U.S. patent application number 15/301674 was filed with the patent office on 2017-01-19 for method for preparing a sulfurized alkaline earth metal dodecylphenate.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Darren J. Becker, Lindsey K. Conant, Mohamed G. Fahmy, Rodney J. Lukaszewski, Roger L. Parsons, Jeremy T. Strauch.
Application Number | 20170015925 15/301674 |
Document ID | / |
Family ID | 52875774 |
Filed Date | 2017-01-19 |
United States Patent
Application |
20170015925 |
Kind Code |
A1 |
Fahmy; Mohamed G. ; et
al. |
January 19, 2017 |
METHOD FOR PREPARING A SULFURIZED ALKALINE EARTH METAL
DODECYLPHENATE
Abstract
An overbased sulfurized alkaline earth metal alkylphenate is
prepared by reacting an alkylphenol with an alkaline earth metal
hydroxide or an alkaline earth metal oxide and sulfur in the
presence of an alkylene glycol or dialkylene glycol, or ether
thereof and in the presence of an oil of lubricating viscosity, and
optionally further reacting the product thereof with carbon
dioxide; thereby forming a sulfurized alkaline earth metal
alkylphenate composition in oil. The composition is heated and
subjected to steam stripping followed by filtration. The resulting
product exhibits an improved rate and efficiency of filtration.
Inventors: |
Fahmy; Mohamed G.;
(Eastlake, OH) ; Parsons; Roger L.; (Chagrin
Falls, OH) ; Conant; Lindsey K.; (Manvel, TX)
; Becker; Darren J.; (Paso Robles, CA) ; Strauch;
Jeremy T.; (Sugar Land, TX) ; Lukaszewski; Rodney
J.; (Pasadena, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
52875774 |
Appl. No.: |
15/301674 |
Filed: |
March 23, 2015 |
PCT Filed: |
March 23, 2015 |
PCT NO: |
PCT/US2015/021949 |
371 Date: |
October 3, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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61975256 |
Apr 4, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10N 2070/00 20130101;
C10M 159/22 20130101; C10N 2010/04 20130101; C10N 2040/25 20130101;
C10M 135/02 20130101; C10M 2219/02 20130101; C10M 2219/087
20130101; C07G 17/00 20130101; C10N 2030/04 20130101 |
International
Class: |
C10M 135/02 20060101
C10M135/02 |
Claims
1. A process for preparing a sulfurized alkaline earth metal
alkylphenate, comprising: (a) reacting (i) an alkylphenol, wherein
the alkyl group contains about 6 to about 24 carbon atoms, with:
(ii) an alkaline earth metal hydroxide or an alkaline earth metal
oxide in an amount of about 0.4 to about 10 moles per mole of
alkylphenol charged to the reaction; and (iii) a sulfur source in
an amount to provide about 0.8 to about 3 moles sulfur (as S) per
mole of alkylphenol charged to the reaction; in the presence of
(iv) an alkylene glycol or dialkylene glycol, or ether thereof, in
an amount of about 0.2 to about 2 moles per mole of alkylphenol
charged to the reaction; and including in the reaction mixture (v)
an oil of lubricating viscosity; and optionally further reacting
the product thereof with: (vi) carbon dioxide; thereby forming a
sulfurized alkaline earth metal alkylphenate composition in oil;
(b) heating said alkylphenate composition to about 120 to
280.degree. C.; (c) supplying steam to said alkylphenate
composition; (d) removing said steam under reduced pressure; and
(e) filtering the resulting composition to provide, as the
filtrate, a sulfurized alkaline earth metal alkylphenate in
oil.
2. The process of claim 1 wherein the alkylphenol comprises
p-dodecyl phenol.
3. (canceled)
4. The process of claim 1 wherein the amount alkaline earth metal
hydroxide or oxide is about 1 to about 5 moles per mole of
alkylphenol charged to the reaction.
5. The process of claim 1 wherein the optional further reacting
with carbon dioxide in optional step (vi) is conducted.
6. The process of claim 1 wherein the amount of alkaline earth
metal hydroxide or oxide is suitable to provide a product with a
total base number of about 200 to about 600 on an oil free
basis.
7. The process of claim 1 wherein the amount of the alkaline earth
metal hydroxide or oxide is suitable to provide a product with a
total base number of about 100 to about 350.
8. (canceled)
9. The process of claim 1 wherein the alkylene glycol or dialkylene
glycol, or ether thereof, comprises ethylene glycol or propylene
glycol.
10. (canceled)
11. (canceled)
12. The process of claim 1 wherein the oil of lubricating viscosity
comprises a mineral oil.
13. (canceled)
14. The process of claim 1 wherein the optional reaction with
carbon dioxide is conducted and the amount of carbon dioxide
supplied is about 10 to about 50 parts by weight per 100 parts by
weight of alkylphenol charged to the reaction.
15. The process of claim 1 wherein the steam is supplied at
superatmospheric pressure and at a temperature of about 120.degree.
C. to about 250.degree. C.
16. The process of claim 1 wherein volatile materials are removed
along with removal of the steam.
17. The process of claim 1 wherein the steam is removed at a
pressure of about 1.3 to about 53 kPa (10 to 400 mmHg).
18. The process of claim 1 wherein the amount of steam is about 3
to about 36 parts by weight per 100 parts by weight of alkylphenol
charged to the reaction.
19. (canceled)
20. The product prepared by the process of claim 1.
21. A lubricant composition comprising an oil of lubricating
viscosity and the product of claim 20.
22. The lubricant composition of claim 21 further comprising at
least one of a supplemental overbased detergent, a dispersant, an
antioxidant, a viscosity improver, an anti-wear agent, a pour point
depressant, or an extreme pressure agent.
23. A method for lubricating an internal combustion engine,
comprising supplying thereto the lubricant composition of claim
21.
24. A method for improving the filterability of an alkaline earth
metal in a process comprising (a) reacting (i) an alkylphenol,
wherein the alkyl group contains about 6 to about 24 carbon atoms,
with: (ii) an alkaline earth metal hydroxide or an alkaline earth
metal oxide in an amount of about 0.4 to about 10 moles per mole of
alkylphenol charged to the reaction; and (iii) a sulfur source in
an amount to provide about 0.8 to about 3 moles sulfur (as S) per
mole of alkylphenol charged to the reaction; in the presence of
(iv) an alkylene glycol or dialkylene glycol, or ether thereof, in
an amount of about 0.2 to about 2 moles per mole of alkylphenol
charged to the reaction; and including in the reaction mixture (v)
an oil of lubricating viscosity; and optionally further reacting
the product thereof with: (vi) carbon dioxide; thereby forming a
sulfurized alkaline earth metal alkylphenate composition in oil;
(b) heating said alkylphenate composition to about 120 to
280.degree. C.; said improvement comprising: (c) supplying steam to
said alkylphenate composition; and (d) removing said steam under
reduced pressure; prior to (e) filtering the resulting composition
to provide, as the filtrate, a sulfurized alkaline earth metal
alkylphenate in oil.
25. The method of claim 24 wherein the filtering is accomplished by
use of a filter aid and the amount of said filter aid used is less
than about 3 weight percent based on the final batch yield.
26. (canceled)
27. A method for reducing the amount of monomeric alkylphenol in
the product of a process comprising (a) reacting (i) an
alkylphenol, wherein the alkyl group contains about 6 to about 24
carbon atoms, with: (ii) an alkaline earth metal hydroxide or an
alkaline earth metal oxide in an amount of about 0.4 to about 10
moles per mole of alkylphenol charged to the reaction; and (iii) a
sulfur source in an amount to provide about 0.8 to about 3 moles
sulfur (as S) per mole of alkylphenol charged to the reaction; in
the presence of (iv) an alkylene glycol or dialkylene glycol, or
ether thereof, in an amount of about 0.2 to about 2 moles per mole
of alkylphenol charged to the reaction; and including in the
reaction mixture (v) an oil of lubricating viscosity; and
optionally further reacting the product thereof with: (vi) carbon
dioxide; thereby forming a sulfurized alkaline earth metal
alkylphenate composition in oil; (b) heating said alkylphenate
composition to about 120 to 280.degree. C.; said reduction arising
from: (c) supplying steam to said alkylphenate composition; and (d)
removing said steam under reduced pressure; prior to (e) filtering
the resulting composition to provide, as the filtrate, a sulfurized
alkaline earth metal alkylphenate in oil.
Description
BACKGROUND OF THE INVENTION
[0001] The disclosed technology relates to a process for preparing
a sulfurized alkaline earth metal dodecylphenate exhibiting
improved ease of filterability.
[0002] Phenol-based detergents are known. Among these are phenates
based on phenolic monomers, linked with sulfur bridges or alkylene
bridges such as methylene linkages derived from formaldehyde. The
phenolic monomers themselves are typically substituted with an
aliphatic hydrocarbyl group to provide a measure of oil
solubility.
[0003] One commonly employed step in the commercial manufacture of
metal phenates, including overbased metal phenates, is filtration.
The filtration typically occurs after the overbasing process, and
slow filtration can have a negative impact on production and
economics, in terms of filtration time or alternatively in amount
of filter aid usage required to maintain an acceptable flow rate.
Moreover, recipe modifications designed to reduce the amount of
monomeric phenolic species may tend to lead to worse filtration
performance. This is of increasing significance because certain
alkylphenols and products prepared from them have come under
increased scrutiny due to their association as potential endocrine
disruptive materials. In particular, alkylphenol detergents which
are based on oligomers of C12 alkyl phenols may contain residual
monomeric C12 alkyl phenol species. There has been interest,
therefore, in developing alkyl-substituted phenate detergents, for
uses in lubricants, fuels, and as industrial additives, which
contain a reduced amount of dodecylphenol component.
[0004] An early reference to basic sulfurized polyvalent metal
phenates is U.S. Pat. No. 2,680,096, Walker et al., Jun. 1, 1954;
see also U.S. Pat. No. 3,372,116, Meinhardt, Mar. 6, 1968.
Additionally, U.S. Pat. No. 3,036,971, Otto, May 29, 1962,
discloses lubricating oils containing carbonated basic sulfurized
calcium phenates. Its preparation includes the use of a glycol
containing less than 6 carbon atoms.
[0005] U.S. Pat. No. 3,464,970, Sakai et al., Sep. 2, 1969,
similarly discloses an overbased sulfurized calcium phenate by
heating a mixture of phenolic compounds, dihydric alcohol,
elementary sulfur and calcium compounds. Somewhat later, U.S. Pat.
No. 5,024,773, Liston, Jun. 18, 1991, discloses a method of
preparing group II metal overbased sulfurized alkylphenols
involving use of a sulfurization catalyst. The product is said to
have lower crude sediment, higher Total Base Number, and lower
viscosity.
[0006] EP 601721, Ethyl Petroleum, Jun. 15, 1994, discloses a
process for preparing overbased phenates.
[0007] PCT publication WO 2013/119623, Lubrizol, Aug. 15, 2013,
discloses a sulfurized alkaline earth metal (e.g., calcium)
dodecylphenate prepared by reacting dodecylphenol with calcium
hydroxide or calcium oxide in an amount of about 0.3 to about 0.7
moles per mole of dodecylphenol charged and an alkylene glycol in
an amount of about 0.13 to about 0.6 moles per mole of
dodecylphenol charged; and reacting the product of the first step
with sulfur in an amount of about 1.6 to about 3 moles per mole of
dodecylphenol charged The product thus prepared has reduced levels
of monomeric dodecylphenol.
[0008] The disclosed technology provides a method for preparing
phenate detergent with improved filterability efficiency. In
certain embodiments, the disclosed technology may also provide a
product which contains a reduced amount of monomeric dodecylphenol
within an oligomeric dodecylphenol composition.
SUMMARY OF THE INVENTION
[0009] The disclosed technology provides a process for preparing a
sulfurized alkaline earth metal alkylphenate, optionally overbased,
comprising:
(a) reacting (i) an alkylphenol, wherein the alkyl group contains 6
to 24 carbon atoms, with (ii) an alkaline earth metal hydroxide or
an alkaline earth metal oxide in an amount of 0.4 to 10 moles per
mole of alkylphenol charged to the reaction; and (iii) a sulfur
source in an amount to provide 0.8 to 3 moles sulfur (as S) per
mole of alkylphenol charged to the reaction; in the presence of
(iv) an alkylene glycol or dialkylene glycol, or ether thereof, in
an amount of 0.2 to 2 moles per mole of alkylphenol charged to the
reaction; and including in the reaction mixture (v) an oil of
lubricating viscosity; and optionally further reacting the product
thereof with (vi) carbon dioxide; thereby forming a sulfurized
alkaline earth metal alkylphenate composition in oil; (b) heating
said alkylphenate composition to 120 to 280.degree. C. or 200 to
250.degree. C.; (c) supplying steam to said alkylphenate
composition; (d) removing said steam under reduced pressure; and
(e) filtering the resulting composition to provide, as the
filtrate, a sulfurized alkaline earth metal alkylphenate in
oil.
[0010] The disclosed technology further provides the product
prepared by the foregoing process; a lubricant composition
comprising an oil of lubricating viscosity and the foregoing
product; and a method for lubricating an internal combustion
engine, comprising supplying thereto the foregoing lubricant
composition.
DETAILED DESCRIPTION OF THE INVENTION
[0011] Various preferred features and embodiments will be described
below by way of non-limiting illustration.
[0012] One of the materials used in the presently disclosed
technology is a sulfur-bridged phenolic compound. Such materials in
general, their methods of preparation, and use in lubricants are
well known from, for instance, the above-referenced U.S. Pat. No.
2,680,096, Walker et al. They may be prepared starting from phenol
or, alternatively, a short chain alkyl phenol such as cresol (o-,
m-, or p-methylphenol), or mixtures thereof, any of which are
readily available as starting materials. The alkylation of phenol
and its homologues is well known, typically by catalyzed reaction
of an olefin, often an .alpha.-olefin, with phenol (or with cresol
or another homologue, as the case may be). Alkylation of phenol is
described in greater detail in the Kirk-Othmer Encyclopedia of
Chemical Technology, third edition (1978) vol. 2, pages 82-86, John
Wiley and Sons, New York.
[0013] Linking of alkyl-substituted (or more generally,
hydrocarbyl-substituted) phenols to form oligomeric species is also
well known. They may be linked together to make sulfur bridged
species, which may include bridges of single sulfur atoms (--S--)
or multiple sulfur atoms (e.g., where n may be 2 to 8, typically 2
or 3). Typically there may be 1, 2, or 3, or often 1, S atom per
linkage. Sulfurized phenols may be prepared by reaction with a
sulfur source, that is, an active sulfur species such as sulfur
monochloride or sulfur dichloride as described on pages 79-80 of
the Kirk-Othmer reference or with elemental sulfur, as described,
for instance, in U.S. Pat. No. 2,680,096. Sulfurization (with
sulfur) may be conducted in the presence of a basic metal compound
such as calcium hydroxide or calcium oxide, thus preparing a metal
salt, as described in greater detail, below.
[0014] The process of the disclosed technology begins with an
alkylphenol which comprises an alkylphenol wherein the alkyl group
contains 6 to 24 carbon atoms, and in certain embodiments, 8 to 18
or 9 to 15 or 10 to 14 carbon atoms, or 12 carbon atoms. Such a
material may include a dodecylphenol (e.g., tetrapropenylphenol,
"TPP") such as, in one embodiment, paradodecylphenol, ("PDDP").
Other substituted phenols may be present in TPP as well as PDDP,
but in certain embodiments the PDDP may comprise at least 50 weight
percent of the monomeric phenolic component and may be 50 to 100
weight percent, or 60 to 99% or 70 to 98% or 80 to 97% or 90-96% or
95 to 98%. Typically, a commercial grade of TPP may be used, such
that phenolic components other than PDDP will be those materials
that are present along with PDDP in the commercial grade material.
Thus, a certain amount of other isomers may be present,
predominantly ortho-dodecylphenol or meta-dodecylphenol, but there
may also be an amount of unsubstituted phenol and an amount of
unreacted dodecene, as well as a certain amount (typically a minor
amount) of dialkylated material. Moreover, since dodecylphenols are
typically prepared by the reaction of a propylene tetramer with a
phenol, certain amounts of material having C9 or C15 alkyl groups,
or a mixture of alkyl groups having 9 (or fewer) to 15 (or more)
carbon atoms, may also be present. Some of these may result from
reaction with propylene trimer or pentamer. Characteristically, the
amount of such other materials may be 5 or 15 to 50 percent or 20
to 40, or 25 to 35, or 35 to 40 percent by weight, in commercial
PDDP. The amounts of PDDP referred to herein generally refer to the
total amount of the commercial grade, which would include such
isomers, by-products, and other materials. However, when the amount
of "residual TPP" is reported, those amounts normally include
mixtures of closely related monomeric materials such as ortho- and
para-isomers from C9 to C15 alkylphenols, typically excluding
dialkylated materials.
[0015] The TPP or other alkylphenol may be, in one embodiment,
initially reacted with a basic alkaline earth metal material,
typically an oxide or a hydroxide, where the alkaline earth metal
may typically be calcium or magnesium, or in some embodiments,
calcium. Suitable basic materials include calcium (or magnesium)
hydroxide or calcium (or magnesium) oxide, typically calcium
hydroxide. The reaction may be carried out in the presence of an
alkylene glycol and sulfur. The amount of the alkaline earth metal
hydroxide or oxide may typically be an amount to provide 0.4 to 10
moles of the metal oxide or hydroxide per mole of the alkylphenol
(such as TPP) that is charged to the reaction. Alternative amounts
may be 0.5 to 8 moles or 0.8 to 6 or 1 to 5 or 1.3 to 3 or 1.5 to 2
or 1.7 to 1.9 moles per moles of alkylphenol. Since alkaline earth
metals are divalent, the broadest above-mentioned amounts would
correspond to 0.8 to 20 equivalents per mole of the alkylphenol.
For amounts less than 1 equivalent per equivalent, the alkylphenol
will not be completely salted or neutralized; for amounts of about
1 equivalent/equivalent, a substantially neutral salt may be
obtained. For amounts in excess of 1 equivalent/equivalent, an
overbased salt may be obtained, as described in greater detail
below. In another embodiment, the alkylphenol may be initially
reacted with a sulfur source to form a sulfur-bridged material, and
thereafter reacted with the selected amount of alkaline earth metal
oxide or hydroxide to effect neutralization.
[0016] An alkylene glycol (that is, diol) is typically present,
especially during the neutralization reaction. The alkylene glycol
may be ethylene glycol or it may, alternatively, be a heavier
glycol such as 1,2- or 1,3-propylene glycol or a butylene glycol.
As it is often considered to be desirable able to remove the
alkylene diol after the reaction is complete, use of a diol having
6 or fewer or 5, 4, or 3 or fewer carbon atoms, or a normal boiling
point of less than 230 or 220 or 210.degree. C. may be desirable.
Ethylene glycol may typically be used. Alternatively, a dialkylene
glycol may be used, that is, a material of the general structure
HO--R--O--R--OH, where R represents an alkylene group (the two R
groups may be the same or different). Alternatively, one or both of
the --OH groups of the alkylene- or dialkylene-glycol may be
replaced by an ether group, that is, an alkoxy group which may
contain 1 to 4 or 1 to 2 carbon atoms, such as methoxy,
--OCH.sub.3.
[0017] The amount of the alkylene glycol or dialkylene glycol, or
ether thereof that is present in the reaction mixture may be 0.2 to
2 moles per mole of alkylphenol charged to the reaction.
Alternative amounts may be 0.4 to 1.5, or 1.0 to 1.5, or 0.5 to
1.2, or 0.6 to 1, or 0.5 to 0.8, or 0.65 to 0.8 moles per mole.
[0018] Another component of the reaction mixture will be a sulfur
source which may be elemental sulfur, which will typically form
sulfur-bridges or linkages between the aromatic groups of two or
more alkylphenol molecules, thereby forming species that may be
considered dimeric or oligomeric species. The amount of the sulfur
source charged to the reaction mixture will typically be an amount
to provide 0.8 to 3 moles of sulfur (calculated assuming monomeric
S units, molecular weight 32) per mole of alkylphenol charged to
the reaction. Other amounts may be 1 to 2.5 or 1 to 2 or 1.2 to 1.8
or 1.3 to 1.5 moles per mole.
[0019] The reaction of the above-described components may be
conducted in a solvent or other medium such as an oil of
lubricating viscosity, also referred to as a base oil. If a
volatile medium is used, it may be subsequently removed from the
reaction mixture by evaporation or other means, e.g.,
steam-stripping. If a base oil is used as the medium, it may be
retained in the reaction medium since, in some embodiments, the
overbased product will be used in the presence of diluent oil. The
base oil may be selected from any of the base oils in Groups I-V of
the American Petroleum Institute (API) Base Oil Interchangeability
Guidelines, namely
TABLE-US-00001 Base Oil Category Sulfur (%) Saturates(%) Viscosity
Index Group I >0.03 and/or <90 80 to 120 Group II
.ltoreq.0.03 and .gtoreq.90 80 to 120 Group III .ltoreq.0.03 and
.gtoreq.90 >120 Group IV All polyalphaolefins (PAOs) Group V All
others not included in Groups I, II, III or IV
[0020] Groups I, II and III are mineral oil base stocks. The oil of
lubricating viscosity can include natural or synthetic oils and
mixtures thereof. Mixture of mineral oil and synthetic oils, e.g.,
polyalphaolefin oils and/or polyester oils, may be used.
[0021] Natural oils include animal oils and vegetable oils (e.g.
vegetable acid esters) as well as 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. In one embodiment, the oil of
lubricating viscosity will be a mineral oil. Hydro treated or
hydrocracked oils are also useful oils of lubricating viscosity.
Oils of lubricating viscosity derived from coal or shale are also
useful.
[0022] Synthetic oils include hydrocarbon oils and halosubstituted
hydrocarbon oils such as polymerized and interpolymerized olefins
and mixtures thereof, alkylbenzenes, polyphenyl, alkylated diphenyl
ethers, and alkylated diphenyl sulfides and their derivatives,
analogs and homologues thereof. Alkylene oxide polymers and
interpolymers and derivatives thereof, and those where terminal
hydroxyl groups have been modified by, e.g., esterification or
etherification, are other classes of synthetic lubricating oils.
Other suitable synthetic lubricating oils comprise esters of
dicarboxylic acids and those made from C5 to C12 monocarboxylic
acids and polyols or polyol ethers. Other synthetic lubricating
oils include liquid esters of phosphorus-containing acids,
polymeric tetrahydrofurans, silicon-based oils such as poly-alkyl-,
polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils, and silicate
oils. Other synthetic oils include those produced by
Fischer-Tropsch reactions, typically hydroisomerized
Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may
be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure
as well as other gas-to-liquid oils.
[0023] Unrefined, refined, and rerefined oils, either natural or
synthetic (as well as mixtures thereof) of the types disclosed
hereinabove can be used. Unrefined oils are those obtained directly
from a natural or synthetic source without further purification
treatment. 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. Rerefined oils are obtained by
processes similar to those used to obtain refined oils applied to
refined oils which have been already used in service. Rerefined
oils often are additionally processed to remove spent additives and
oil breakdown products.
[0024] The amount of oil of lubricating viscosity present during
the reaction of the alkylphenol with the sulfur source and the
alkaline earth compound may be an amount suitable to provide a
mixture that can be readily processed, that is, stirred and
otherwise handled. To the extent that the final product will be
used as a lubricant additive, the oil may serve as the conventional
diluent oil in which the product is commercially supplied.
Additional oil may be added subsequently if desired, in order to
adjust the concentration, viscosity, or other parameters of the
final product. The amount of oil included in the above-described
reaction mixture may be 10 to 100 parts by weight per 100 parts by
weight of alkylphenol charged to the reaction. Alternative amounts
may be 15 to 50, or 20 to 50, or 20 to 60, or 21 to 40, or 22 to
30, or 23 to 28 parts by weight per 100 parts by weight of the
alkylphenol charged to the reaction mixture. Such amounts may be
present at the time of initial mixture of the alkylphenol with
other reactants, or the initial amount of oil may be less and then
increased to any of the above values during subsequent processing.
In one embodiment, the oil of lubricating viscosity is present in
any of the above-identified amounts at the time of the removal of
the steam in step (d), described below. In certain embodiments the
oil of lubricating viscosity will be present during the step of
neutralizing the sulfur-bridged phenol but need not be present
during the sulfurization step, if the sulfurization is conducted in
a step prior to neutralization.
[0025] In the case where the amount of alkaline earth metal
hydroxide or oxide is present in an amount in excess of the
stoichiometric amount needed to neutralize the alkylphenol
moieties, the resulting salt is said to be overbased. Overbased
materials in general, otherwise referred to as overbased or
superbased salts, are generally homogeneous Newtonian systems
characterized by a metal content in excess of that which would be
present for neutralization according to the stoichiometry of the
metal and the particular acidic organic compound reacted with the
metal. Overbased materials are prepared by reacting an acidic
material (typically an inorganic acid or lower carboxylic acid,
typically carbon dioxide) with a mixture comprising an acidic
organic compound (in this instance, the sulfurized phenol or
phenate), a reaction medium of at least one inert, organic solvent
(e.g., mineral oil, naphtha, toluene, xylene) for said acidic
organic material, a stoichiometric excess of a metal base, and a
promoter such as a phenol or alcohol. The amount of excess metal is
commonly expressed in terms of metal ratio. The term "metal ratio"
is the ratio of the total equivalents of the metal to the
equivalents of the acidic organic compound. A neutral metal salt
has a metal ratio of one. A salt having 4.5 times as much metal as
present in a normal salt will have metal excess of 3.5 equivalents,
or a ratio of 4.5.
[0026] In order to facility preparation of an overbased detergent,
the basic composition may be optionally further reacted with carbon
dioxide. Such treatment will convert excess basicity arising from
the stoichiometric excess of alkaline earth hydroxide or oxide to
the carbonate. The amount of carbon dioxide may be an amount added
until an excess is observed that is not absorbed by the reaction
mixture. Such an amount will depend on the amount of basic alkaline
earth material that is present, and any other basic materials, but
in some embodiments may amount to 0.5 to 2 or 1 to 1.5 or 1.1 to
1.3 or 0.9 to 1.1 moles per mole alkylphenol charged. In some
embodiments, the amount of carbon dioxide supplied may be 10 to 50
parts by weight per 100 parts by weight of alkylphenol charged to
the system, alternatively 12 to 25 or 15 to 20 parts per 100 parts.
The reaction with the carbon dioxide may take place over 1 to 10
hours, or 2 to 8 or 3 to 6 or 3.5 to 5 hours.
[0027] Overbased detergents are often characterized by Total Base
Number (TBN, as measured by ASTM D-2896). TBN is the amount of
strong acid needed to neutralize all of the overbased material's
basicity, expressed as potassium hydroxide equivalents (mg KOH per
gram of sample). Since overbased detergents are commonly provided
in a form which contains a certain amount of diluent oil, for
example, 40-50% oil, the actual TBN value for such a detergent will
depend on the amount of such diluent oil present, irrespective of
the "inherent" basicity of the overbased material. For the purposes
of the present invention, the TBN of an overbased detergent is to
be recalculated to an oil-free basis, except as noted. Detergents
which are useful in the present technology typically have a TBN
(oil-free basis) of 100 to 800, and in one embodiment 150 to 750,
and in another, 400 to 700. In certain embodiments, the amount of
alkaline earth metal hydroxide or oxide will be the amount suitable
to provide a product with a TBN of 200 to 600 on an oil-free basis;
such materials are typically considered "overbased." Products that
are substantially "neutral," that is, not overbased or not
significantly overbased, may nevertheless exhibit a TBN of 100-350.
The overall TBN of the composition, including oil, will be derived
from the TBN contribution of the individual components. In the case
of a final lubricant formulation, the various components
contributing TBN may include dispersants, the detergents, and other
basic materials.
[0028] Metal compounds useful in making basic metal salts are
generally any Group 1 or Group 2 metal compounds (CAS version of
the Periodic Table of the Elements). The Group 1 metals of the
metal compound include Group 1a alkali metals such as sodium,
potassium, and lithium, as well as Group 1b metals such as copper.
The Group 2 metals of the metal base include the Group 2a alkaline
earth metals such as magnesium, calcium, and barium, as well as the
Group 2b metals such as zinc or cadmium. In one embodiment the
Group 2 metals are magnesium, calcium, barium, or zinc, and in
another embodiments magnesium or calcium or, in particular,
calcium. In certain embodiments the metal is calcium or sodium or a
mixture of calcium and sodium. Generally the metal compounds are
delivered as metal salts. The anionic portion of the salt can be
hydroxide, oxide, carbonate, borate, or nitrate.
[0029] Such overbased materials are well known to those skilled in
the art. Patents describing techniques for making basic salts of
sulfonic acids, carboxylic acids, (hydrocarbyl-substituted)
phenols, phosphonic acids, and mixtures of any two or more of these
include U.S. Pat. Nos. 2,501,731; 2,616,905; 2,616,911; 2,616,925;
2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809;
3,488,284; and 3,629,109.
[0030] The order of addition of the components for the
above-described reaction, and the conditions of reaction, can be
varied as will be apparent to the person skilled in the art. For
instance, the alkylphenol, the alkaline earth metal compound,
sulfur source, and alkylene glycol or dialkylene glycol, and oil,
may be added to a reaction vessel simultaneously or in varying
orders of addition. In one embodiment, the alkylphenol may be first
mixed (in oil) with an approximately stoichiometric amount of the
alkaline earth metal compound and thereafter sulfur may be charged
to the mixture, along with the glycol material. The sulfur may be
supplied in one or in multiple charges. Likewise, the alkaline
earth metal compound may be provided in one or in multiple charges.
Particularly if the product is to be overbased, addition of the
alkaline earth metal compound and treatment with carbon dioxide may
be done in multiple stages. In another embodiment, the alkylphenol
may be first reacted with the sulfur source, in the presence of the
alkylene glycol (or dialkylene glyocol, or ether thereof) in the
absence (or in the presence) of oil, and thereafter the resulting
sulfur-bridged component may be reacted with the alkaline earth
metal compound, typically in the presence of oil.
[0031] During the reaction sequence, the mixture is typically
maintained at elevated temperature, such as 80 to 150.degree. C.,
or 100 to 149.degree. C., or 95 to 130.degree. C., or 100 to
125.degree. C. Temperatures and reaction times may vary depending
on the order of addition of reagents; if different reagents are
added in different stages or times, the temperature and reaction
time of each stage may be adjusted as will be apparent to the
skilled person. In one embodiment the temperature of the reaction
mixture is increased during a first stage, in that the alkylphenol
may be initially heated to 90 to 110.degree. C., e.g., about
100.degree. C., and after the other components are added, the
mixture may be further heated to 120 to 130.degree. C., e.g., about
124 or 125.degree. C. Alternatively, reaction with the sulfur may
be conducted at an elevated temperature, such as 160 to 230.degree.
C., or 170 to 230.degree. C., or 180 to 230.degree. C., or 190 to
225, or 200 to 220, or 210 to 220.degree. C. At any stage during
the reaction, volatile materials may be removed by distillation or
they may be retained in the reaction mixture. The reaction mixture
may be maintained at an elevated temperature for a period of time
sufficient to permit reaction to occur to the desired extent, which
will, of course, depend to some extent on the temperature selected.
Typical overall times of reaction may be 1/2 to 20 hours, or 1 to
10, or 2 to 9, or 3 to 8, or 4 to 7, or 5 to 6 hours.
[0032] Following reaction and, if desired, treatment with carbon
dioxide, the reaction mixture will be subjected to treatment with
steam. In this steam-treatment process, the alkylphenate
composition thus prepared will be heated to 120 to 280.degree. C.
or alternatively 200 to 250.degree. C., or 210 to 230, or 216 to
240.degree. C., and steam will be supplied thereto. The steam may
be provided at superatmospheric pressure and at a temperature of
120.degree. C. to 250.degree. C., or alternatively 190-240.degree.
C., but in any event should be supplied as steam and not as liquid
water. Supplying the steam at superatmospheric pressure means that
the steam may be provided from a source of steam at
superatmospheric pressure; the actual contact between the steam and
the reaction mixture is not necessarily conducted at
superatmospheric pressure.
[0033] The steam which has been added is subsequently removed, and
with it a portion of the volatile byproducts or unreacted
components from the reaction mixture. The steam will be both added
and removed in a continuous or semi-continuous manner commonly
referred to as steam stripping, which is a well-known industrial
process. If desired, the steam may be re-used in multiple passes
through the reaction mixture, or it may be used once after a single
pass. The steam (and other volatile components) may be removed
under reduced pressure of 1.3 to 53 kPa (10 to 400 mmHg), or
alternatively 2.7-13 or 4.0-6.6 kPa (20-100 mmHg or 30-50 mmHg).
The total amount of steam employed in the stripping process may be
1 to 40 parts by weight steam per 100 parts by weight of
alkylphenol charged to the reaction, or alternatively 3 to 36, or
10 to 30, parts by weight. Greater than 36 or 40 parts by weight of
steam may also be used, although the relative benefit obtained by
using higher amounts may be less.
[0034] After the steam stripping, the reaction mixture will contain
a commercial grade of overbased, sulfur-bridged alkylphenate in
oil. The mixture will typically be filtered to remove any insoluble
materials. This filtration may be conducted at 130-200.degree. C.
or 149-185.degree. C. and may make use of a filter aid such as
diatomaceous earth in a method which is well known to those skilled
in the art. In brief, the filter aid may be mixed with the batch to
be filtered and the mixture passed through any of several types of
pressure leaf filters, such as those using screens or cloth, to
form a cake of filter aid. The cake of filter aid performs the
actual removal of solids. The filtration may optionally be assisted
by vacuum. Since, a small amount of liquid and dissolved solids are
necessarily retained within the filter cake, it is desirable that
the smallest possible amount of filter aid be used in order to
provide the highest yield of product.
[0035] The preparation of the optionally overbased, sulfur-bridged
alkylphenate by means of the disclosed technology provides a
material with significantly improved filterability and ease of
filtration. In an industrial environment, improved filterability is
reflected in a reduced amount of filter aid required to permit
effective filtration. If too little filter aid is used, the filter
will become plugged, resulting in reduced flow of filtrate and
inefficiency in production of product. If excessive filter aid is
used or required, the filtrate may flow unimpeded but an
unacceptably large amount of liquid will be retained in the filter
pad, with a loss of yield. It is therefore desired to have an
amount of filter aid sufficient to absorb all the solid materials,
but still having porosity or channels to permit flow of the
filtrate liquids therethrough.
[0036] Filtration efficiency may thus be expressed in terms of
filter aid usage consumption (FAUC). FAUC, which is expressed in
units of weight percent of the final batch yield, may be determined
by a manual batch test or series of batch tests, in which filter
aid is added in increasing amounts until the amount is just
sufficient to obtain good flow of filtrate. "Good flow" is defined
as a filtration time of no longer than 60 seconds or,
alternatively, 90 seconds, for a mixture of 100 mL sample mixed
with 100 mL diluent oil, containing the specified amount of filter
aid, through a screen filter assisted by vacuum to provide a
sensibly dry filter cake. In certain embodiments, the present
technology can be employed with a FAUC of less than 3 percent, such
as 0.5 to 2.5 percent or 0.8 to 2 percent or 1 to 1.5 percent.
[0037] It is unexpected that treatment of the optionally overbased
alkylphenate with a steam-stripping step should lead to improved
filterability. It has been recognized that the presence of water in
the overbasing process can cause the CaCO.sub.3 component formed
thereby to convert to the vaterite form, which leads to problems
with solubility and filtration. It appears that contact with high
temperature steam has a contrary impact on filterability.
[0038] The sulfurized calcium alkylphenate prepared by the
disclosed technology may also have a reduced level of free
monomeric alkylphenate or alkylphenol than materials prepared by
conventional means without the steam-stripping step. When the
alkylphenol starting material is a tetrapropenyl phenol (TPP) such
as, in one instance, paradodecyl phenol (PDDP), the resulting
product may thereby be reduced in amount of residual, monomeric or
unreacted, PDDP or its salt.
[0039] The amount of monomeric TPP within the product may be
determined, if desired, by reverse phase ultra-high performance
liquid chromatography by comparison with calibration standards
prepared containing known amounts of TPP, using a UV detector at
225 nm. The solvent for the sample may be a mixture of 15% acetic
acid in methyl-t-butyl ether. Suitable conditions may involve
injection of a 2 .mu.L sample of filtered material onto a
100.times.2.1 mm Waters UPLC.RTM. column with 1.7 .mu.m particle
size packing. The column temperature may be 40.degree. C. and a
flow rate of eluent may be 0.35 .mu.L/min, with a gradient of
eluent composition from 75% methanol/25% water to 100% methanol.
The TPP monomer amount is determined by integration of the
appropriate peaks.
[0040] The materials of the disclosed technology are typically
employed in an oil to form a composition that may be used as a
lubricant. The oil is typically referred to as an oil of
lubricating viscosity, and various types thereof have been
described above. The amount of the oil of lubricating viscosity
present in a lubricant is typically the balance remaining after
subtracting from 100 weight % the sum of the amount of the compound
of the disclosed technology and the other performance
additives.
[0041] The bridged phenolic compound may be used as one component
of a lubricant formulation. Its amount, when so used, may vary
depending on the end-use application. When used in a passenger car
lubricant it may be present as low as 0.1 weight percent, and when
used in a marine diesel cylinder lubricant it may be present in
amounts as high as 25 percent by weight of the lubricant.
Therefore, suitable ranges may include 0.1 to 25%, or 0.5 to 20%,
or 1 to 18% or 3 to 13% or 5 to 10%, or 0.7 to 5 weight percent or
1 to 3 weight percent, all on an oil-free basis Similar overall
amounts may also be used if the bridged phenolic compound is not
overbased.
[0042] In lubricants containing the material of the disclosed
technology, either a single detergent (that of the disclosed
technology) or multiple detergents may be present. If there are
multiple detergents, the additional detergents may be additional
phenate detergents, or they may be detergents of other types. An
example of another type of detergent is a sulfonate detergent,
prepared from a sulfonic acid. Suitable sulfonic acids include
sulfonic and thiosulfonic acids, including mono or polynuclear
aromatic or cycloaliphatic compounds. Certain oil-soluble
sulfonates can be represented by R.sup.2T(SO.sub.3.sup.-).sub.a or
R.sup.3(SO.sub.3.sup.-).sub.b, where a and b are each at least one;
T is a cyclic nucleus such as benzene or toluene; R.sup.2 is an
aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl;
(R.sup.2)-T typically contains a total of at least 15 carbon atoms;
and R.sup.3 is an aliphatic hydrocarbyl group typically containing
at least 15 carbon atoms. The groups T, R.sup.2, and R.sup.3 can
also contain other inorganic or organic substituents. In one
embodiment the sulfonate detergent may be a predominantly linear
alkylbenzenesulfonate detergent having a metal ratio of at least 8
as described in paragraphs [0026] to [0037] of US Patent
Application 2005-065045. In some embodiments the linear alkyl group
may be attached to the benzene ring anywhere along the linear chain
of the alkyl group, but often in the 2, 3 or 4 position of the
linear chain, and in some instances predominantly in the 2
position.
[0043] In one embodiment, an overbased material is an overbased
saligenin detergent. Overbased saligenin detergents are commonly
overbased magnesium salts which are based on saligenin derivatives.
A general example of such a saligenin derivative can be represented
by the formula
##STR00001##
[0044] where X is --CHO or --CH.sub.2OH, Y is --CH.sub.2-- or
--CH.sub.2OCH.sub.2--, and the --CHO groups typically comprise at
least 10 mole percent of the X and Y groups; M is hydrogen,
ammonium, or a valence of a metal ion (that is, if M is
multivalent, one of the valences is satisfied by the illustrated
structure and other valences are satisfied by other species such as
anions or by another instance of the same structure), R.sup.1 is a
hydrocarbyl group of 1 to 60 carbon atoms, m is 0 to typically 10,
and each p is independently 0, 1, 2, or 3, provided that at least
one aromatic ring contains an R.sup.1 substituent and that the
total number of carbon atoms in all R.sup.1 groups is at least 7.
When m is 1 or greater, one of the X groups can be hydrogen. In one
embodiment, M is a valence of a Mg ion or a mixture of Mg and
hydrogen. Saligenin detergents are disclosed in greater detail in
U.S. Pat. No. 6,310,009, with special reference to their methods of
synthesis (Column 8 and Example 1) and preferred amounts of the
various species of X and Y (Column 6).
[0045] Salixarate detergents are overbased materials that can be
represented by a compound comprising at least one unit of formula
(I) or formula (II) and each end of the compound having a terminal
group of formula (III) or (IV):
##STR00002##
such groups being linked by divalent bridging groups A, which may
be the same or different. In formulas (I)-(IV) R.sup.3 is hydrogen,
a hydrocarbyl group, or a valence of a metal ion; R.sup.2 is
hydroxyl or a hydrocarbyl group, and j is 0, 1, or 2; R.sup.6 is
hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl
group; either R.sup.4 is hydroxyl and R.sup.5 and R.sup.7 are
independently either hydrogen, a hydrocarbyl group, or
hetero-substituted hydrocarbyl group, or else R.sup.5 and R.sup.7
are both hydroxyl and R.sup.4 is hydrogen, a hydrocarbyl group, or
a hetero-substituted hydrocarbyl group; provided that at least one
of R.sup.4, R.sup.5, R.sup.6 and R.sup.7 is hydrocarbyl containing
at least 8 carbon atoms; and wherein 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 0.1:1 to 2:1. The divalent bridging group "A," which
may be the same or different in each occurrence, includes
--CH.sub.2-- and --CH.sub.2OCH.sub.2--, either of which may be
derived from formaldehyde or a formaldehyde equivalent (e.g.,
paraform, formalin).
[0046] Salixarate derivatives and methods of their preparation are
described in greater detail in U.S. Pat. No. 6,200,936 and PCT
Publication WO 01/56968. It is believed that the salixarate
derivatives have a predominantly linear, rather than macrocyclic,
structure, although both structures are intended to be encompassed
by the term "salixarate."
[0047] Glyoxylate detergents are similar overbased materials which
are based on an anionic group which, in one embodiment, may have
the structure
##STR00003##
wherein each R is independently an alkyl group containing at least
4 or 8 carbon atoms, provided that the total number of carbon atoms
in all such R groups is at least 12 or 16 or 24. Alternatively,
each R can be an olefin polymer substituent. The acidic material
upon from which the overbased glyoxylate detergent is prepared is
the condensation product of a hydroxyaromatic material such as a
hydrocarbyl-substituted phenol with a carboxylic reactant such as
glyoxylic acid or another omega-oxoalkanoic acid. Overbased
glyoxylic detergents and their methods of preparation are disclosed
in greater detail in U.S. Pat. No. 6,310,011 and references cited
therein.
[0048] This supplemental overbased detergent can also be an
overbased salicylate, e.g., an alkali metal or alkaline earth metal
salt of a substituted salicylic acid. The salicylic acids may be
hydrocarbyl-substituted wherein each substituent contains an
average of at least 8 carbon atoms per substituent and 1 to 3
substituents per molecule. The substituents can be polyalkene
substituents. In one embodiment, the hydrocarbyl substituent group
contains 7 to 300 carbon atoms and can be an alkyl group having a
molecular weight of 150 to 2000. Overbased salicylate detergents
and their methods of preparation are disclosed in U.S. Pat. Nos.
4,719,023 and 3,372,116.
[0049] Other overbased detergents can include overbased detergents
having a Mannich base structure, as disclosed in U.S. Pat. No.
6,569,818.
[0050] The amount of any supplemental overbased detergent or
detergents, if present in a lubricant, may be 0.1 to 20, or 0.5 to
18, or 1, 2, or 3 to 13 percent by weight.
[0051] Lubricants prepared using the materials of the
presently-disclosed technology will typically contain one or more
additional additive of the types that are known to be used as
lubricant additives. One such additive is a dispersant. Dispersants
are well known in the field of lubricants and include primarily
what is known as ashless-type dispersants and polymeric
dispersants. Ashless type dispersants are characterized by a polar
group attached to a relatively high molecular weight hydrocarbon
chain. Typical ashless dispersants include nitrogen-containing
dispersants such as N-substituted long chain alkenyl succinimides,
also known as succinimide dispersants. Succinimide dispersants are
more fully described in U.S. Pat. Nos. 4,234,435 and 3,172,892.
Another class of ashless dispersant is high molecular weight
esters, prepared by reaction of a hydrocarbyl acylating agent and a
polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or
sorbitol. Such materials are described in more detail in U.S. Pat.
No. 3,381,022. Another class of ashless dispersant is Mannich
bases. These are materials which are formed by the condensation of
a higher molecular weight, alkyl substituted phenol, an alkylene
polyamine, and an aldehyde such as formaldehyde and are described
in more detail in U.S. Pat. No. 3,634,515. Other dispersants
include polymeric dispersant additives, which are generally
hydrocarbon-based polymers which contain polar functionality to
impart dispersancy characteristics to the polymer. Dispersants can
also be post-treated by reaction with any of a variety of agents.
Among these are urea, thiourea, di-mercaptothiadiazoles, carbon
disulfide, aldehydes, ketones, carboxylic acids,
hydrocarbon-substituted succinic anhydrides, nitriles, epoxides,
boron compounds, and phosphorus compounds. References detailing
such treatment are listed in U.S. Pat. No. 4,654,403. The amount of
dispersant in the present composition can typically be 1 to 10
weight percent, or 1.5 to 9.0 percent, or 2.0 to 8.0 percent, all
expressed on an oil-free basis.
[0052] Another component is an antioxidant. Antioxidants encompass
phenolic antioxidants, which may comprise a butyl substituted
phenol containing 2 or 3 t-butyl groups. The para position may also
be occupied by a hydrocarbyl group, an ester-containing group, or a
group bridging two aromatic rings. Antioxidants also include
aromatic amine, such as nonylated diphenylamines or (optionally
alkylated) phenylnaphthylamine. Other antioxidants include
sulfurized olefins, titanium compounds, and molybdenum compounds.
U.S. Pat. No. 4,285,822, for instance, discloses lubricating oil
compositions containing a molybdenum and sulfur containing
composition. U.S. Patent Application Publication 2006-0217271
discloses a variety of titanium compounds, including titanium
alkoxides and titanated dispersants, which materials may also
impart improvements in deposit control and filterability. Other
titanium compounds include titanium carboxylates such as
neodecanoate. Typical amounts of antioxidants will, of course,
depend on the specific antioxidant and its individual
effectiveness, but illustrative total amounts can be 0.01 to 5
percent by weight or 0.15 to 4.5 percent or 0.2 to 4 percent.
Additionally, more than one antioxidant may be present, and certain
combinations of these can be synergistic in their combined overall
effect.
[0053] Viscosity improvers (also sometimes referred to as viscosity
index improvers or viscosity modifiers) may be included in the
compositions of this invention. Viscosity improvers are usually
polymers, including polyisobutenes, polymethacrylic acid esters,
hydrogenated diene polymers, polyalkylstyrenes, esterified
styrene-maleic anhydride copolymers, hydrogenated
alkenylarene-conjugated diene copolymers and polyolefins.
Multifunctional viscosity improvers, which also have dispersant
and/or antioxidancy properties are known and may optionally be
used.
[0054] Another additive is an antiwear agent. Examples of anti-wear
agents include phosphorus-containing antiwear/extreme pressure
agents such as metal thiophosphates, phosphoric acid esters and
salts thereof, phosphorus-containing carboxylic acids, esters,
ethers, and amides; and phosphites. In certain embodiments a
phosphorus antiwear agent may be present in an amount to deliver
0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08
percent phosphorus. Often the antiwear agent is a zinc
dialkyldithiophosphate (ZDP). For a typical ZDP, which may contain
11 percent P (calculated on an oil free basis), suitable amounts
may include 0.09 to 0.82 percent. Non-phosphorus-containing
anti-wear agents include borate esters (including borated
epoxides), dithiocarbamate compounds, molybdenum-containing
compounds, and sulfurized olefins.
[0055] Other materials that may be used as antiwear agents include
tartrate esters, tartramides, and tartrimides. Examples include
oleyl tartrimide (the imide formed from oleylamine and tartaric
acid) and alkyl diesters (from, e.g., mixed C12-16 alcohols). Other
related materials that may be useful include esters, amides, and
imides of other hydroxy-carboxylic acids in general, including
hydroxy-polycarboxylic acids, for instance, acids such as tartaric
acid, citric acid, lactic acid, glycolic acid, hydroxy-propionic
acid, hydroxyglutaric acid, and mixtures thereof. These materials
may also impart additional functionality to a lubricant beyond
antiwear performance. These materials are described in greater
detail in US Publication 2006-0079413 and PCT publication
WO2010/077630. Such derivatives of (or compounds derived from) a
hydroxy-carboxylic acid, if present, may typically be present in
the lubricating composition in an amount of 0.1 weight % to 5
weight %, or 0.2 weight % to 3 weight %, or greater than 0.2 weight
% to 3 weight %.
[0056] Other additives that may optionally be used in lubricating
oils include pour point depressing agents, extreme pressure agents,
color stabilizers and anti-foam agents. In one embodiment the
lubricant may comprise at least one of a supplemental overbased
detergent, a dispersant, an antioxidant, a viscosity improver, an
anti-wear agent, a pour point depressant, or an extreme pressure
agent.
[0057] Lubricants containing the materials of the disclosed
technology may be used for the lubrication of a wide variety of
mechanical devices, including internal combustion engines, both
two-stroke cycle and four-stroke cycle, spark-ignited and
compression-ignited, sump-lubricated or non-sump-lubricated. The
engines may be run on a variety fuels including gasoline, diesel
fuel, alcohols, bio-diesel fuel, and hydrogen, as well as mixtures
of these (such as gasoline-alcohol mixtures, e.g., E-10, E-15,
E-85).
[0058] The disclosed lubricants are suitable for use as lubricants
for marine diesel engines, particularly as cylinder lubricants. In
one embodiment, the present technology provides a method for
lubricating an internal combustion engine, comprising supplying
thereto a lubricant comprising the composition as described herein.
The invention is suitable for 2-stroke or 4-stroke engines,
including marine diesel engines, such as 2-stroke marine diesel
engines.
[0059] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include: hydrocarbon substituents,
including aliphatic, alicyclic, and aromatic substituents;
substituted hydrocarbon substituents, that is, substituents
containing non-hydrocarbon groups which, in the context of this
invention, do not alter the predominantly hydrocarbon nature of the
substituent; and hetero substituents, that is, substituents which
similarly have a predominantly hydrocarbon character but contain
other than carbon in a ring or chain. A more detailed definition of
the term "hydrocarbyl substituent" or "hydrocarbyl group" is found
in paragraphs [0137] to [0141] of published application US
2010-0197536.
[0060] The amount of each chemical component described is presented
exclusive of any solvent or diluent oil, which may be customarily
present in the commercial material, that is, on an active chemical
basis, unless otherwise indicated. However, 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.
[0061] It is known that some of the materials described above may
interact in the final formulation, so that the components of the
final formulation may be different from those that are initially
added. For instance, metal ions (of, e.g., a detergent) can migrate
to other acidic or anionic sites of other molecules. The products
formed thereby, including the products formed upon employing the
composition of the present invention in its intended use, may not
be susceptible of easy description. Nevertheless, all such
modifications and reaction products are included within the scope
of the present invention; the present invention encompasses the
composition prepared by admixing the components described
above.
Examples
Example 1
[0062] A calcium overbased alkylphenol sulfide is manufactured via
a process as set forth generally in Example 1 of PCT Publication
WO2013/119623 (Lubrizol), Aug. 15, 2013, although typically
conducted on a larger, commercial scale, and without the specific
stripping step as described therein. That is, as it is generally
described in WO2013/119623: to a 3 L four-necked round-bottom
flask, equipped with a thermowell and nitrogen inlet, with
subsurface sparge tube, a Dean-Stark trap, Friedrichs condenser,
and a scrubber, is charged 501.0 g para-dodecylphenol (PDDP). The
PDDP is heated to 100.degree. C. and 59.6 g hydrated lime and 22.7
g ethylene glycol are added. The temperature is increased to
121.degree. C. and 163.9 g sulfur is added. The mixture is heated
over the course of 20 minutes to 215.degree. C. and maintained at
that temperature for an additional 6 hours, at which time 123.3 g
diluent oil is added and the reaction is allowed to cool. During
this reaction, 32.9 g distillate is collected from the reactor.
[0063] The material in the reactor is heated to 135.degree. C., and
204.4 g hydrated lime, 138.2 g ethylene glycol, 43.3 g
alkylbenzenesulfonic acid, and 173.5 g decyl alcohol are added. The
mixture is heated to 168.degree. C. and maintained at that
temperature for 10 minutes, until liquid is no longer readily
distilling. Flow of carbon dioxide is begun at 17-25 L/hr (0.6-0.9
ft.sup.3/hr) and continued for 4 hours.
[0064] Volatile materials are removed from a commercial-scale
product corresponding to Example 1, above, by the stripping process
described either in Example 2 or Reference Example 3, below:
Example 2
[0065] A batch of carbon dioxide-treated material is stripped by
circulating the batch, originating in a feed tank, though an
external heat exchanger and then a flash tank, and finally back to
the feed tank, for a period of time referred to as "strip-back."
During the strip-back, the external heat exchanger batch exit
temperature target it 218-238.degree. C. Heat is also applied
directly to the stripper feed tank throughout the strip-back phase,
until the batch reaches a target temperature of 218-226.degree. C.
The flash tank is operated at a target pressure of 8-16 kPa (60-120
mm Hg absolute), with a residence time of approximately 3 minutes.
Flow through the flash tank provides 2 to 3 volumetric turnovers of
the batch through the flash tank during the strip-back phase, over
approximately 6 hours. Thereafter, the liquid outflow from the
flash tank is redirected to a filter-feed tank, with stripping
conditions otherwise maintained. Throughout the stripping process,
steam is fed to the flash tank via a sub-surface inlet line, at an
approximately uniform rate, targeting delivery of approximately 18
parts by weight total steam (based on 100 parts by weight of
initial alkylphenol reactant, before sulfur coupling and
neutralization/overbasing). The batch is filtered by use of 1
weight % filter aid (FAUC).
Example 3 (Reference)
[0066] A batch of carbon dioxide-treated material is stripped as
described in Example 2, except that no steam is fed to the flash
tank at any time. The batch is filtered by use of 3.5 weight %
filter aid (FAUC).
[0067] Each of the documents referred to above is incorporated
herein by reference, including any prior applications, whether or
not specifically listed above, from which priority is claimed. The
mention of any document is not an admission that such document
qualifies as prior art or constitutes the general knowledge of the
skilled person in any jurisdiction. Except in the Examples, or
where otherwise explicitly indicated, all numerical quantities in
this description specifying amounts of materials, reaction
conditions, molecular weights, number of carbon atoms, and the
like, are to be understood as modified by the word "about." It is
to be understood that the upper and lower amount, range, and ratio
limits set forth herein may be independently combined. Similarly,
the ranges and amounts for each element of the invention can be
used together with ranges or amounts for any of the other
elements.
[0068] As used herein, the transitional term "comprising," which is
synonymous with "including," "containing," or "characterized by,"
is inclusive or open-ended and does not exclude additional,
un-recited elements or method steps. However, in each recitation of
"comprising" herein, it is intended that the term also encompass,
as alternative embodiments, the phrases "consisting essentially of"
and "consisting of" where "consisting of" excludes any element or
step not specified and "consisting essentially of" permits the
inclusion of additional un-recited elements or steps that do not
materially affect the essential or basic and novel characteristics
of the composition or method under consideration. The expression
"consisting of" or "consisting essentially of," when applied to an
element of a claim, is intended to restrict all species of the type
represented by that element, notwithstanding the presence of
"comprising" elsewhere in the claim.
[0069] While certain representative embodiments and details have
been shown for the purpose of illustrating the subject invention,
it will be apparent to those skilled in this art that various
changes and modifications can be made therein without departing
from the scope of the subject invention. In this regard, the scope
of the invention is to be limited only by the following claims. In
certain jurisdictions, recitation of one or more of narrower values
for a numerical range or recitation of a narrower selection of
elements from a broader list means that such recitations represent
preferred embodiments.
* * * * *