Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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TITLE
Lubricating Compositions Containing Sulphonates
FIELD OF INVENTION
The present invention relates to a lubricating composition containing a
detergent package a dispersant and an oil of lubricating viscosity. The
invention
further relates to the use of the lubricating composition in marine diesel
cylinder
lubricants.
BACKGROUND OF THE INVENTION
[0001] It is known to add various additives to an oil of lubricating
viscosity
for diesel or gasoline engines to reduce wear and improve cleanliness. In
diesel
engines an oil of lubricating viscosity is used particularly to reduce wear of
cylinder liners and piston rings. Often engine operating temperatures and
pressures are sufficient to break down the film of the oil of lubricating
viscosity
on the internal walls of the cylinder. As a consequence of this, the cylinder
experiences increased wear and decreased engine cleanliness due to deposits.
Formation of high levels of deposits around the piston rings can also result
in
excessive wear.
[0002] International Publication WO 03/018728 Al (Moreton et al.)
discloses a lubricating composition containing a metal salt of linear
compounds
containing phenolic and salicylic units or derivatives thereof. The
lubricating
composition may also contain an ashless dispersant and a zinc dithiophosphate.
[0003] US
Patent 6,277,794, Dunn, discloses the use of a marine diesel
engine lubricant composition containing (a) an overbased metal detergent
having a TBN of at least 300 and/or (b) a metal detergent other than component
(a), provided that if detergent (b) is present the composition does not
contain a
minor amount of an extreme pressure additive; and (c) ashless antiwear
additives; and (d) an oil of lubricating viscosity.
[0004] US
Patent 6,339,051, Carey et al., discloses diesel cylinder oils with
improved cleanliness and load carrying capabilities by using an additive
package containing at least one detergent, an antioxidant, an antiwear agent
and
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a dispersant. The detergent component contains at least one of an overbased
phenate, phenylate, salicylate or sulphonate.
[0005] US Patent 6,376,434, Katafuchi, discloses lubricating oil
compositions for diesel engines containing at least one of (a) overbased
sulphonate, overbased phenates and overbased salicylates; and (b) a bis-type
succinic imide compound.
[0006] US Patent 6,551,965, Nagamatsu, discloses a marine diesel
lubricating oil composition containing an overbased alkyl sulphonate detergent
and an overbased sulphurised alkylphenate detergent. The overbased
sulphurised alkylphenate has a TBN of 110 or more.
[0007]
British Patent application GB 2,328,217A discloses marine diesel
lubricating oil compositions containing a polyalkylene succinimide compound
for improving anti-wear. The lubricating oil composition can further include
up
to 6% of at least one highly overbased detergent selected from alkyl or
alkenyl
phenates, alkyl or alkenyl phenate-carboxylates, alkyl or alkenyl aromatic
sulphonates; and mixtures thereof.
[0008]
European Patent application EP 1,086,960 discloses a lubricating oil
composition containing novel succinimide compounds and at least one detergent
selected from overbased sulphonates, phenates and salicylates of alkaline
earth
metals.
[0009] It
would be advantageous to have a lubricating composition with at
least one of cleanliness properties, antiwear performance and deposit control.
The present invention provides a lubricating composition with at least one of
cleanliness properties, antiwear performance and deposit control.
SUMMARY OF THE INVENTION
[0010] The
present invention provides a lubricating composition comprising:
(a) a detergent package comprising:
(i) an oligomeric reaction product of (1) a hydrocarbyl-substituted
phenol; (2) an aldehyde; and (3) a carboxyl-substituted phenol
or a carboxyl-substituted phenylamine; or a salt of the reaction
product;
(ii) a sulphonate; and
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(iii) optionally a phenate;
(b) a optionally dispersant; and
(c) an oil of lubricating viscosity,
wherein the sulphonate detergent is overbased with a metal ratio of about
12.5:1
to about 40:1.
[0011] The invention further provides a process to prepare a
lubricating
composition comprising mixing:
(a) a detergent package comprising:
(i) an oligomeric reaction product of (1) a hydrocarbyl-substituted
phenol; (2) an aldehyde; and (3) a carboxyl-substituted phenol or
a carboxyl-substituted phenylamine; or a salt of the reaction
product;
(ii) a sulphonate; and
(iii) optionally a phenate;
(b) optionally a dispersant; and
(c) an oil of lubricating viscosity,
wherein the sulphonate detergent is overbased with a metal ratio of about
12.5:1
to about 40:1.
[0012] The invention further provides a method for lubricating an
internal
combustion engine, comprising supplying thereto a lubricant comprising the
composition as described herein.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present invention provides a lubricating composition
comprising:
(a) a detergent package comprising:
(i) an oligomeric reaction product of (1) a hydrocarbyl-substituted
phenol; (2) an aldehyde; and (3) a carboxyl-substituted phenol or
a carboxyl-substituted phenylamine; or a salt of the reaction
product;
(ii) a sulphonate; and
(iii) optionally a phenate;
(b) optionally a dispersant; and
(c) an oil of lubricating viscosity,
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wherein the sulphonate detergent is overbased with a metal ratio of about
12.5:1
to about 40:1.
[0014] The
total base number (TBN) of the lubricating composition in one
embodiment is 30 or higher, in another embodiment 40 or higher, in another
embodiment 50 or higher and in another embodiment 60 or higher. Examples of
the TBN of the lubricating composition include 65, 70, 75 or 80.
Oligomeric Reaction Product
[0015] The
invention includes an oligomeric reaction product of (1) a
hydrocarbyl-substituted phenol; (2) an aldehyde; and (3) a carboxyl-
substituted
phenol or a carboxyl-substituted phenylamine; or a salt of the reaction
product.
The oligomeric reaction product is a detergent. In one embodiment the
oligomeric reaction product is a metal salt and in another embodiment the
oligomeric product is metal-free. The
oligomeric reaction product is
commercially available from The Lubrizol Corporation.
[0016] The hydrocarbyl-substituted phenol in one embodiment contains an
alkyl group containing 1 to 60 carbon atoms, in another embodiment 4 to 50
carbon atoms, in another embodiment 6 to 40 carbon atoms and in another
embodiment 7 to 30 carbon atoms, for instance 10, 12, 14 or 16. The alkyl
substituent is often derived from a polyolefin which may be a homopolymer
from one olefin monomer or a copolymer from a mixture of two or more olefin
monomers. The molecular weight Mw of the homopolymer and/or copolymer in
one embodiment is 250 to 5000, in another embodiment 350 to 3000 and in
another embodiment 450 to 2000, for instance 550, 1000 or 1600. The olefin
monomer may be an alpha-olefin, an internal olefin, or a polyene and includes
ethylene, propylene, butene isomers, pentene isomers, decene isomers, and
dienes. Useful polyolefins are polypropylenes and polyisobutylenes. Methods
to prepare the polyolefins and the alkylphenols via alkylation of phenol with
olefins or polyolefins are well known.
[0017] The
aldehyde in one embodiment has 1 to 6 carbon atoms and in
another embodiment 1 to 3 carbon atoms. The aldehyde may be formaldehyde
in one of its reactive forms such as formalin or paraformaldehyde.
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[0018] The oligomeric reaction product in one embodiment is represented
by
a substantially linear compound comprising at least one unit of the formulae
(I)
or (II):
(R2)i
___________________________ ¨
(I)
COOR3
or
(OH)f
(R4)9
each end of the compound having a terminal group of formulae (III) or (IV):
(OH)f
(R2)i
(RI)g
COOR3
(III) (W)
such groups being linked by divalent bridging groups, which may be the same or
different for each linkage; wherein in formulas (I)-(IV) f is 1, 2 or 3, in
one
embodiment 1 or 2; U is ¨OH, -NH2 -NHRI, -N(R1)2 or mixtures thereof, R1 is a
hydrocarbyl group containing 1 to 5 carbon atoms; R2 is hydroxyl or a
hydrocarbyl group and j is 0, 1, or 2; R3 is hydrogen or a hydrocarbyl group;
R4
is a hydrocarbyl group or a substituted hydrocarbyl group; g is 1, 2 or 3,
provided at least one R4 group contains 8 or more carbon atoms; and wherein
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the molecules on average contain at least one of unit (I) or (III) and at
least one
of unit (II) or (IV) and the ratio of the total number of units (I) and (III)
to the
total number of units of (II) and (IV) in the composition is about 0.1:1 to
about
2:1.
[0019] The U group in
formulae (i) and (iii) may be located in one or more
positions ortho, meta, or para to the -COOR3 group. In one embodiment the U
group is located ortho to the -COOR3 group. When the U group is a ¨OH group,
formulae (i) and (iii) are derived from 2-hydroxybenzoic acid (often called
salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid or mixtures
thereof. When U is a ¨NH2 group, formulae (i) and (iii) are derived from 2-
aminobenzoic acid (often called anthranilic acid), 3-aminobenzoic acid,
4-aminobenzoic acid or mixtures thereof.
[0020] The
divalent bridging group, which may be the same or different in
each occurrence, includes -CH2- (methylene bridge) and -CH2OCH2- (ether
bridge), either of which may be derived from an aldehyde such as formaldehyde
or a formaldehyde equivalent (e.g., paraform, formalin), ethanal or propanal.
[0021] In
one embodiment the oligomeric reaction product is a metal salt and
the metal is often mono-valent, di-valent or mixtures thereof. In
one
embodiment the metal is an alkali metal or alkaline earth metal such as
magnesium, calcium, potassium or sodium. In one embodiment the metal is
magnesium, in another embodiment calcium and in another embodiment
potassium. When the oligomeric reaction product is a metal salt the product is
often referred to as a salixarate or metal salixarate. In one embodiment the
oligomeric reaction product contains a metal and in an amount sufficient to
neutralise the product. In one embodiment the oligomeric reaction product
contains metal present in an amount sufficient to overbase the product. In one
embodiment the oligomeric reaction product contains the organic compound
represented by formulae (I) or (II) as defined above.
[0022] It is
believed that a significant fraction of oligomeric reaction product
molecules (prior to neutralisation) may be represented on average by the
following formula:
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0 OH OH OH OH 0
HO
I OH
HO OH
R5 R5
wherein each R5 can be the same or different, and are hydrogen or an alkyl
group, provided at least one R5 is alkyl. In a one embodiment, R5 is a
polyisobutene group (especially of molecular weight 200 to 1,000, or 550).
Significant amounts of di-or trinuclear species may also be present containing
one salicylic end group of formula (III).
[0023] The oligomeric reaction product and derivatives thereof are
described
in greater detail in U.S. patent number 6,200,936 and PCT Publications WO
01/56968 and WO 03/18728. In one embodiment the oligomeric reaction
product additionally provides antiwear performance.
[0024] The oligomeric reaction product is present at in one embodiment
at
0.01 to 15, in another embodiment 0.05 to 10, in another embodiment 0.1 to 8
and another embodiment 0.2 to 5 weight percent of the lubricating composition.
Overbased Sulphonate Detergent
[0025] The invention
further includes a sulphonate detergent. The
sulphonate detergent of the composition includes compounds represented by the
formula:
(R6)k¨A¨S03M (VI)
wherein each R6 is a hydrocarbyl group in one embodiment containing 6 to 40
carbon atoms, in another embodiment 8 to 25 carbon atoms and in another
embodiment 9 to 20 carbon atoms; A may be independently a cyclic or acyclic
hydrocarbon group; M is hydrogen, a valence of a metal ion, an ammonium ion
or mixtures thereof; and k is an integer of 0 to 5, for example 0, 1, 2, 3, 4,
5. In
one embodiment k is 1, 2 or 3, in another embodiment 1 or 2 and in another
embodiment 1. In non-overbased precursors of the sulfonate detergent, M can
be hydrogen and be present, for example, on less than 30%, in another
embodiment less than 20%, in another embodiment less than 10% and in another
embodiment less than 5% of the available M entities. When the sulfonate
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detergent is overbased, most or substantially all of the M entities will
represent
metal ions.
[0026] In one embodiment k is 1 and R6 is a branched alkyl group with 6
to
40 carbon atoms. In one embodiment k is 1 and R6 is a linear alkyl group with
6 to 40 carbon atoms.
[0027] Examples of suitable sulphonic acids capable of forming the
overbased sulphonate detergent include polypropene benzene sulphonic acid,
undecyl benzene sulphonic acid, dodecyl benzene sulphonic acid, tridecyl
benzene sulphonic acid, tetradecyl benzene sulphonic acid, pentadecyl benzene
sulphonic acid, hexadecyl benzene sulphonic acid and mixtures thereof. In one
embodiment the sulphonic acid includes undecyl benzene sulphonic acid,
dodecyl benzene sulphonic acid, tridecyl benzene sulphonic acid, tetradecyl
benzene sulphonic acid, octadecyl benzene sulphonic acid, tetraeicosyl benzene
sulphonic acid or mixtures thereof. In one embodiment of the invention the
sulphonic acid is a polypropene benzene sulphonic acid, where the polypropene
often contains 18 to 30 carbon atoms.
[0028] In one embodiment of the invention the sulphonate components are
calcium polypropene benzenesulphonate and calcium monoalkyl and dialkyl
benzenesulphonates wherein the alkyl groups contain at least 10 carbons, for
example 11, 12, 13, 14, or 15 carbon atoms.
[0029] When M is a valence of a metal ion, the metal may be monovalent,
divalent, trivalent or mixtures of such metals. When monovalent, the metal M
includes an alkali metal such as lithium, sodium, or potassium and when
divalent, the metal M includes an alkaline earth metal such as magnesium,
calcium or barium. When trivalent, the metal M may be aluminium. In one
embodiment the metal is an alkaline earth metal. In one embodiment the metal
is calcium.
[0030] When A is a cyclic hydrocarbon group, suitable groups include
phenyl or fused bicyclic groups such as naphthalene, indenyl, indanyl,
bicyclopentadienyl or mixtures thereof. In one embodiment A is a benzene ring.
[0031] When A is an acyclic hydrocarbon group, the carbon chain may be
linear or branched. In one embodiment A is an acyclic linear hydrocarbon
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group. Suitable groups include derivatives of carboxylic acids containing 7 to
30 carbon atoms, in another embodiment 7 to 20 carbon atoms, in another
embodiment 8 to 20 carbon atoms and in another embodiment 8 to 15 carbon
atoms. Further the chain may be saturated or unsaturated.
[0032] The overbased sulphonate detergent in one embodiment has a TBN
(total base number) of at least 350, in another embodiment at least 400, in
another embodiment at least 425, in another embodiment at least 450 and in
another embodiment at least 475. In one embodiment the overbased sulphonate
detergent has a TBN of 400 or 500.
[0033] The sulphonate detergent is present in one embodiment at 0.1 to 35,
in another embodiment 2 to 30, in another embodiment 5 to 25 and in another
embodiment 10 to 25 weight percent of the lubricating composition.
Overbasing the Detergent
[0034] In one embodiment the detergents of (i) or (ii) or both are
overbased.
Overbased materials, otherwise referred to as overbased or superbased salts,
are
generally single phase, homogeneous Newtonian systems characterised by a
metal content in excess of that which would be present for neutralisation
according to the stoichiometry of the metal and the particular acidic organic
compound reacted with the metal. The overbased materials are prepared by
reacting an acidic material (typically an inorganic acid or lower carboxylic
acid,
often carbon dioxide) with a mixture comprising an acidic organic compound, a
reaction medium comprising at least one organic solvent and promoter such as
phenol or a mixture of alcohols. A mixture of alcohols typically contains
methanol and at least one alcohol with 2 to 7 carbon atoms, and may contain 50-
60 mole percent methanol. The acidic material will normally have a sufficient
number of carbon atoms to provide a degree of solubility in oil. The amount of
excess metal is commonly expressed in terms of substrate to metal ratio. The
term "substrate to metal ratio" is the ratio of the total equivalents of the
metal to
the equivalents of the substrate. An overbased sulphonate detergent in one
embodiment has a metal ratio of 12.5:1 to 40:1, in another embodiment 13.5:1
to
40:1, in another embodiment 14.5:1 to 40:1, in another embodiment 15:1 to
40:1; in another embodiment 15.5:1 to 40:1 and in another embodiment 16.5:1
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to 40:1. Furthermore the overbased sulphonate detergent often has a low in-
process viscosity and a low final viscosity.
[0035] A sulphonate detergent with 500 TBN and its preparation are
disclosed in U.S. Patent 5,792,732. In Example 2 thereof, a 500 TBN all-linear
alkylbenzene sulphonate is prepared by reacting an alkyl benzene sulphonate
from Witco Corp. (now known as Crompton) with Ca(OH)2 and CaO in n-
heptane and methanol and bubbling with CO2. It is also reported in the
aforementioned patent (col. 5) that a 500 TBN overbased sulphonate containing
highly branched alkylbenzene sulphonate is available from Witco Corp. (now
known as Crompton) as Petronate C-500. Another method for preparing an
overbased sulphonate detergent of high metal ratio is disclosed in U.S. Patent
6,444,625 (see, for instance, column 3, bottom). The latter process includes
providing a sulphonic acid to a reactor, adding a lime reactant for
neutralization
and overbasing, adding a lower aliphatic C1 to C4 alcohol and a hydrocarbon
solvent, and carbonating the process mixture with carbon dioxide during which
process the exotherm of the reaction is maintained between 27 C and 57 C.
Alternatively, a high metal-ratio detergent may be prepared by using a mixture
of short chain alcohols, with or without a hydrocarbon solvent, conducting the
addition of lime reactants and carbon dioxide in multiple iterations, and, if
desired the process of adding lime and carbon dioxide and of removal of
volatile
materials may be repeated. The overbased sulphonate detergent in the present
invention may be used alone or with other overbased sulphonates. In one
embodiment the sulphonate detergent is in a mixture with other sulphonate
detergents. Alternatively a 500 TBN sulphonate detergent may be prepared by
the process shown in Preparative Example S-1.
Preparative Example 5-1
[0036] A sample of a 500 TBN sulphonate detergent is prepared using a
flange vessel with flange and clip, overhead stirrer with paddle and
polytetrafluoroethylene (PTFE) stirrer gland, Dean Stark trap and double
surface condenser, a mantle/thermocouple temperature controller system, the
equipment from just above the mantle to just below the condenser being covered
with glass wool. The vessel is charged with 35.1 parts by weight of C16-C24
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alkylbenzene sulphonic acid and 31.8 parts by weight of mineral oil (SN 150)
and heated to 30 C. The reactor is charged through a port with alcohols
containing methanol and a mixture of iso-butanol/amyl alcohol present at 11.6
parts by weight. The weight ratio of methanol to the mixture of iso-
butanol/amyl alcohol is 1.31. The reactor is charged with 14.9 parts by weight
of calcium hydroxide and the mixture is heated to 54 C where carbon dioxide is
added to form a carbonated product. The carbonated product is further treated
three more times with similar (or equal) portions of calcium hydroxide and
carbon dioxide. Water is removed by stripping before repeating the addition of
alcohol, calcium hydroxide and carbon dioxide 2 times. The product is stripped
and filtered.
Phenate Detergent
[0037] Optionally the detergent package further includes a phenate.
Phenate
detergents are known and include neutral and overbased metal salts of a
sulphur-containing phenate, a non-sulphurised phenate or mixtures thereof.
Suitable metal salts are the same as those described for the sulphonate
detergent.
[0038] The phenate detergent in one embodiment has a TBN from 30 to
290,
in another embodiment 40 to 265, in another embodiment 50 to 190 and in
another embodiment 70 to 175. In one embodiment the sulphur containing
phenate detergent has a TBN of 150 and in another embodiment a TBN of 225.
[0039] The sulphur containing phenate detergent in one embodiment has a
metal ratio of not more than 4, in another embodiment not more than 3, in
another embodiment not more than 2.7, in another embodiment not more than
2.5, in another embodiment not more than 2.3 and in another embodiment not
more than 2.1.
[0040] The phenate detergent is present in one embodiment at 0 to 15,
in
another embodiment 0 to 10, in another embodiment 0 to 5 and in another
embodiment 0.5 to 3 weight percent of the lubricating composition.
Dispersant
[0041] The invention optionally includes a dispersant. The dispersant is
known and includes an ash-containing dispersant or an ashless-type dispersant.
The dispersant may be used alone or in combination with other dispersants. In
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one embodiment the ashless dispersant does not contain ash-forming metals.
Ashless type dispersants are characterised by a polar group attached to a
relatively high molecular weight hydrocarbon chain.
Typical ashless
dispersants include N-substituted long chain alkenyl succinimides. Examples of
N-substituted long chain alkenyl succinimides include polyisobutylene
succinimide with number average molecular weight of the polyisobutylene
substituent in one embodiment from 350 to 5000, and in another embodiment
500 to 3000. Succinimide dispersants and their preparation are disclosed, for
instance in US Patent 4,234,435. Succinimide dispersants are typically the
imide formed from a polyamine, typically a poly(ethyleneamine).
[0042] In
one embodiment the invention further comprises a dispersant. In
one embodiment the dispersant is derived from polyisobutylene, an amine and
zinc oxide to form a polyisobutylene succinimide complex with zinc.
[0043]
Another class of ashless dispersant is Mannich bases. Mannich
dispersants are the reaction products of alkyl phenols with aldehydes
(especially
formaldehyde) and amines (especially polyalkylene polyamines). The alkyl
group typically contains at least 30 carbon atoms.
[0044] The
dispersant may also be post-treated by conventional methods by a
reaction with any of a variety of agents. Among these are urea, thiourea,
dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic
acids,
hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles,
epoxides, boron compounds, and phosphorus compounds.
[0045] In
one embodiment of the invention the dispersant is borated using a
variety of agents selected from the group consisting of the various forms of
boric acid (including metaboric acid, HB02, orthoboric acid, H3B03, and
tetraboric acid, H2B407), boric oxide, boron trioxide, and alkyl borates.
[0046] The
borated dispersant may be prepared by blending the boron
compound and the N-substituted long chain alkenyl succinimides and heating
them at a suitable temperature in one embodiment from 80 C to 250 C, in
another embodiment 90 C to 230 C and in another embodiment 100 C to 210 C,
until the desired reaction has occurred. The molar ratio of the boron
compounds
to the N-substituted long chain alkenyl succinimides is typically 10:1 to 1:4,
in
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another embodiment 4:1 to 1:3, and in another embodiment 1:2. An inert liquid
may be used in performing the reaction. The liquid may include toluene,
xylene,
chlorobenzene, dimethylformamide and mixtures thereof.
[0047] The dispersant is present in one embodiment from 0 wt % to 10 wt
%
or 0.01 to 10 wt %, in another embodiment 0.05 wt % to 7 wt %, in another
embodiment 0.1 wt % to 5 wt % and in another embodiment 0.2 wt % to 3 wt %
of the lubricating composition.
Oils of Lubricating Viscosity
[0048] The invention further includes oil of lubricating viscosity.
Such oils
include natural and synthetic oils, oil derived from hydrocracking,
hydrogenation, and hydrofinishing, unrefined, refined and re-refined oils and
mixtures thereof.
[0049] Unrefined oils are those obtained directly from a natural or
synthetic
source generally without (or with little) further purification treatment.
[0050] Refined oils are similar to the unrefined oils except they have been
further treated in one or more purification steps to improve one or more
properties. Purification techniques are known in the art and include solvent
extraction, secondary distillation, acid or base extraction, filtration,
percolation
and the like.
[0051] Re-refined oils are also known as reclaimed or reprocessed oils, and
are obtained by processes similar to those used to obtain refined oils and
often
are additionally processed by techniques directed to removal of spent
additives
and oil breakdown products.
[0052] Natural oils useful in making the inventive lubricants include
animal
oils, vegetable oils (e.g., castor oil, lard oil), mineral lubricating oils
such as
liquid petroleum oils and solvent-treated or acid-treated mineral lubricating
oils
of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils
derived from coal or shale or mixtures thereof.
[0053] Synthetic lubricating oils are useful and include hydrocarbon
oils
such as polymerised and interpolymerised olefins (e.g., polybutylenes,
polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-
octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g.
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dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-
benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls);
alkylated diphenyl ethers and alkylated diphenyl sulphides and the
derivatives,
analogs and homologs thereof or mixtures thereof.
[0054] Other synthetic lubricating oils include but are not limited to
liquid
esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl
phosphate, and the diethyl ester of decane phosphonic acid), and polymeric
tetrahydrofurans. Synthetic oils may be produced by Fischer-Tropsch reactions
and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.
[0055] Oils of lubricating viscosity may also be defined as specified in
the
American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
The five base oil groups are as follows: Group I (sulphur content >0.03 wt %,
and/or <90 wt % saturates, viscosity index 80-120); Group II (sulphur content
<0.03 wt %, and >90 wt % saturates, viscosity index 80-120); Group III
(sulphur
content <0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV
(all polyalphaolefins (PA0s)); and Group V (all others not included in Groups
I,
II, III, or IV). The oil of lubricating viscosity comprises an API Group I,
Group
II, Group III, Group IV, Group V oil and mixtures thereof. In one embodiment
the oil of lubricating viscosity is a monograde often with a SAE-50 or above
grade.
[0056] The oil of lubricating viscosity is present in one embodiment at
10 wt
% to 99.8 wt %, in another embodiment 30 wt % to 97.9 wt %, in another
embodiment 46 wt % to 94.8 wt % and in another embodiment 57 wt % to 89 wt
% of the lubricating composition.
Performance Additives
[0057] Optionally the lubricating composition may include at least one
performance additive other than components (a)-(c), selected from the group
consisting of metal deactivators, dispersant, antioxidants, antiwear agents,
corrosion inhibitors, antiscuffing agents, extreme pressure agents, foam
inhibitors, demulsifiers, friction modifiers, viscosity modifiers, pour point
depressants and mixtures thereof. Typically, fully-formulated lubricating oil
will contain one or more of these performance additives.
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[0058] The total combined amount of the other performance additives
present in one embodiment from 0 wt % to 15 wt %, in another embodiment 0
wt % to 13 wt %, in another embodiment 0.01 wt % to 11 wt % and in another
embodiment 0.05 wt % to 7 wt % of the lubricating composition.
Antiwear Agent
[0059] In one embodiment of the invention the composition further
comprises an antiwear agent such as a metal hydrocarbyl dithiophosphate.
Examples of a metal hydrocarbyl dithiophosphate include zinc dihydrocarbyl
dithiophosphates (often referred to as ZDDP, ZDP or ZDTP). In one
embodiment the lubricating composition is free of a metal hydrocarbyl
dithiophosphate.
[0060] In an alternative embodiment the antiwear agent is ashless i.e.
the
antiwear agent is metal-free. In one embodiment the metal-free antiwear agent
is an amine salt. The ashless antiwear agent often contains an atom including
sulphur, phosphorus, boron or mixtures thereof. In one embodiment the
lubricating composition is free of an ashless antiwear agent.
[0061] The amine is often a primary amine, a secondary amine a tertiary
amine or mixtures thereof. Often a primary amine and/or a secondary amine
contains at least one hydrocarbyl group with the number of carbon atoms
present in one embodiment from 2 to 30, in another embodiment 8 to 26, in
another embodiment 10 to 20, and in another embodiment 11 to 18 such as 11 to
14.
[0062] Examples of primary amines useful in the present invention
include
ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine and
dodecylamine. Also suitable primary fatty amines which include n-octylamine,
n-decyl amine, n-dodec yl amine, n-tetradecylamine, n-hexadecylamine, n-
octadecylamine and oleyamine. Other useful fatty amines include commercially
available fatty amines such as "Armeen " amines (products available from
Akzo Chemicals, Chicago, Illinois), such as Armeen C, Armeen 0, Armeen OL,
Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter
designation relates to the fatty group, such as coco, oleyl, tallow, or
stearyl
groups.
CA 02583420 2012-05-01
. ,
[0063]
Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine,
diheptylamine, methylethylamine, ethylbutylamine and ethylamyl amine. The
secondary amines may be cyclic amines such as piperidine, piperazine and
morpholine.
[0064]
The amine may also be a tertiary-aliphatic primary amine. Often the
aliphatic group is an alkyl group containing a number of carbon atoms in one
embodiment from 2 to 30, in another embodiment 6 to 26 and in another
embodiment 8 to 24. Often the tertiary alkyl primary amines are monoamines
such as tert-butylamine, terthexylamine, 1-methyl-1-amino-cyclohexane, tert-
octylamine, tert-decylamine, tertdodecylamine, tert-tetradecylamine, tert-
hexadecyl amine, tert-octadecylamine, terttetracos anyl amine,
and tert-
octacosanylamine.
[0065]
Mixtures of amines may also be used in the invention. Especially
useful mixtures of amines are "Primene 81R"* and "Primene JMT."* Primene
81R and Primene JMT (both produced and sold by Rohm & Haas) are mixtures
of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl
primary
amines respectively.
[0066]
The ashless antiwear agent may also include phosphoric acid esters or
salt thereof; dialkyldithiophosphoric acid esters or salt thereof; phosphites;
and
phosphorus-containing carboxylic esters, ethers, and amides or mixtures
thereof.
[0067]
Other ashless antiwear agent compounds include sulphur-containing
ashless anti-wear additives include thiocarbamate-containing compounds, such
as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-
coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulphides. In one
embodiment the lubricating composition is free of thiocarbamate-containing
compounds.
[0068]
The dithiocarbamate-containing compounds may be prepared by
reacting a dithiocarbamate acid or salt with an unsaturated compound. The
dithiocarbamatecontaining compounds may also be prepared by simultaneously
reacting an amine, carbon disulfide and an unsaturated compound. Generally,
*Trade-mark
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the reaction occurs at a temperature from 25 C to125 C. US Patents 4,758,362
and 4,997,969 describe dithiocarbamate compounds and methods of making them.
[0069]
Useful fatty amines include commercially available fatty amines such
as "Armeen " amines (products available from Akzo Chemicals, Chicago,
Illinois), such as Armeen C, Armeen 0, Armeen OL, Armeen T,
Armeen HT, Armeen S and Armeen SD, wherein the letter designation
relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
[0070] In an
alternative embodiment of the invention, the ashless antiwear
agent may be a monoester of a polyol and an aliphatic carboxylic acid, often
an
acid containing 12 to 24 carbon atoms. Often the monoester of a polyol and an
aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or
the
like, which may be present in the friction modifier mixture in one embodiment
from 5 to 95, in another embodiment 10 to 90, in another embodiment 20 to 85
and in another embodiment 20 to 80 weight percent of the mixture. The
aliphatic carboxylic acids (including a monocarboxylic acid) which form the
esters are those acids containing in one embodiment 12 to 24 carbon atoms and
in another embodiment 14 to 20 carbon atoms. In one embodiment the
composition is free of a monoester of a polyol and an aliphatic carboxylic
acid.
[0071]
Polyols include diols, triols, and alcohols with higher numbers of
alcoholic OH groups. Polyhydric alcohols include ethylene glycols, including
di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri-
and
tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol;
arabitol;
mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and
pentaerythritols, including di- and tripentaerythritol. Often
the polyol is
diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol or
dipentaerythritol.
[0072]
Examples of carboxylic acids include dodecanoic acid, stearic acid,
lauric acid, behenic acid, and oleic acid. The commercially available
monoester
is believed to include 60 + 5 percent by weight of the chemical species
"glycerol
monooleate," along with 35 + 5 percent glycerol dioleate, and less than 5
percent trioleate and oleic acid. The amounts of the monoesters, described
17
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above, are calculated based on the actual, corrected, amount of polyol
monoester
present in any such mixture.
[0073] In one embodiment of the invention the antiwear agent is a
borate
ester. The borate ester may be prepared by the reaction of a boron compound
and at
least one compound selected from epoxy compounds, halohydrin compounds,
epihalohydrin compounds, alcohols and mixtures thereof. Typically the alcohols
include monohydric alcohols, dihydric alcohols, trihydric alcohols or higher
alcohols.
[0074] Boron compounds suitable for preparing the borate ester include
a boric
acid (including metaboric acid, HB02, orthoboric acid, H3B03, and a tetraboric
acid, H2B407), a boric oxide, a boron trioxide and an alkyl borate. The borate
ester may also be prepared from boron halides. The borated ester further
contains at least one hydrocarbyl group often containing about 8 to about 30
carbon atoms. In one embodiment the lubricating composition is free of a
borated ester.
[0075] The antiwear agent is present in one embodiment from 0 wt % to 8 wt
%, in another embodiment 0 wt % to 6 wt %, in another embodiment 0.01 wt %
to 4 wt % and in another embodiment 0.01 wt % to 2 wt % of the lubricating
composition. The antiwear agent may be used alone or in combination with
other antiwear agents. In one embodiment the lubricating composition is free
of
an antiwear agent
[0076] Other performance additives such as an antioxidant including a
diphenylamine, a hindered phenol, a molybdenum dithiocarbamate, a
sulphurised olefin and mixtures thereof and in one embodiment the lubricating
composition is free of an antioxidant; corrosion inhibitors including
octylamine
octanoate, condensation products of dodecenyl succinic acid or anhydride and a
fatty acid such as oleic acid with a polyamine; metal deactivators including
derivatives of benzotriazoles, 1,2,4-triazoles, benzimidazoles, 2-
alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles; foam inhibitors
including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally
vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene
glycols,
polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene
oxide) polymers; pour point depressants including esters of maleic anhydride-
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styrene, polymethacrylates, polyacrylates or polyacrylamides; viscosity
modifiers including styrene-butadiene rubbers, ethylene-propylene copolymers,
hydrogenated styrene-isoprene polymers, hydrogenated radical isoprene
polymers, poly(meth)acrylate acid esters, polyalkyl styrenes, polyolefins,
polyalkylmethacrylates and esters of maleic anhydride-styrene copolymers; and
friction modifiers including fatty acid derivatives such as amines, esters,
epoxides, fatty imidazolines, condensation products of carboxylic acids and
polyalkylene-polyamines and amine salts of alkylphosphoric acids may also be
used in the composition of the invention.
Process
[0077] The
invention also includes a process to prepare the lubricating
composition of the present invention, comprising mixing:
(a) detergent package comprising:
(i) an oligomeric reaction product of (1) a hydrocarbyl-substituted
phenol; (2) an aldehyde; and (3) a carboxyl-substituted phenol or
a carboxyl-substituted phenylamine; or salts of the reaction
product;
(ii) a sulphonate; and
(iii) optionally a phenate;
(b) optionally a dispersant; and
(c) an oil of lubricating viscosity,
wherein the sulphonate detergent is overbased with a metal ratio of about
12.5:1
to about 40:1.
[0078] The
mixing conditions include a temperature in one embodiment from
15 C to 130 C, in another embodiment 20 C to 120 C and in another
embodiment 25 C to 110 C; and for a period of time in one embodiment from
seconds to 48 hours, in another embodiment 2 minutes to 24 hours, and in
another embodiment 5 minutes to 16 hours or 1 to 4 hours; and at pressures in
one embodiment from 86.4 kPa to 266 kPa (650 mm Hg to 2000 mm Hg), in
30 another
embodiment 91.8 kPa to 200 kPa (690 mm Hg to 1500 mm Hg), and in
another embodiment 95.1 kPa to 133 kPa (715 mm Hg to 1000 mm Hg).
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[0079] The process optionally includes mixing other performance
additives
as described above. The optional performance additives may be added
sequentially, separately or as a concentrate.
[0080] If the present invention is in the form of a concentrate (which
may be
combined with additional oil to form, in whole or in part, a finished
lubricant),
the ratio of each of the above-mentioned detergent and/or dispersant, as well
as
other components, to diluent oil is typically in the range of 80:20 to 10:90
by
weight.
Industrial Application
[0081] The lubricating composition of the present invention is useful for
an
internal combustion engine, for example a diesel fuelled engine, a gasoline
fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol
fuelled
engine. In one embodiment the internal combustion engine is a 4-stroke and in
another embodiment a 2-stroke engine. In one embodiment the diesel fuelled
engine is a marine diesel engine.
[0082] In one embodiment of the invention provides a method for
lubricating
an internal combustion engine, comprising supplying thereto a lubricant
comprising the composition as described herein. The use of the composition
may impart one or more of cleanliness properties, antiwear performance and
deposit control.
[0083] The following examples provide an illustration of the invention.
These examples are non exhaustive and are not intended to limit the scope of
the
invention.
EXAMPLES
Examples 1-10 and Reference Example 1
[0084] Lubricating compositions are prepared by mixing additives as
defined
in Table 1; and all additives contain conventional amounts of diluent oil. The
compositions prepared are:
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Table 1: Compositions of the Invention
Sulphonate Oligomeric Reaction
Dispersant Oil
Product
Example a* b* c* d* e* f* g*
EX1 17.2 1 1.5
balance
EX2 17.2 2 1.5
balance
EX3 17.2 4 1.5
balance
EX4 17.2 1 1.5
balance
EX5 17.2 2 1.5
balance
EX6 17.2 4 1.5
balance
EX7 17.2 1 1 1.5
balance
EX8 17.2 2 1.5
balance
EX9 13.8 2 - 1.5
balance
EX10 13.8 2 1.5
balance
REF1 17.2 1.5
balance
Foot note to Table 1:
(a*) is a 400 TBN sulphonate detergent;
(b*) is a 500 TBN sulphonate;
(c*) is metal salixarate detergent;
(d*) is a metal-free oligomeric reaction product of (1) a 550 molecular weight
hydrocarbyl-substituted phenol; (2) an aldehyde; and (3) a carboxyl-
substituted
phenol;
(e*) is a dodecyl-substituted phenol equivalent of component (d*);
(f*) is a dispersant; and
(g*) is an oil of lubricating viscosity.
Test 1: Panel Coker
[0085]
Approximately 233g of sample is placed in a 250 ml Panel Coker
apparatus and heated to 325 C. The sample is splashed against a metal plate
for
15 seconds and then baked for 45 seconds. The splashing and baking cycle is
continued for approximately 3 hours. The sample is cooled to room temperature
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and the amount of deposits left on the metal plate is weighed. The results
obtained by testing the lubricants of the indicated Examples are as shown:
Example Deposit (mg)
EX1 220.3
EX2 132.5
EX3 92.1
EX4 105.9
EX5 60.4
EX6 47.2
EX7 107.1
EX8 60.9
EX9 125.8
EX10 122.3
REF! 346.2
[0086] The analysis of the data indicates that the lubricating composition
of
the invention has reduced deposit formation compared with the reference
example. Consequently the invention provides one or more properties of
cleanliness properties, antiwear performance and deposit control into a
lubricating composition.
Examples 11 to 16 and Reference Example 2
[0087] Lubricating compositions are prepared by mixing additives as
defined
in Table 1; and all additives contain conventional amounts of diluent oil. The
compositions prepared are:
22
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Table 2: Compositions of the Invention
Sulphonate Phenate Oligomeric Dispersant Antiwear
Oil
Reaction additive
Product
Example a* b* c* d* e* f" g* h*
= *
EX11 17.2 2 1.5 balance
EX12 17.2 2 1.5 balance
EX13 17.2 2 1.5 0.75 0.25
0.25 balance
EX14 17.2 2 1.5 0.75 balance
EX15 17.2 1 2 1.5 balance
EX16 17.2 2.5 balance
REF2 17.2 1.5 balance
Foot note to Table 1:
(a*), (c*) and (d*) are as defined above;
(b*) is a phenate;
(e*) is a dispersant;
(f*) is a borated dispersant;
(g*) is a zinc dialkyl dithiophosphate;
(h*) is a sulphurised olefin;
(i*) is an oil of lubricating viscosity.
Test 1: Cameron Plint Wear Test
100881 The Cameron Flint TE-77T" is a reciprocating wear tester. In this
test
a steel ball upper specimen is reciprocated against a steel flat lower
specimen.
The Cameron Flint is then charged with 10 ml of the sample and heated to 50 C
and held for 20 minutes. The samples (EX12 to 16) are then subject to a load
of
150 N over two minutes while at the same time reciprocation is started at 10
Hz
over 15 mm stroke length. Samples EX11 and REF1 are subjected to a load of
240 N. The sample is then heated to 350 C at 2 C per minute and then held at
temperature for 3 hours. At the end of the test the onset of film failure is
measured. The onset of film failure is determined by the temperature at which
the oil film as measured by the contact potential, first falls to 80 % of its
23
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starting value. The results obtained by testing the lubricants of the
indicated
Examples are as shown:
Exam le Onset of Film Failure (240 N Onset of Film Failure (150 N
load) Temperature ( C) load) Temperature ( C)
REF2 230
EX11 340
EX12 290
EX13 270
EX14 200
EX15 260
EX16 300
[0089] The analysis of the data indicates that the lubricating composition
of
the invention has an increased temperature for the onset of film failure.
100901 In summary the lubricating composition of the invention has one
or
more of cleanliness properties, antiwear performance and deposit control.
100911 Except in the Examples, or where otherwise explicitly indicated,
all
numerical quantities in this description specifying amounts of materials, reac-
tion conditions, molecular weights, number of carbon atoms, and the like, are
to
be understood as modified by the word "about." Unless otherwise indicated,
each chemical or composition referred to herein should be interpreted as being
a
commercial grade material which may contain the isomers, by-products,
derivatives, and other such materials which are normally understood to be
present in the commercial grade. However, the amount of each chemical
component is presented exclusive of any solvent or diluent oil, which may be
customarily present in the commercial material, unless otherwise indicated. It
is
to be understood that the upper and lower amount, range, and ratio limits set
forth herein may be independently combined. Similarly, the ranges and amounts
for each element of the invention may be used together with ranges or amounts
for any of the other elements. As used herein, the expression "consisting
essentially of' permits the inclusion of substances that do not materially
affect
the basic and novel characteristics of the composition under consideration.
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Various materials are referred to herein as "ashless" because they, at least
initially, do not contain ash-forming metals. It is recognized that such
materials
may associate with ash-forming metals when formulated in a lubricant;
nevertheless, they are still to be considered "ashless."
[0092] As used
herein, the term "hydrocarbyl substituent" or "hydrocarbyl
group" is used in its ordinary sense, which is well-known to those skilled in
the
art. Specifically, it refers to a group having a carbon atom directly attached
to
the remainder of the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-,
aliphatic-,
and alicyclic-substituted aromatic substituents, as well as cyclic
substituents
wherein the ring is completed through another portion of the molecule (e.g.,
two
substituents together form a ring);
substituted hydrocarbon substituents, that is, substituents containing non-
hydrocarbon groups which, in the context of this invention, do not alter the
predominantly hydrocarbon nature of the substituent (e.g., halo (especially
chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso,
and sulfoxy);
hetero substituents, that is, substituents which, while having a
predominantly hydrocarbon character, in the context of this invention, contain
other than carbon in a ring or chain otherwise composed of carbon atoms.
Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as
pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, in one
embodiment no more than one, non-hydrocarbon substituent will be present for
every ten carbon atoms in the hydrocarbyl group; typically, there will be no
non-hydrocarbon substituents in the hydrocarbyl group.
