 to
5, mass %.
The anhydride may be mono or polycarboxylic, preferably dicarboxylic. The
polyalkenyl
group preferably has from 8 to 400, such as 8 to 100, carbon atoms.
General formulae of exemplary anhydrides may be depicted as
R1
1
HC-CO
1
0
H2C - CO
where RI represents a C8 to C100 branched or linear polyalkenyl group.
The polyalkenyl moiety may have a number average molecular weight of from 200
to
3000, preferably from 350 to 950.
Suitable hydrocarbons or polymers employed in the formation of the anhydrides
used in
the present invention to generate the polyalkenyl moieties include
homopolymers, interpolymers
or lower molecular weight hydrocarbons. One family of such polymers comprise
polymers of
12

CA 02833977 2013-11-21
ethylene and/or at least one C3 to Cu alpha-olefin having the formula H2C=CHR1
wherein R1 is
straight or branched-chain alkyl radical comprising 1 to 26 carbon atoms and
wherein the
polymer contains carbon-to-carbon unsaturation, preferably a high degree of
terminal
ethenylidene unsaturation. Preferably, such polymers comprise interpolymers of
ethylene and at
least one alpha-olefin of the above formula, wherein R1 is alkyl of from 1 to
18 carbon atoms,
and more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably
still of from 1 to 2
carbon atoms. Therefore, useful alpha-olefin monomers and comonomers include,
for example,
propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, decene-1, dodecene-
1, tridecene-1,
tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1,
nonadecene-1, and
mixtures thereof (e.g., mixtures of propylene and butene-1, and the like).
Exemplary of such
polymers are propylene homopolymers, butene-1 homopolymers, ethylene-propylene

copolymers, ethylene-butene-1 copolymers, propylene-butene copolymers and the
like, wherein
the polymer contains at least some terminal and/or internal unsaturation.
Preferred polymers are
unsaturated copolymers of ethylene and propylene and ethylene and butene-1.
The
interpolymers may contain a minor amount, e.g. 0.5 to 5 mole %, of a C4 to C18
non-conjugated
diolefin comonomer. However, it is preferred that the polymers comprise only
alpha-olefin
homopolymers, interpolymers of alpha-olefin comonomers and interpolymers of
ethylene and
alpha-olefin comonomers. The molar ethylene content of the polymers employed
is preferably in
the range of 0 to 80 %, and more preferably 0 to 60 %. When propylene and/or
butene-1 are
employed as comonomer(s) with ethylene, the ethylene content of such
copolymers is most
preferably between 15 and 50 %, although higher or lower ethylene contents may
be present.
These polymers may be prepared by polymerizing an alpha-olefin monomer, or
mixtures
of alpha-olefin monomers, or mixtures comprising ethylene and at least one C3
to C28 alpha-
olefin monomer, in the presence of a catalyst system comprising at least one
metallocene (e.g., a
cyclopentadienyl-transition metal compound) and an alumoxane compound. Using
this process,
a polymer in which 95 % or more of the polymer chains possess terminal
ethenylidene-type
unsaturation can be provided. The percentage of polymer chains exhibiting
terminal ethenylidene
unsaturation may be determined by FTIR spectroscopic analysis, titration, or
C13 NMR.
Interpolymers of this latter type may be characterized by the formula POLY-
C(R1)=CH2
13

CA 02833977 2013-11-21
wherein RI is C1 to C26 alkyl, preferably C1 to C18 alkyl, more preferably CI
to C8 alkyl, and
most preferably C1 to C2 alkyl, (e.g., methyl or ethyl) and wherein POLY
represents the polymer
chain. The chain length of the RI alkyl group will vary depending on the
comonomer(s) selected
for use in the polymerization. A minor amount of the polymer chains can
contain terminal
ethenyl, i.e., vinyl, unsaturation, i.e. POLY-CH=CH2, and a portion of the
polymers can contain
internal monounsaturation, e.g. POLY-CH=CH(R1), wherein 11.' is as defined
above. These
terminally unsaturated interpolymers may be prepared by known metallocene
chemistry and may
also be prepared as described in U.S. Patent Nos. 5,498,809; 5,663,130;
5,705,577; 5,814,715;
6,022,929 and 6,030,930.
Another useful class of polymers is that of polymers prepared by cationic
polymerization
of isobutene, styrene, and the like. Common polymers from this class include
polyisobutenes
obtained by polymerization of a C4 refinery stream having a butene content of
35 to 75 mass %,
and an isobutene content of 30 to 60 mass %, in the presence of a Lewis acid
catalyst, such as
aluminum trichloride or boron trifluoride. A preferred source of monomer for
making poly-n-
butenes is petroleum feedstreams such as Raffinate II. These feedstocks are
disclosed in the art
such as in U.S. Patent No. 4,952,739. Polyisobutylene is a most preferred
backbone because it is
readily available by cationic polymerization from butene streams (e.g., using
AlC13 or BF3
catalysts). Such polyisobutylenes generally contain residual unsaturation in
amounts of one
ethylenic double bond per polymer chain, positioned along the chain. A
preferred embodiment
utilizes polyisobutylene prepared from a pure isobutylene stream or a
Raffinate I stream to
prepare reactive isobutylene polymers with terminal vinylidene olefins.
Preferably, these
polymers, referred to as highly reactive polyisobutylene (HR-PIB), have a
terminal vinylidene
content of at least 65%, e.g., 70%, more preferably at least 80%, most
preferably, at least 85%.
The preparation of such polymers is described, for example, in U.S. Patent No.
4,152,499. HR-
PIB is known and HR-PIB is commercially available under the tradenames
GlissopalTM (from
BASF) and UltravisTM (from BP-Amoco).
Polyisobutylene polymers that may be employed are generally based on a
hydrocarbon
chain of from 400 to 3000. Methods for making polyisobutylene are known.
Polyisobutylene
14

CA 02833977 2013-11-21
can be functionalized by halogenation (e.g. chlorination), the thermal "ene"
reaction, or by free
radical grafting using a catalyst (e.g. peroxide), as described below.
To produce (C) the hydrocarbon or polymer backbone may be functionalized with
carboxylic anhydride-producing moieties selectively at sites of carbon-to-
carbon unsaturation on
the polymer or hydrocarbon chains, or randomly along chains using any of the
three processes
mentioned above or combinations thereof, in any sequence.
Processes for reacting polymeric hydrocarbons with unsaturated carboxylic,
anhydrides
and the preparation of derivatives from such compounds are disclosed in U.S.
Patent Nos.
3,087,936; 3,172,892; 3,215,707; 3,231,587; 3,272,746; 3,275,554; 3,381,022;
3,442,808;
3,565,804; 3,912,764; 4,110,349; 4,234,435; 5,777,025; 5,891,953; as well as
EP 0 382 450 Bl;
CA-1,335,895 and GB-A-1,440,219. The polymer or hydrocarbon may be
functionalized, with
carboxylic acid anhydride moieties by reacting the polymer or hydrocarbon
under conditions that
result in the addition of functional moieties or agents, i.e., acid anhydride,
onto the polymer or
hydrocarbon chains primarily at sites of carbon-to-carbon unsaturation (also
referred to as
ethylenic or olefinic unsaturation) using the halogen assisted
functionalization (e.g. chlorination)
process or the thermal "ene" reaction.
Selective functionalization can be accomplished by halogenating, e.g.,
chlorinating or
brominating, the unsaturated a-olefin polymer to 1 to 8, preferably 3 to 7,
mass % chlorine, or
bromine, based on the weight of polymer or hydrocarbon, by passing the
chlorine or bromine
through the polymer at a temperature of 60 to 250 C, preferably 110 to 160 C,
e.g., 120 to
140 C, for 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer or
hydrocarbon
(hereinafter backbone) is then reacted with sufficient monounsaturated
reactant capable of
adding the required number of functional moieties to the backbone, e.g.,
monounsaturated
carboxylic reactant, at 100 to 250 C, usually 180 C to 235 C, for 0.5 to 10,
e.g., 3 to 8 hours,
such that the product obtained will contain the desired number of moles of the
monounsaturated
carboxylic reactant per mole of the halogenated backbones. Alternatively, the
backbone and the

CA 02833977 2013-11-21
monounsaturated carboxylic reactant are mixed and heated while adding chlorine
to the hot
material.
While chlorination normally helps increase the reactivity of starting olefin
polymers with
monounsaturated functionalizing reactant, it is not necessary with some of the
polymers or
hydrocarbons contemplated for use in the present invention, particularly those
preferred
polymers or hydrocarbons which possess a high terminal bond content and
reactivity. Preferably,
therefore, the backbone and the monounsaturated functionality reactant,
(carboxylic reactant),
are contacted at elevated temperature to cause an initial thermal "ene"
reaction to take place. Ene
reactions are known.
The hydrocarbon or polymer backbone can be functionalized by random attachment
of
functional moieties along the polymer chains by a variety of methods. For
example, the polymer,
in solution or in solid form, may be grafted with the monounsaturated
carboxylic reactant, as
described above, in the presence of a free-radical initiator. When performed
in solution, the
grafting takes place at an elevated temperature in the range of 100 to 260 C,
preferably 120 to
240 C. Preferably, free-radical initiated grafting would be accomplished in a
mineral lubricating
oil solution containing, e.g., 1 to 50, preferably 5 to 30, mass % polymer
based on the initial total
oil solution.
The free-radical initiators that may be used are peroxides, hydroperoxides,
and azo
compounds, preferably those that have a boiling point greater than 100 C and
decompose
thermally within the grafting temperature range to provide free-radicals.
Representative of these
free-radical initiators are azobutyronitrile, 2,5-dimethylhex-3-ene-2, 5-bis-
tertiary-butyl peroxide
and dicumene peroxide. The initiator, when used, is typically in an amount of
between 0.005%
and 1% by weight based on the weight of the reaction mixture solution.
Typically, the aforesaid
monounsaturated carboxylic reactant material and free-radical initiator are
used in a weight ratio
range of from 1.0:1 to 30:1, preferably 3:1 to 6:1. The grafting is preferably
carried out in an
inert atmosphere, such as under nitrogen blanketing. The resulting grafted
polymer is
characterized by having carboxylic acid (or derivative) moieties randomly
attached along the
16

CA 02833977 2013-11-21
, .
polymer chains, it being understood, of course, that some of the polymer
chains remain ungrafted.
The free radical grafting described above can be used for the other polymers
and hydrocarbons
used in the present invention.
The preferred monounsaturated reactants that are used to functionalize the
backbone
comprise mono- and dicarboxylic acid material, i.e., acid, or acid derivative
material, including
(i) monounsaturated C4 to C10 dicarboxylic acid wherein (a) the carboxyl
groups are vicinyl, (i.e.,
located on adjacent carbon atoms) and (b) at least one, preferably both, of
the adjacent carbon
atoms are part of the mono unsaturation; (ii) derivatives of (i) such as
anhydrides or C1 to C5
alcohol derived mono- or diesters of (i); (iii) monounsaturated C3 to C10
monocarboxylic acid
wherein the carbon-carbon double bond is conjugated with the carboxy group,
i.e., of the
structure -C=C-00-; and (iv) derivatives of (iii) such as CI to C5 alcohol
derived mono- or
diesters of (iii). Mixtures of monounsaturated carboxylic materials (i) - (iv)
also may be used.
Upon reaction with the backbone, the monounsaturation of the monounsaturated
carboxylic
reactant becomes saturated. Thus, for example, maleic anhydride becomes
backbone-substituted
succinic anhydride, and acrylic acid becomes backbone-substituted propionic
acid. Exemplary
of such monounsaturated carboxylic reactants are fumaric acid, itaconic acid,
maleic acid, maleic
anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid,
methacrylic acid, crotonic
acid, cinnamic acid, and lower alkyl (e.g., C1 to C4 alkyl) acid esters of the
foregoing, e.g.,
methyl maleate, ethyl fumarate, and methyl fumarate.
To provide the required functionality, the monounsaturated carboxylic
reactant,
preferably maleic anhydride, typically will be used in an amount ranging from
equimolar amount
to 100 mass % excess, preferably 5 to 50 mass % excess, based on the moles of
polymer or
hydrocarbon. Unreacted excess monounsaturated carboxylic reactant can be
removed from the
final dispersant product by, for example, stripping, usually under vacuum, if
required.
17

CA 02833977 2013-11-21
. .
CO-ADDITIVES
The lubricating oil composition of the invention may comprise further
additives, different
from and additional to (B) and (C). Such additional additives may, for example
include ashless
dispersants, other metal detergents, anti-wear agents such as zinc
dihydrocarbyl dithiophosphates,
anti-oxidants and demulsifiers. In some cases, an ashless dispersant need not
be provided.
It may be desirable, although not essential, to prepare one or more additive
packages or
concentrates comprising the additives, whereby additives (B) and (C) can be
added
simultaneously to the base oil to form the lubricating oil composition.
Dissolution of the
additive package(s) into the lubricating oil may be facilitated by solvents
and by mixing
accompanied with mild heating, but this is not essential. The additive
package(s) will typically
be formulated to contain the additive(s) in proper amounts to provide the
desired concentration,
and/or to carry out the intended function in the final formulation when the
additive package(s)
is/are combined with a predetermined amount of base oil. Thus, additives (B)
and (C), in
accordance with the present invention, may be admixed with small amounts of
base oil or other
compatible solvents together with other desirable additives to form additive
packages containing
active ingredients in an amount, based on the additive package, of, for
example, from 2.5 to 90,
preferably from 5 to 75, most preferably from 8 to 60, mass % of additives in
the appropriate
proportions, the remainder being base oil.
The final formulation as a trunk piston engine oil may typically contain 30,
preferably 10
to 28, more preferably 12 to 24, mass % of the additive package(s), the
remainder being base oil.
The trunk piston engine oil may have a compositional TBN (using ASTM D2896) of
20 to 60,
such as, 30 to 55. For example, it may be 40 to 55 or 35 to 50.
EXAMPLES
The present invention is illustrated by but in no way limited to the following
examples.
18

CA 02833977 2013-11-21
COMPONENTS
The following components were used:
Ester Basestocks (Al)
= a polyol ester (PRIOLUBE (Registered Trade Mark) 3970), a
trimethylolpropane ester
with C8-10 fatty acids, having a viscosity of 4.4 mm2s-I at 100 C, ex Croda
Lubricants;
= a polymer ester (KETJENLUBE (Registered Trade Mark) 115), in the form of
a
copolymer of alpha-olefins and a dicarboxylic acid dibutylester with an
average
molecular weight of approximately 1400.
Basestocks (A2)
= a Group I oil (XOMAPE 600) (for comparison)
= a Group II oil (RLOP 600)
= a Group III oil (YUBASE 8)
Commercial identifications are in parentheses.
Detergents (B)
= calcium alkyl salicylate (BI 8.0)
= calcium alkyl salicylate (BI 3.0)
Basicity indices are in parentheses.
19

CA 02833977 2013-11-21
. ,
PIBSA (C)
a polyisobutene succinic anhydride derived from a polyisobutene having a
number average
molecular weight of 950
HFO
a heavy fuel oil (ISO-F-RMK 380)
TRUNK PISTON MARINE ENGINE LUBRICATING OILS (TPEO'S)
Selections of the above components were blended to give a range of TPEO's.
Some are
examples of the invention; others are reference examples for comparison
purposes. The
compositions of the TPEO's tested when each contained an HFO are given (in
mass %) in the
tables below under the RESULTS heading.
TESTING
Light Scattering
Test trunk piston marine engine lubricating oils (TPEO's) were evaluated for
asphaltene
dispersancy using light scattering according to the Focused Beam Reflectance
Method
("FBRM"), which predicts asphaltene agglomeration and hence 'black sludge'
formation.
The FBRM test method was disclosed at the 7th International Symposium on
Marine
Engineering, Tokyo, 24th - 28th October 2005, and was published in "The
Benefits of Salicylate
Detergents in TPEO Applications with a Variety of Base Stocks" in the
Conference Proceedings.
Further details were disclosed at the CIMAC Congress, Vienna, 21st -24th May
2007 and
published in "Meeting the Challenge of New Base Fluids for the Lubrication of
Medium Speed

CA 02833977 2013-11-21
' =
Marine Engines ¨ An Additive Approach" in the Congress Proceedings. In the
latter paper it is
disclosed that, by using the FBRM method, it is possible to obtain
quantitative results for
asphaltene dispersancy that predict performance for lubricant systems based on
base stocks
containing greater than or less than 90% saturates, and greater than or less
than 0.03% sulphur.
The predictions of relative performance obtained from FBRM were confirmed by
engine tests in
marine diesel engines.
The FBRM probe contains fibre optic cables through which laser light travels
to reach the
probe tip. At the tip, an optic focuses the laser light to a small spot. The
optic is rotated so that
the focussed beam scans a circular path between the window of the probe and
the sample. As
particles flow past the window, they intersect the scanning path giving
backscattered light from
the individual particles.
The scanning laser beam travels much faster than the particles; this means
that the
particles are effectively stationary. As the focussed beam reaches one edge of
the particle, the
amount of backscattered light increases; the amount will decrease when the
focussed beam
reaches the other edge of the particle.
The instrument measures the time of the increased backscatter. The time period
of
backscatter from one particle is multiplied by the scan speed and the result
is a distance or chord
length. A chord length is a straight line between any two points on the edge
of a particle. This is
represented as a chord length distribution, a graph of numbers of chord
lengths (particles)
measured as a function of the chord length dimensions in microns. As the
measurements are
performed in real time, the statistics of a distribution can be calculated and
tracked. FBRM
typically measures tens of thousands of chords per second, resulting in a
robust number-by-chord
length distribution. The method gives an absolute measure of the particle size
distribution of the
asphaltene particles.
The Focused beam Reflectance Probe (FBRM), model Lasentec D600L, was supplied
by
Mettler Toledo, Leicester, UK. The instrument was used in a configuration to
give a particle size
21

CA 02833977 2013-11-21
. i ' =
resolution of 1 gm to 1 mm. Data from FBRM can be presented in several ways.
Studies have
suggested that the average counts per second can be used as a quantitative
determination of
asphaltene dispersancy. This value is a function of both the average size and
level of
agglomerate. In this application, the average count rate (over the entire size
range) was
monitored using a measurement time of 1 second per sample.
The test TPEO's were heated to 60 C and stirred at 400rpm; when the
temperature
reached 60 C the FBRM probe was inserted into the sample and measurements made
for 15
minutes. An aliquot of heavy fuel oil (10% w/w) was introduced into the TPEO
under stirring
using a four-blade stirrer (at 400 rpm). A value for the average counts per
second was taken
when the count rate had reached an equilibrium value (typically overnight).
RESULTS
Light Scattering
The results of the FBRM tests are summarized in the tables below, where lower
particle
count indicates better performance.
Reference examples are designated "Ref'.
TABLE 1
Each TPEO tested had a BN of 40, contained 1.23 mass% (in terms of calcium) of

calcium salicylate of BI 8.0 and 0.24 mass % (in terms of calcium) of calcium
salicylate of BI
3.0, and contained the same amount of Zn and of silicone antifoam. The
remainder of the
finished oil components are given in the table below:
22

CA 02833977 2013-11-21
Example PIBSA Priolube Group Group I Lasentec Counts
(C) 3970 II Oil
(% (Al) Oil (A2)
active (wt %)
matter)
Ref 1 - Balance 2,032.43
Ref 2 - Balance - 5,988.84
Ref 3 10.00 Balance - 9,613.23
Ref 4 30.00 Balance - 732.81
Ref 5 4.80 - Balance - 2,205.86
1 4.80 10.00 Balance - 786.41
2 4.80 30.00 Balance - 12.82
3 4.80 80.83 13.89
Ref 3 and Ref 4 are illustrative of US Patent Application Publication No.
2011/0319304
Al (`304).
Ref 4 (use of ester alone) confirms the teaching of '304.
Ref 5 (use of PIBSA alone) confirms the teaching of '594.
Examples 1-3 confirm the synergy of PIBSA and ester.
TABLE 2
Each TPEO tested had a BN of 40, contained 0.75 mass % (in terms of calcium)
of calcium
salicylate of 131 8.0 and 0.68 mass % (in terms of calcium) of calcium
salicylate of BI 3.0, and
23

CA 02833977 2013-11-21
' , = .
contained the same amount of Zn. The remainder of the finished oil components
are given in the
table below:
Example PIBSA (C) Priolube Ketjenlube Group Group
Group Lasentec
(% active 3970 (Al) 115 II (A2) I III
(A2) Counts
matter) (wt %) (Al)
(wt A)
Ref 6 - - - - Balance -
933.83
4 4.80 1.00- Balance - - 391.79
5 4.80 3.00- Balance - - 223.56
6 4.80 5.00- Balance - - 251.08
7 4.80 7.00- Balance - - 161.13
8 4.80 10.00- Balance - - 48.38
9 0.80 10.00- Balance - - 3,499.45
10 1.60 10.00- Balance - - 1,333.98
11 2.40 10.00- Balance - - 421.74
12 3.20 10.00- Balance - - 268.40
13 4.00 10.00- Balance - - 47.87
14 4.80 10.00- - - Balance 737.14
15 4.80 - 10 Balance - - 110.03
The results show that varying the treat rate of PIBSA and ester affects
performance: in
Examples 4-8, the PIBSA treat rate is kept constant and the ester treat rate
progressively
increased; in Examples 9-13, the ester treat rate is kept constant and the
PIBSA treat rate is
progressively increased. Example 14 shows the applicability of the invention
to a Group III base
oil eyond that of Ref 6 (a Group I oil) and Example 15 shows the applicability
of the invention to
esters other than Priolube 3970.
24

CA 02833977 2013-11-21
' ,/ .
TABLE 3
Each TPEO treated had a BN of 30, contained 0.56 mass % (in terms of calcium)
of
calcium salicylate of BI 8.0 and 0.51 mass % (in terms of calcium) of calcium
salicylate of BI
3.0, and contained the same amount of Zn. The remainder of the finished oil
components are
given in the table below:
Example PIBSA Priolube Group II Group I Lasentec
(C) 3970 (A2) Counts
(% active (Al)
matter) (wt %)
Ref 7 - - - Balance 1,755.35
Ref 8 2.40 - Balance - 3,638.42
17 2.40 1.00 Balance - 1,622.23
18 2.40 3.00 Balance - 1,805.06
19 2.40 5.00 Balance - 1,626.40
20 2.40 7.00 Balance - 1,135.09
21 2.40 10.00 Balance - 899.70
The results show that the effect of the invention is exhibited in lower BN
TPEO's.

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Title Date
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(22) Filed 2013-11-21
(41) Open to Public Inspection 2014-05-21
Examination Requested 2018-05-30

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Registration of Documents $100.00 2013-11-21
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