FIELD OF THE INVENTION
[0001] 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
[0002] Marine trunk piston engines generally use Heavy Fuel Oil ('HFO') 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 which 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 which 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.
[0003] It is therefore highly desirable that trunk piston engine oils ('TPEO's) prevent
or inhibit asphaltene precipitation. The prior art describes ways of doing this.
[0004] WO 96/26995 discloses the use of a hydrocarbyl-substituted phenol to reduce 'black paint' in
a diesel engine.
WO 96/26996 discloses the use of a demulsifier for water-in-oil emulsions, for example, a polyoxyalkylene
polyol, to reduce 'black paint' in diesel engines.
US-B2-7,053,027 describes use of one or more overbased metal carboxylate detergents in combination
with an antiwear additive in a dispersant-free TPEO.
[0005] The problem of asphaltene precipitation is more acute at higher basestock saturate
levels.
WO 2008/128656 describes a solution by use of an overbased metal hydrocarbyl-substituted hydroxybenzoate
detergent having a basicity index of less than 2 and a degree of carbonation of 80%
or greater in a marine trunk piston engine lubricant to reduce asphaltene precipitation
in the lubricant. Exemplified are lubricants comprising a Group II basestock, which
has a higher basestock saturate level than a Group I basestock.
[0006] The above-described solution is however restricted to a specific class of detergents.
It is now found, in the present invention, that the problem in
WO 2008/128656 is solved for a different range of overbased metal carboxylate detergents by employing,
in combination therewith, a hydrocarbyl-substituted carboxylic acid, anhydride, ester
or amide in Group II basestocks.
SUMMARY OF THE INVENTION
[0007] 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 an
oil of lubricating viscosity, in a major amount, containing 50 mass % or more of a
Group II basestock, and, in respective minor amounts:
- (A) an overbased metal hydrocarbyl-substituted hydroxybenzoate detergent having:
(A1) a basicity index of two or greater and a degree of carbonation of 80% or greater;
or
(A2) a basicity index of two or greater and a degree of carbonation of less than 80%;
or
(A3) a basicity index of less than two and a degree of carbonation of less than 80%;
where degree of carbonation is the percentage of carbonate present in the overbased
metal hydrocarbyl-substituted hydroxybenzoate detergent expressed as a mole percentage
relative to the total excess base in the detergent; and
- (B) a hydrocarbyl-substituted carboxylic acid or anhydride thereof, wherein the or
at least one hydrocarbyl group contains at least eight carbon atoms; the acid or anhydride
constituting at least 1 and up to 10 mass % of the lubricating oil composition;
wherein the treat rate of additives (A) and (B) contained in the lubricating oil composition
is in the range of 2 to 20 mass %.
[0008] A second aspect of the invention is the use of a detergent (A) in combination with
a carboxylic acid or anhydride (B), 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 in a major amount and contains 50 mass % or more of a Group II basestock,
to improve asphaltene handling during operation of the engine, fueled by a heavy fuel
oil, and its lubrication by the composition, in comparison with analogous operation
when the same amount of detergent (A) is used in the absence of(B).
[0009] A third aspect of the invention is a method of operating a trunk piston medium-speed
compression-ignited marine engine comprising
- (i) fueling the engine with a heavy fuel oil; and
- (ii) lubricating the crankcase of the engine with a composition as defined in the
first aspect of the invention.
[0010] A fourth 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 as defined in 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.
[0011] 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 in excess of 50 mass % of a composition;
"minor amount" means less than 50 mass % of a composition;
"TBN" means total base number as measured by ASTM D2896.
Furthermore in this specification:
"calcium content" is as measured by ASTM 4951;
"phosphorus content" is as measured by ASTM D5185;
"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.
[0012] 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.
[0013] 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
[0014] The features of the invention will now be discussed in more detail below.
OIL OF LUBRICATING VISCOSITY
[0015] The lubricating oils may range in viscosity from light distillate mineral oils to
heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to 40 mm
2/sec, as measured at 100°C.
[0016] Natural oils include animal oils and vegetable oils (e.g., caster 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.
[0017] 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, analogs
and homologs thereof.
[0018] Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal
hydroxyl groups have been modified by esterification, etherification, etc., constitute
another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene
polymers prepared by polymerization of ethylene oxide or propylene oxide, and the
alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene
glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene
glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters
thereof, for example, the acetic acid esters, mixed C
3-C
8 fatty acid esters and C
13 Oxo acid diester of tetraethylene glycol.
[0019] Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic
acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic
acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic
acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids)
with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). 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.
[0020] Esters useful as synthetic oils also include those made from C
5 to C
12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol and tripentaerythritol.
[0021] Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone
oils and silicate oils comprise another useful class of synthetic lubricants; such
oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,
tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane,
poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other synthetic lubricating
oils include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate,
trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
[0022] 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; petroleum oil obtained directly from distillation; or ester oil obtained
directly from an esterification and used without further treatment would be an unrefined
oil. 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 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.
[0023] Definitions for the base stocks and base oils in this invention are the same as those
found in the
American Petroleum Institute (API) publication "Engine Oil Licensing and Certification
System", Industry Services Department, Fourteenth Edition, December 1996, Addendum
1, December 1998. Said publication categorizes base stocks as follows:
- a) 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.
- b) 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.
- c) 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.
- d) Group IV base stocks are polyalphaolefins (PAO).
- e) Group V base stocks include all other base stocks not included in Group I, II,
III, or IV.
[0024] Analytical Methods for Base Stock are tabulated below:
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 |
[0025] As stated, the oil of lubricating viscosity in this invention contains 50 mass %
or more of a Group II basestock. Preferably, it contains 60, such as 70, 80 or 90,
mass % or more of a Group II basestock. The oil of lubricating viscosity may be substantially
all Group II basestock.
OVERBASED METAL DETERGENT (A)
[0026] 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.
[0027] In the present invention, overbased metal detergents (A) are overbased metal hydrocarbyl-substituted
hydroxybenzoate, preferably hydrocarbyl-substituted salicylate, detergents.
[0028] "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. The overbased metal hydrocarbyl-substituted
hydroxybenzoate typically has the structure shown:
wherein R is a linear or branched aliphatic hydrocarbyl group, and more preferably
an alkyl group, including straight- or branched-chain alkyl groups. There may be more
than one R group attached to the benzene ring. M is an alkali metal (e.g. lithium,
sodium or potassium) or alkaline earth metal (e.g. calcium, magnesium barium or strontium).
Calcium or magnesium is preferred; calcium is especially preferred. The COOM group
can be in the ortho, meta or para position with respect to the hydroxyl group; the
ortho position is preferred. The R group can be in the ortho, meta or para position
with respect to the hydroxyl group.
[0029] Hydroxybenzoic 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 uncarboxylated phenol. Hydroxybenzoic acids may be non-sulphurized
or sulphurized, and may be chemically modified and/or contain additional substituents.
Processes for sulphurizing a hydrocarbyl-substituted hydroxybenzoic acid are well
known to those skilled in the art, and are described, for example, in
US 2007/0027057.
[0030] In hydrocarbyl-substituted hydroxybenzoic acids, the hydrocarbyl group is preferably
alkyl (including straight- or branched-chain alkyl groups), and the alkyl groups advantageously
contain 5 to 100, preferably 9 to 30, especially 14 to 24, carbon atoms.
[0031] 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.
[0032] 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.
[0033] Carbonated overbased metal detergents typically comprise amorphous nanoparticles.
Additionally, there are disclosures of nanoparticulate materials comprising carbonate
in the crystalline calcite and vaterite forms.
[0034] The basicity of the detergents may be expressed as a total base number (TBN). 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). In this invention, Basicity Index and Degree of Carbonation may be used.
Basicity Index is the molar ratio of total base to total soap in the overbased detergent.
Degree of Carbonation is the percentage of carbonate present in the overbased detergent
expressed as a mole percentage relative to the total excess base in the detergent.
[0035] Overbased metal hydrocarbyl-substituted hydroxybenzoates can be prepared by any of
the techniques employed in the art. A general method is as follows:
- 1. Neutralisation of hydrocarbyl-substituted hydroxybenzoic acid with a molar excess
of metallic base to produce a slightly overbased metal hydrocarbyl-substituted hydroxybenzoate
complex, in a solvent mixture consisting of a volatile hydrocarbon, an alcohol and
water;
- 2. Carbonation to produce colloidally-dispersed metal carbonate followed by a post-reaction
period;
- 3. Removal of residual solids that are not colloidally dispersed; and
- 4. Stripping to remove process solvents.
[0036] Overbased metal hydrocarbyl-substituted hydroxybenzoates can be made by either a
batch or a continuous overbasing process.
[0037] Metal base (e.g. metal hydroxide, metal oxide or metal alkoxide), preferably lime
(calcium hydroxide), may be charged in one or more stages. The charges may be equal
or may differ, as may the carbon dioxide charges which follow them. When adding a
further calcium hydroxide charge, the carbon dioxide treatment of the previous stage
need not be complete. As carbonation proceeds, dissolved hydroxide is converted into
colloidal carbonate particles dispersed in the mixture of volatile hydrocarbon solvent
and non-volatile hydrocarbon oil.
[0038] Carbonation may by effected in one or more stages over a range of temperatures up
to the reflux temperature of the alcohol promoters. Addition temperatures may be similar,
or different, or may vary during each addition stage. Phases in which temperatures
are raised, and optionally then reduced, may precede further carbonation steps.
[0039] The volatile hydrocarbon solvent of the reaction mixture is preferably a normally
liquid aromatic hydrocarbon having a boiling point not greater than about 150°C. Aromatic
hydrocarbons have been found to offer certain benefits, e.g. improved filtration rates,
and examples of suitable solvents are toluene, xylene, and ethyl benzene.
[0040] The alkanol is preferably methanol although other alcohols such as ethanol can be
used. Correct choice of the ratio of alkanol to hydrocarbon solvents, and the water
content of the initial reaction mixture, are important to obtain the desired product.
[0041] Oil may be added to the reaction mixture; if so, suitable oils include hydrocarbon
oils, particularly those of mineral origin. Oils which have viscosities of 15 to 30
mm
2/sec at 38°C are very suitable.
[0042] After the final treatment with carbon dioxide, the reaction mixture is typically
heated to an elevated temperature, e.g. above 130°C, to remove volatile materials
(water and any remaining alkanol and hydrocarbon solvent). When the synthesis is complete,
the raw product is hazy as a result of the presence of suspended sediments. It is
clarified by, for example, filtration or centrifugation. These measures may be used
before, or at an intermediate point, or after solvent removal.
[0043] The products are generally used as an oil solution. If the reaction mixture contains
insufficient oil to retain an oil solution after removal of the volatiles, further
oil should be added. This may occur before, or at an intermediate point, or after
solvent removal.
[0044] In this invention, (A) may have:
(A1) a basicity index of two or greater and a degree of carbonation of 80% or greater;
or
(A2) a basicity index of two or greater and a degree of carbonation of less than 80%;
or
(A3) a basicity index of less than two and a degree of carbonation of less than 80%.
CARBOXYLIC ACID OR ANHYDRIDE THEREOF (B)
[0045] As stated, the acid or anhydride thereof constitutes at least 1 mass % and up to
10 mass % of the lubricating oil composition. Preferably it constitutes from 1.5 and
up to 10, such as 2 to 10, for example 3 to 6, mass %. (B) may be a mixture.
[0046] The acid may be mono or polycarboxylic, preferably dicarboxylic, acid. The hydrocarbyl
group preferably has from 8 to 400, such as 8 to 100, carbon atoms.
[0047] As (B), an anhydride of a dicarboxylic acid is preferred.
[0048] Preferably, the hydrocarbyl group is a polyalkenyl group. Such polyalkenyl moiety
may have a number average molecular weight of from 200 to 3000, preferably from 350
to 950.
[0049] Suitable hydrocarbons or polymers employed in the formation of the acid/derivative
of the present invention include homopolymers, interpolymers or lower molecular weight
hydrocarbons. One family of such polymers comprise polymers of ethylene and/or at
least one C
3 to C
28 alpha-olefin having the formula H
2C=CHR
1 wherein R
1 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 R
1 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 of this invention may contain a minor amount, e.g. 0.5 to 5 mole % of
a C
4 to C
18 non-conjugated diolefin comonomer. However, it is preferred that the polymers of
this invention 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 in this invention 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.
[0050] These polymers may be prepared by polymerizing alpha-olefin monomer, or mixtures
of alpha-olefin monomers, or mixtures comprising ethylene and at least one C
3 to C
28 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 C
13 NMR. Interpolymers of this latter type may be characterized by the formula POLY-C(R
1)=CH
2 wherein R
1 is C
1 to C
26 alkyl, preferably C
1 to C
18 alkyl, more preferably C
1 to C
8 alkyl, and most preferably C
1 to C
2 alkyl, (e.g., methyl or ethyl) and wherein POLY represents the polymer chain. The
chain length of the R
1 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=CH
2, and a portion of the polymers can contain internal monounsaturation, e.g. POLY-CH=CH(R
1), wherein R
1 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.
[0051] Another useful class of polymers is polymers prepared by cationic polymerization
of isobutene, styrene, and the like. Common polymers from this class include polyisobutenes
obtained by polymerization of a C
4 refinery stream having a butene content of about 35 to about 75 mass %, and an isobutene
content of about 30 to about 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 of the present invention because it
is readily available by cationic polymerization from butene streams (e.g., using AlCl
3 or BF
3 catalysts). Such polyisobutylenes generally contain residual unsaturation in amounts
of about one ethylenic double bond per polymer chain, positioned along the chain.
A preferred embodiment utilizes poiyisobutyiene 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 Glissopal™
(from BASF) and Ultravis™ (from BP-Amoco).
[0052] 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
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.
[0053] To produce (B) the hydrocarbon or polymer backbone may be functionalized, with carboxylic
acid producing moieties (acid or anhydride 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.
[0054] Processes for reacting polymeric hydrocarbons with unsaturated carboxylic acids and
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 B1;
CA-1,335,895 and
GB-A-1,440,219. The polymer or hydrocarbon may be functionalized, with carboxylic acid producing
moieties (acid or anhydride) by reacting the polymer or hydrocarbon under conditions
that result in the addition of functional moieties or agents, i.e., acid or anhydride
moieties, etc., 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.
[0055] Selective functionalization can be accomplished by halogenating, e.g., chlorinating
or brominating the unsaturated α-olefin polymer to about 1 to 8 mass %, 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 about 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 about 180°C to 235°C, for about 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 monounsaturated carboxylic reactant are mixed and heated while adding chlorine
to the hot material.
[0056] 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, e.g., carboxylic reactant, are contacted at elevated temperature to cause
an initial thermal "ene" reaction to take place. Ene reactions are known.
[0057] 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 about 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 mass %, preferably 5 to 30 mass % polymer based on the initial total
oil solution.
[0058] The free-radical initiators that may be used are peroxides, hydroperoxides, and azo
compounds, preferably those that have a boiling point greater than about 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, typically
is used 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 about
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 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 of the present invention.
[0059] 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 C
4 to C
10 dicarboxylic acid wherein (a) the carboxyl groups are vicinyl, (i.e., located on
adjacent carbon atoms) and (b) at least one, preferably both, of said adjacent carbon
atoms are part of said mono unsaturation; (ii) derivatives of (i) such as anhydrides;
and (iii) monounsaturated C
3 to C
10 monocarboxylic acid wherein the carbon-carbon double bond is conjugated with the
carboxy group, i.e., of the structure -C=C-CO-. 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 and cinnamic
acid.
[0060] To provide the required functionality, the monounsaturated carboxylic reactant, preferably
maleic anhydride, typically will be used in an amount ranging from about equimolar
amount to about 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.
[0061] The treat rate of additives (A) and (B) contained in the lubricating oil composition
is in the range of 2, preferably 2.5, to 20, more preferably 5 to 18, mass %.
CO-ADDITIVES
[0062] The lubricating oil composition of the invention may comprise further additives,
different from and additional to (A) and (B). Such additional additives may, for example
include ashless dispursants, other metal detergents, anti-wear agents such as zinc
dihydrocarbyl dithiophosphates, anti-oxidants and demulsifiers.
[0063] It may be desirable, although not essential, to prepare one or more additive packages
or concentrates comprising the additives, whereby additives (A) and (B) 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 lubricant. Thus, additives (A) and (B), 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.
[0064] The final formulations 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. Preferably, the trunk piston engine oil has a compositional TBN (using
ASTM D2896) of 20 to 60, such as 25 to 55.
EXAMPLES
[0065] The present invention is illustrated by but in no way limited to the following examples.
COMPONENTS
[0066] The following components were used:
Component (A):
(A1) a calcium salicylate detergent having a TBN of 350 (basicity index of two or
greater; a degree of carbonation of 80% or greater)
(A2) a calcium salicylate detergent having a TBN of 225 (basicity index of two or
greater; a degree of carbonation of less than 80%)
(A3) a calcium salicylate detergent having a TBN of 65 (basicity index of less than
two; a degree of carbonation of less than 80%)
Component (B):
(B1) oleic acid
(B2) polyisobutene succinic acid derived from a polyisobutene having a number average
weight of 450
(B3) a polyisobutene succinic anhydride ("PIBSA") derived from a polyisobutene of
number average molecular weight 950 (72% ai)
(B4) polyisobutene succinic anhydride ("PIBSA") derived from polyisobutene having
a number average molecular weight of 450 (75% ai)
(B5) iso-octadecyl succinic anhydride
(B6) bis (2-hydroxypropyl) 2-dodecyl succinate
(B7) oleamide
(B8) tetraethylenepentamine, di-iso-octadecyl amide.
Base oil I: |
an API Group I base oil known as XOMAPE600 |
Base oil II: |
an API Group II base oil known as CHEV600R |
HFO: |
a heavy fuel oil, ISO-F-RMK 380 |
Phenate: |
a calcium phenate detergent having a TBN of 255 |
Sulfonate: |
a calcium sulfonate detergent having a TBN of 425 |
LUBRICANTS
[0067] Selections of the above components were blended to give a range of trunk piston marine
engine lubricants. Some of the lubricants are examples of the invention; others are
reference examples for comparison purposes. The compositions of the lubricants tested
when each contained HFO are shown in the tables below under the "Results" heading.
TESTING
Panel Coker Test
[0068] The Panel Coker test was used to evaluate the performance of test lubricants. The
test method involved splashing the oil under test onto a heated metal plate by spinning
a metal comb-like device within a sump containing the oil. At the end of the test
period, deposits formed may be assessed by weight and by visual inspection of the
plate's appearance.
[0069] The testing was performed using a panel coker tester, model PK-S, supplied by the
Yoshida Kagaku Kikai Co., of Osaka, Japan. Test panels were thoroughly cleaned and
then weighed before inserting them into the apparatus. The test oil was mixed with
2.5% HFO and 225g of the resulting mixture added to the sump of the apparatus. When
the temperature of the oil was at 100°C and the test plate at 320°C, a metal comb
device was automatically rotated causing the oil to be splashed onto the test plate.
[0070] The test sequence lasted for 120 cycles, each cycle consisting of 15 seconds in which
the oil was splashed onto the plate and 45 seconds without splashing.
[0071] At the end of test, the plate was washed with n-heptane, dried, reweighed and visually
examined. The deposit weight was reported.
Light Scattering
[0072] Test lubricants were also evaluated for asphaltene dispersancy using light scattering
according to the Focused Beam Reflectance Method ("FBRM"), which predicts asphaltene
agglomeration and hence 'black sludge' formation.
[0074] 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.
[0075] 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 there is an increase in the amount of backscattered light; the amount will
decrease when the focussed beam reaches the other edge of the particle.
[0076] 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.
[0077] 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 resolution of 1 µm to 1mm. 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.
[0078] The test lubricant formulations 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
lubricant formulation 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
Panel Coker Test
[0079] The results of the Panel Coker tests are summarized in the tables below where figures
are mass % of active ingredient unless otherwise stated.
TABLE 1
Ex |
Ca salicylate (A1) |
PIBSA (B3) |
Base oil I |
Base oil II |
Deposits (g) |
1 |
8.57 |
7.00 |
- |
84.43 |
0.0221 |
X |
8.57 |
- |
|
91.43 |
0.0759 |
Y |
8.57 |
- |
91.43 |
|
0.0450 |
[0080] Each lubricant contained 44.6 mM of soap and had a TBN of 30. Also, each lubricant
contained 0.5 mass % HFO.
[0081] The results show that the example of the invention (Ex 1) gave rise to much lower
deposits, i.e. improved asphaltene dispersency, than a corresponding example lacking
PIBSA (Ex X) and also than an example in a Group I base oil lacking PIBSA (Ex Y).
TABLE 2
Ex |
Ca phenate |
Ca sulfonate |
PIBSA (B3) |
Base oil II |
Deposits (g) |
P |
4.40 |
4.40 |
7.00 |
84.20 |
0.1489 |
Q |
4.40 |
4.40 |
- |
91.20 |
0.1009 |
[0082] Each lubricant contained 42 mM of soap and had a TBN of 30. Also, each lubricant
contained 0.5 mass % HFO.
[0083] The results show that the presence of PIBSA (Ex P) diminishes the asphaltene handling
performance when the detergent is a phenate/sulfonate combination. This contrasts
with the finding of TABLE 1 that, when the detergent is a salicylate, the performance
is improved.
Light Scattering
[0084] Results of the FBRM tests are summarised in TABLE 3 below.
TABLE 3
Ex |
Ca salicylate (A1) (mass % a.i.) |
Component (B) (2.6 mass % a.i.) |
Particle count/s |
Ref |
2.6 |
- |
1,128 |
|
- |
B 1 |
4,777 |
|
2.6 |
B1 |
175 |
|
- |
B2 |
3,944 |
|
2.6 |
B2 |
486 |
|
- |
B3 |
3,763 |
|
2.6 |
B3 |
168 |
|
- |
B4 |
5,640 |
|
2.6 |
B4 |
167 |
|
- |
B5 |
5,073 |
|
2.6 |
B5 |
240 |
|
- |
B6 |
6,559 |
|
2.6 |
B6 |
363 |
|
- |
B7 |
16,523 |
|
2.6 |
B7 |
859 |
|
- |
B8 |
2,110 |
|
2.6 |
B8 |
294 |
[0085] The results show that, in all cases, (A) plus (B) is better than (A) alone.
[0086] Further results of FBRM, carried out separately from those of TABLE 3 in a recalibrated
instrument, are summarised in TABLE 4 below.
TABLE 4
Ex |
Ca Salicylate (A) (mass % a.i.) |
Component (B3) (mass % a.i.) |
Particle count/s |
Ref |
- |
2.6 |
13,710 |
|
A1 (2.6) |
- |
15,888 |
|
A1 (2.6) |
2.6 |
4,355 |
Ref |
- |
2.1 |
15,191 |
|
A2 (2.1) |
- |
8,782 |
|
A2 (2.1) |
2.1 |
6,149 |
|
A2 (2.1) |
2.6 |
3,438 |
Ref |
- |
1.8 |
15,564 |
|
A3 (1.8) |
- |
10,748 |
|
A3 (1.8) |
1.8 |
5,803 |
|
A3 (1.8) |
2.6 |
3,629 |
[0087] The results show that (A), represented by each of A1, A2 and A3, in combination with
(B3) is better than (A) alone and better than (B3) alone.