U.S. patent application number 13/328797 was filed with the patent office on 2012-06-28 for glycerol-containing functional fluid.
This patent application is currently assigned to Chevron Oronite Company LLC. Invention is credited to Yue-Rong Li, Patrick J. McDougall, Kenneth Nelson, Deane S. Walker.
Application Number | 20120165235 13/328797 |
Document ID | / |
Family ID | 46314783 |
Filed Date | 2012-06-28 |
United States Patent
Application |
20120165235 |
Kind Code |
A1 |
Li; Yue-Rong ; et
al. |
June 28, 2012 |
GLYCEROL-CONTAINING FUNCTIONAL FLUID
Abstract
A functional fluid comprising a major amount of an oil of
lubricating viscosity, and greater than about 0.05 wt-% glycerol. A
method of preparing a functional fluid comprising adding glycerol
to a functional fluid, wherein the glycerol is not glycerol
monooleate. A method of preparing an additive concentrate
comprising adding glycerol to a diluent oil wherein the concentrate
contains from about 1% to about 99% by weight of said diluent. A
method of reducing friction comprising contacting a metal surface
with a functional fluid comprising a major amount of an oil of
lubricating viscosity and greater than about 0.05 wt-%
glycerol.
Inventors: |
Li; Yue-Rong; (Alameda,
CA) ; Walker; Deane S.; (Concord, CA) ;
McDougall; Patrick J.; (Berkeley, CA) ; Nelson;
Kenneth; (Napa, CA) |
Assignee: |
Chevron Oronite Company LLC
San Ramon
CA
|
Family ID: |
46314783 |
Appl. No.: |
13/328797 |
Filed: |
December 16, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61426444 |
Dec 22, 2010 |
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Current U.S.
Class: |
508/369 ;
508/391; 508/501 |
Current CPC
Class: |
C10N 2030/06 20130101;
C10M 2207/046 20130101; C10M 2201/087 20130101; C10M 2219/046
20130101; C10M 2207/289 20130101; C10M 2207/028 20130101; C10M
129/08 20130101; C10M 2215/042 20130101; C10M 2215/08 20130101;
C10M 2207/022 20130101; C10N 2030/52 20200501; C10M 2203/1025
20130101; C10M 2219/106 20130101; C10M 141/10 20130101; C10M
2219/068 20130101; C10M 2209/084 20130101; C10M 2223/045 20130101;
C10N 2040/08 20130101; C10M 2219/046 20130101; C10N 2010/04
20130101; C10M 2223/045 20130101; C10N 2010/04 20130101; C10M
2219/068 20130101; C10N 2010/12 20130101; C10M 2201/087 20130101;
C10N 2010/02 20130101; C10M 2207/028 20130101; C10N 2010/04
20130101; C10M 2219/068 20130101; C10N 2010/12 20130101; C10M
2201/087 20130101; C10N 2010/02 20130101; C10M 2219/046 20130101;
C10N 2010/04 20130101; C10M 2223/045 20130101; C10N 2010/04
20130101; C10M 2207/028 20130101; C10N 2010/04 20130101 |
Class at
Publication: |
508/369 ;
508/501; 508/391 |
International
Class: |
C10M 137/02 20060101
C10M137/02; C10M 135/10 20060101 C10M135/10; C10M 129/74 20060101
C10M129/74 |
Claims
1. A functional fluid comprising a. a major amount of an oil of
lubricating viscosity, and b. greater than about 0.05 wt-%
glycerol.
2. The functional fluid of claim 1 wherein the functional fluid
does not contain more than 0.5 wt-% of glycerol monooleate.
3. The functional fluid of claim 1 wherein the functional fluid
also contains at least one detergent.
4. The functional fluid of claim 3 wherein the detergent further
comprises at least one low overbased sulfonate, at least one medium
overbased sulfonate, at least one high overbased sulfonate, or at
least one non-sulfonate detergent.
5. The functional of claim 4 wherein the low overbased sulfonate is
a low overbased calcium sulfonate.
6. The functional fluid of claim 4 wherein the non-sulfonate
detergent is at least one phenate detergent or at least one
carboxylate detergent.
7. The functional fluid of claim 4 wherein the high overbased
sulfonate is a high overbased calcium sulfonate.
8. The functional fluid of claim 1 wherein the functional fluid
also contains at least one antiwear additive.
9. The functional fluid of claim 8 wherein the at least one
antiwear additive is zinc dialkyl dithiophosphate.
10. The functional fluid of claim 9 wherein the zinc dialkyl
dithiophosphate is derived from a primary alcohol.
11. The functional fluid of claim 1 wherein the functional fluid is
a tractor hydraulic fluid.
12. The functional fluid of claim 1 wherein the amount of glycerol
in the functional fluid is at least about 0.05 weight %.
13. The functional fluid of claim 1 wherein the amount of glycerol
in the functional fluid is from about 0.05 to about 1.0 wt %.
14. The functional fluid of claim 10 wherein the amount of glycerol
in the functional fluid is from about 0.1 to about 0.3 wt %.
15. The functional fluid of claim 1 wherein the functional fluid
also contains a glycerol monooleate.
16. A method of preparing a functional fluid comprising adding
glycerol to a functional fluid, wherein the glycerol is not
glycerol monooleate.
17. A method of preparing an additive concentrate comprising adding
glycerol to a diluent oil wherein the concentrate contains from
about 1% to about 99% by weight of said diluent.
18. A method of reducing friction comprising contacting a metal
surface with a functional fluid comprising a. a major amount of an
oil of lubricating viscosity and b. greater than about 0.05 wt-%
glycerol.
Description
FIELD OF INVENTION
[0001] The present invention relates to functional fluids useful in
systems requiring power transmission fluids, hydraulic fluids
and/or lubrication of moving parts. In particular, the present
invention relates to a functional fluid containing an organic
friction modifier for use in tractor hydraulic fluids.
BACKGROUND OF THE INVENTION
[0002] Modern lubricating oil formulations are formulated to
exacting specifications often set by original equipment
manufacturers. To meet such specifications, various additives are
used, together with base oil of lubricating viscosity. Depending on
the application, a typical lubricating oil composition may contain
dispersants, detergents, anti-oxidants, wear inhibitors, rust
inhibitors, corrosion inhibitors, foam inhibitors, and friction
modifiers just to name a few. Different applications will govern
the type of additives that will go into a lubricating oil
composition.
[0003] A functional fluid is a term which encompasses a variety of
fluids including but not limited to tractor hydraulic fluids, power
transmission fluids including automatic transmission fluids,
continuously variable transmission fluids and manual transmission
fluids, hydraulic fluids, including tractor hydraulic fluids, gear
oils, power steering fluids, fluids used in wind turbines and
fluids related to power train components. It should be noted that
within each of these fluids such as, for example, automatic
transmission fluids, there are a variety of different types of
fluids due to the various transmissions having different designs
which have led to the need for fluids of markedly different
functional characteristics.
[0004] With respect to tractor hydraulic fluids, these fluids are
all-purpose products used for all lubricant applications in a
tractor except for lubricating the engine. Also included as a
tractor hydraulic fluid for the purposes of this invention are
so-called Super Tractor Oil Universal fluids or "STOU" fluids,
which also lubricate the engine. These lubricating applications may
include lubrication of gearboxes, power take-off and clutch(es),
rear axles, reduction gears, wet brakes, and hydraulic accessories.
The components included within a tractor fluid must be carefully
chosen so that the final resulting fluid composition will provide
all the necessary characteristics required in the different
applications. Such characteristics may include the ability to
provide proper frictional properties for preventing wet brake
chatter of oil immersed brakes while simultaneously providing the
ability to actuate wet brakes and provide power take-off (PTO)
clutch performance. A tractor fluid must provide sufficient
antiwear and extreme pressure properties as well as water
tolerance/filterability capabilities. The extreme pressure (EP)
properties of tractor fluids, important in gearing applications,
may be demonstrated by the ability of the fluid to pass a spiral
bevel test as well as a straight spur gear test. The tractor fluid
may need to pass wet brake chatter tests while providing adequate
wet brake capacity when used in oil immersed disk brakes which are
comprised of a bronze, graphitic-compositions and asbestos. The
tractor fluid may need to demonstrate its ability to provide
friction retention for power shift transmission clutches such as
those clutches which include graphitic and bronze clutches.
[0005] When the functional fluid is an automatic transmission
fluid, the automatic transmission fluids must have enough friction
for the clutch plates to transfer power. However, the friction
coefficient of fluids has a tendency to decline due to the
temperature effects as the fluid heats up during operation. It is
important that the tractor hydraulic fluid or automatic
transmission fluid maintain its high friction coefficient at
elevated temperatures, otherwise brake systems or automatic
transmissions may fail.
[0006] A need exists for an alternative organic friction modifier
for use in tractor hydraulic fluids that maintains the protection
of gears at slow speeds.
[0007] JP05-105895 teaches lubricating oil compositions for wet
clutches and brakes used in power transmission units in among other
uses in agricultural, construction, and other industrial machinery,
containing 0.01-10 parts by weight of a C2-C14 aliphatic compound
having two or more hydroxyl groups per 100 parts by weight of a
base oil. In particular JP05-105895 teaches such oils are
especially useful as transmission fluids. Glycerol is disclosed as
such a C2-C14 aliphatic compound having two or more hydroxyl groups
but is not exemplified.
[0008] Bayles, Jr. et al., U.S. Pat. No. 5,284,591, is directed to
a multipurpose functional fluid which is comprised of a major
amount of a hydrocarbon oil and a minor amount, sufficient to
improve characteristics of the fluid of a novel additive. The
additive is comprised of a calcium salt complex, a group II metal
dithiophosphate salt, a borated epoxide, a carboxylic solubilizer
and a sulfurized composition.
[0009] Stoffa et al., U.S. Pat. No. 5,635,459 is directed to a
function fluid composition having improved gear performance which
comprises an oil of lubricating viscosity, and added thereto (a) an
alkali or alkaline earth metal salt complex in the form of borated
and/or non-borated salts; (b) an EP/antiwear agent comprising a
mixture of zinc salts of dialkylphosphorodithioic acid and
2-ethylhexanoic acid heated with triphenyl phosphite or an olefin;
and (c) a borated epoxide.
SUMMARY OF THE INVENTION
[0010] The present invention is directed to a functional fluid
comprising a major amount of an oil of lubricating viscosity and
greater than about 0.05 wt-% glycerol.
[0011] The present invention is directed to a method of preparing a
functional fluid comprising adding glycerol to a functional fluid,
wherein the glycerol is not glycerol monooleate.
[0012] The present invention is directed to a method of preparing
an additive concentrate comprising adding glycerol to a diluent oil
wherein the concentrate contains from about 1% to about 99% by
weight of said diluent.
[0013] The present invention is directed to a method of reducing
friction comprising contacting a metal surface with a functional
fluid comprising a major amount of an oil of lubricating viscosity
and greater than about 0.05 wt-% glycerol.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Prior to discussing the present invention in detail, the
following terms will have the following meanings unless expressly
stated to the contrary.
DEFINITIONS
[0015] The term "alkaline earth metal" refers to calcium, barium,
magnesium, strontium, or mixtures thereof.
[0016] The term "alkyl" refers to both straight- and branched-chain
alkyl groups.
[0017] The term "metal" refers to alkali metals, alkaline earth
metals, transition metals or mixtures thereof.
[0018] The term "Metal to Substrate ratio" refers to the ratio of
the total equivalents of the metal to the equivalents of the
substrate. An overbased sulphonate detergent typically has a metal
ratio of 12.5:1 to 40:1, in one aspect 13.5:1 to 40:1, in another
aspect 14.5:1 to 40:1, in yet another aspect 15.5:1 to 40:1 and in
yet another aspect 16.5:1 to 40:1.
[0019] TBN numbers reflect more alkaline products and therefore a
greater alkalinity reserve. The TBN of a sample can be determined
by ASTM Test No. D2896 or any other equivalent procedure. In
general terms, TBN is the neutralization capacity of one gram of
the lubricating composition expressed as a number equal to the mg
of potassium hydroxide providing the equivalent neutralization.
Thus, a TBN of 10 means that one gram of the composition has a
neutralization capacity equal to 10 mg of potassium hydroxide. TBN
of the actives should be measured.
[0020] The term "low overbased" or "LOB" refers to an overbased
detergent having a low TBN of the actives of about 0 to about
60.
[0021] The term "high overbased" or "HOB" refers to an overbased
detergent having a high TBN of the actives of greater than about 60
to about 400.
[0022] As stated above, the present invention provides a method of
improving the brake and clutch capacity of a functional fluid by
adding an antiwear improving amount of glycerol to the functional
fluid.
Functional Fluids
[0023] The functional fluids of the present invention use base oils
derived from mineral oils, synthetic oils or vegetable oils. A base
oil having a viscosity of at least about 2.5 cSt at about
40.degree. C. and a pour point below about 20.degree. C.,
preferably at or below 0.degree. C., is desirable. The base oils
may be derived from synthetic or natural sources. Base oils may be
derived from any of one or combination of Group I through Group V
base stocks as defined in American Petroleum Institute Publication
1509, which is herein incorporated for all purposes.
[0024] Mineral oils for use as the base oil in this invention
include, for example, paraffinic, naphthenic and other oils that
are ordinarily used in lubricating oil compositions.
[0025] Vegetable oils may include, for example, canola oil or
soybean oil.
[0026] Synthetic oils include, for example, both hydrocarbon
synthetic oils and synthetic esters and mixtures thereof having the
desired viscosity. Hydrocarbon synthetic oils may include, for
example, oils prepared from the polymerization of ethylene, i.e.,
polyalphaolefin or PAO, or from hydrocarbon synthesis procedures
using carbon monoxide and hydrogen gases such as in a
Fisher-Tropsch process. Useful synthetic hydrocarbon oils include
liquid polymers of alpha olefins having the proper viscosity.
Especially useful are the hydrogenated liquid oligomers of C.sub.6
to C.sub.12 alpha olefins such as 1-decene trimer. Likewise, alkyl
benzenes of proper viscosity, such as didodecyl benzene, can be
used. Useful synthetic esters include the esters of monocarboxylic
acids and polycarboxylic acids, as well as mono-hydroxy alkanols
and polyols. Typical examples are didodecyl adipate,
pentaerythritol tetracaproate, di-2-ethylhexyl adipate,
dilaurylsebacate, and the like. Complex esters prepared from
mixtures of mono and dicarboxylic acids and mono and dihydroxy
alkanols can also be used. Blends of mineral oils with synthetic
oils are also useful.
[0027] The functional fluid of the present invention also contains
a friction-modifying amount of the glycerol described herein.
Typically, the total amount of glycerol contained in the functional
fluid will be at least about 0.05 wt %. In other embodiment, the
total amount of glycerol contained in the functional fluid is
greater than about 0.05 wt %. In other embodiments the functional
fluid contains at least about 0.1 wt-% glycerol, or at least about
0.15 wt-% glycerol, or at least about 0.2 wt-% glycerol, or at
least about 0.3 wt-% glycerol, or at least about 0.5 wt-% glycerol.
Typically the functional fluid contains less than about 2 wt-%
glycerol, or less than about 1 wt-%, or less than about 0.75 wt-%
glycerol, or less than about 0.6 wt-% glycerol, or less than about
0.5 wt-%. In one embodiment, the functional fluid contains from
about 0.05 wt. % to about 1 wt. % of glycerol; in another
embodiment, from about 0.05 wt. % to about 0.3 wt. % of glycerol;
and in another embodiment, from about 0.1 wt. % to about 0.3 wt. %
of glycerol.
[0028] In one embodiment the functional fluid of the invention may
also contain a glycerol fatty acid ester in addition to glycerol.
When the glycerol fatty acid ester is contained in the functional
fluid, the functional fluid contains glycerol and does not contain
more than 0.5 wt-% of the glycerol fatty acid ester. In one
embodiment, the functional fluid contains glycerol and does not
contain more than 0.25 wt-% of the glycerol fatty acid ester; in
one embodiment, the functional fluid contains glycerol and does not
contain more than 0.20 wt-% of the glycerol fatty acid ester; in
one embodiment, the functional fluid contains glycerol and does not
contain more than 0.15 wt-% of the glycerol fatty acid ester; in
one embodiment, the functional fluid contains glycerol and does not
contain more than 0.10 wt-% of the glycerol fatty acid ester; and,
in one embodiment, the functional fluid contains glycerol and does
not contain more than 005 wt-% of the glycerol fatty ester.
[0029] A specific glycerol fatty acid ester is glycerol monooleate.
For the purposes of this invention it is understood that glycerol
monooleate refers to the commercial materials sold as glycerol
monooleate that are the reaction product of commercially available
glycerol and mixtures of fatty acids that are predominantly oleic
acid. The reaction product generally contains a mixture of the
mono-, di- and tri-ester, although the mono-ester is the
predominant ester. Examples of commercial glycerol monoleate
include Priolube.TM. 1408 and Radiasurf.TM. 7149 (i.e., esters of
fatty acids including glycerol trioleate).
[0030] In one embodiment the functional fluid contains glycerol,
but does not contain any of the glycerol fatty acid ester
derivative.
[0031] In one embodiment, the glycerol fatty acid ester derivative
is a mixture of glycerol mono-oleate, di-oleate and tri-oleate in
which glycerol mono-oleate is the species with the highest
concentration in the mixture. Typically, the mixture comprises
about 40-60 wt % of glycerol mono-oleate.
[0032] In one embodiment the functional fluid of the invention may
contain glycerol which is added into the functional fluid, or
associated additive package, separately from any glycerol fatty
acid ester derivative.
[0033] In one embodiment the functional fluid of the present
invention may also contain at least one low overbased detergent, at
least one high overbased detergent and at least one antiwear
additive.
The Overbased Detergent Additive
[0034] Overbased detergent additives are well known in the art and
preferably are alkali or alkaline earth metal overbased detergent
additives. Such detergent additives are prepared by reacting a
metal oxide or metal hydroxide with a substrate and carbon dioxide
gas. The substrate is typically an acid, usually an acid selected
from the group consisting of aliphatic substituted sulfonic acids,
aliphatic substituted carboxylic acids, and aliphatic substituted
phenols.
[0035] The terminology "overbased" relates to metal salts,
preferably, metal salts of sulfonates, carboxylates and phenates,
wherein the amount of metal present exceeds the stoichiometric
amount. Such salts are said to have conversion levels in excess of
100% (i.e., they comprise more than 100% of the theoretical amount
of metal needed to convert the acid to its "normal", "neutral"
salt). The expression "metal ratio", often abbreviated as MR, is
used in the prior art and herein to designate the ratio of total
chemical equivalents of metal in the overbased salt to chemical
equivalents of the metal in a neutral salt according to known
chemical reactivity and stoichiometry. Thus, in a normal or neutral
salt, the metal ratio is one and in an overbased salt, MR, is
greater than one. They are commonly referred to as overbased,
hyperbased or superbased salts and are usually salts of organic
sulfur acids, carboxylic acids, or phenols.
[0036] The overbased detergent typically has a metal to substrate
ratio of at least 1.1:1, preferably at least 2:1, more preferably
at least 4:1, or at least 10:1.
[0037] Sulfonic acids include the mono or polynuclear aromatic or
cycloaliphatic compounds which, when overbased, are called
sulfonates.
[0038] Specific examples of sulfonic acids useful in this invention
are mahogany sulfonic acids; bright stock sulfonic acids; sulfonic
acids derived from lubricating oil fractions having a Saybolt
viscosity from about 100 seconds at 100.degree. F. to about 200
seconds at 210.degree. F.; petrolatum sulfonic acids; mono and
polywax substituted sulfonic and polysulfonic acids of, e.g.,
benzene, naphthalene, phenol, diphenyl ether, naphthalene
disulfide, diphenylamine, thiophene, alphachloronaphthalene, etc.;
other substituted sulfonic acids such as alkyl benzene sulfonic
acids (where the alkyl group has at least 8 carbons), cetylphenol
monosulfide sulfonic acids, dicetyl thianthrene disulfonic acids,
dilauryl beta naphthyl sulfonic acid, dicapryl nitronaphthalene
sulfonic acids, and alkaryl sulfonic acids such as dodecyl benzene
"bottoms" sulfonic acids.
[0039] The bottoms acids are derived from benzene that has been
alkylated with propylene tetramers or isobutene trimers to
introduce 1, 2, 3 or more branched chain C.sub.12 substituents on
the benzene ring. Dodecyl benzene bottoms, principally mixtures of
mono and didodecyl benzenes, are available as by-products from the
manufacture of household detergents. Similar products obtained from
alkylation bottoms formed during manufacture of linear alkyl
sulfonates (LAS) are also useful in making the sulfonates used in
this invention.
[0040] The production of sulfonates from detergent manufacture
products by reaction with, e.g., SO.sub.3, is well known to those
skilled in the art. See, for example, the articles "Sulfonation and
Sulfation", Vol. 23, pp. 146 et seq. and "Sulfonic Acids", Vol. 23,
pp. 194 et seq, both in Kirk Othmer "Encyclopedia of Chemical
Technology", Fourth Edition, published by John Wiley & Sons,
N.Y. (1997).
[0041] Also included are aliphatic sulfonic acids containing at
least about 7 carbon atoms, often at least about 12 carbon atoms in
the aliphatic group, such as paraffin wax sulfonic acids,
unsaturated paraffin wax sulfonic acids, hydroxy substituted
paraffin wax sulfonic acids, hexapropylene sulfonic acids,
tetraamylene sulfonic acids, polyisobutene sulfonic acids wherein
the polyisobutene contains from 20 to 7000 or more carbon atoms,
chloro substituted paraffin wax sulfonic acids, nitroparaffiin wax
sulfonic acids, etc.; cycloaliphatic sulfonic acids such as
petroleum naphthene sulfonic acids, cetyl cyclopentyl sulfonic
acids, lauryl cyclohexyl sulfonic acids, bis(isobutyl)cyclohexyl
sulfonic acids, etc.
[0042] With respect to the sulfonic acids or salts thereof
described herein, it is intended that the term "petroleum sulfonic
acids" or "petroleum sulfonates" includes all sulfonic acids or the
salts thereof derived from petroleum products. A particularly
valuable group of petroleum sulfonic acids are the mahogany
sulfonic acids (so called because of their reddish brown color)
obtained as a by-product from the manufacture of petroleum white
oils by a sulfonic acid process.
[0043] Other descriptions of overbased sulfonate salts and
techniques for making them can be found in the following U.S. Pat.
Nos. 2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800;
2,202,781; 2,212,786; 2,213,360; 2,228,598; 2,223,676; 2,239,974;
2,263,312; 2,276,090; 2,276,297; 2,315,514; 2,319,121; 2,321,022;
2,333,568; 2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027;
2,374,193; 2,383,319; 3,312,618; 3,471,403; 3,488,284; 3,595,790;
and 3,798,012. Each of these patents is hereby incorporated by
reference in its entirety.
[0044] In one embodiment, a low overbased detergent is employed.
Preferably, the low overbased detergent is a low overbased
sulfonate detergent. More preferred, the low overbased sulfonate
detergent is a low overbased alkaline earth metal sulfonate
detergent. Most preferred, the alkaline earth metal is selected
from calcium, magnesium, sodium, strontium or barium. Even more
preferred, the low overbased alkaline earth metal sulfonate
detergent is a low overbased calcium sulfonate detergent.
[0045] In one embodiment, a medium overbased detergent is employed.
Preferably, the medium overbased detergent is medium overbased
calcium sulfonate.
[0046] Preferably, the high overbased detergent is a high overbased
sulfonate detergent. More preferred, the high overbased sulfonate
detergent is a high overbased alkaline earth metal sulfonate
detergent. Most preferred, the alkaline earth metal is selected
from calcium, magnesium, sodium or barium. Even more preferred, the
high overbased alkaline earth metal sulfonate detergent is a high
overbased calcium sulfonate detergent or a high overbased magnesium
detergent.
[0047] In one embodiment, non-sulfonate containing detergents are
employed. Such detergents include, but are not limited to,
carboxylate and phenate detergents. These carboxylate detergents or
phenate detergents or both may be in the functional fluid
containing the glycerol additive.
[0048] Typical carboxylate detergents employed are those that are
described in U.S. Pat. Nos. 7,163,911; 7,465,696 and the like which
are herein incorporated by reference.
[0049] Typical phenate detergents employed are those that are
described in U.S. Pat. No. 7,435,709 and the like, which are herein
incorporated by reference.
Antiwear Additive
[0050] Examples of antiwear additives that may be employed in the
present invention include zinc dialky-1-dithiophosphate (primary
alkyl, secondary alkyl, and aryl type), diphenyl sulfide, methyl
trichlorostearate, chlorinated naphthalene,
fluoroalkylpolysiloxane, lead naphthenate, neutralized phosphates,
dithiophosphates, and sulfur-free phosphates. Preferably, the
antiwear additive is zinc dialkyl thiophospate. More preferred, the
zinc dialkyl dithiophosphate is derived from a primary alcohol.
[0051] Besides the glycerol, the detergents and the antiwear
additives employed in the functional fluid of the present
invention, the functional fluid may also comprise other additives
described below. These additional components can be blended in any
order and can be blended as combinations of components.
Other Additive Components
[0052] The following additive components are examples of some of
the components that can be favorably employed in the present
invention. These examples of additives are provided to illustrate
the present invention, but they are not intended to limit it:
A. Metal Detergents
[0053] Sulfurized or unsulfurized alkyl or alkenyl phenates,
sulfonates derived from synthetic or natural feedstocks,
carboxylates, salicylates, phenalates, sulfurized or unsulfurized
metal salts of multi-hydroxy alkyl or alkenyl aromatic compounds,
alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or
unsulfurized alkyl or alkenyl naphthenates, metal salts of
alkanoic, acids, metal salts of an alkyl or alkenyl multiacid, and
chemical and physical mixtures thereof.
B. Anti-Oxidants
[0054] Anti-oxidants reduce the tendency of mineral oils to
deteriorate in service which deterioration is evidenced by the
products of oxidation such as sludge and varnish-like deposits on
the metal surfaces and by an increase in viscosity. Antioxidants
may include, but are not limited to, such anti-oxidants as phenol
type (phenolic) oxidation inhibitors, such as
4,4'-methylene-bis(2,6-di-tert-butylphenol),
4,4'-bis(2,6-di-tert-butylphenol),
4,4'-bis(2-methyl-6-tert-butylphenol),
2,2'-methylene-bis(4-methyl-6-tert-butylphenol),
4,4'-butyldene-bis(3-methyl-6-tert-butyl phenol),
4,4'-isopropylidene-bis(2,6-di-tert-butylphenol),
2,2'-methylene-bis(4-methyl-6-nonylphenol),
2,2'-isobutylidene-bis(4,6-dimethylphenol),
2,2'-methylene-bis(4-methyl-6-cyclohexylphenol),
2,6-di-tert-butyl-1-4-methylphenol,
2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butyl-phenol,
2,6-di-tert-dimethylamino-p-cresol,
2,6-di-tert-4-(N,N'-dimethylaminomethylphenol),
4,4'-thiobis(2-methyl-6-tert-butylphenol),
2,2'-thiobis(4-methyl-6-tert-butylphenol),
bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)-sulfide, and
bis(3,5-di-tert-butyl-4-hydroxybenzyl). Diphenylamine-type
oxidation inhibitors include, but are not limited to, alkylated
diphenylamine, phenyl-.alpha.-naphthylamine, and
alkylated-.alpha.-naphthylamine. Other types of oxidation
inhibitors include metal dithiocarbamate (e.g., zinc
dithiocarbamate), and methylenebis(dibutyldithiocarbamate). The
anti-oxidant is generally incorporated into an oil in an amount of
about 0 to about 10 wt %, preferably 0.05 to about 3.0 wt %, per
total amount of the engine oil.
C. Anti-Wear/Extreme Pressure Agents
[0055] As their name implies, these agents reduce wear of moving
metallic parts. Examples of such agents include, but are not
limited to, phosphates, phosphites, carbamates, esters, sulfur
containing compounds, molybdenum complexes, zinc
dialkyldithiophosphate (primary alkyl, secondary alkyl, and aryl
type), sulfurized oils, sulfurized isobutylene, sulfurized
polybutene, diphenyl sulfide, methyl trichlorostearate, chlorinated
naphthalene, fluoroalkylpolysiloxane, and lead naphthenate.
D. Rust Inhibitors (Anti-rust Agents)
[0056] 1) Nonionic polyoxyethylene surface active agents:
polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether,
polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl
ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl
ether, polyoxyethylene sorbitol monostearate, polyoxyethylene
sorbitol monooleate, and polyethylene glycol monooleate. [0057] 2)
Other compounds: stearic acid and other fatty acids, dicarboxylic
acids, metal soaps, fatty acid amine salts, metal salts of heavy
sulfonic acid, partial carboxylic acid ester of polyhydric alcohol,
and phosphoric ester.
E. Demulsifiers
[0058] Addition product of alkylphenol and ethylene oxide,
polyoxyethylene alkyl ether, and polyoxyethylene sorbitan
ester.
F. Friction Modifiers
[0059] Fatty alcohols, 1,2-diols, borated 1,2-diols, fatty acids,
amines, fatty acid amides, borated esters, and other esters.
G. Multifunctional Additives
[0060] Sulfurized oxymolybdenum dithiocarbamate, sulfurized
oxymolybdenum organo phosphorodithioate, oxymolybdenum
monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum
complex compound, and sulfur-containing molybdenum complex
compound.
H. Viscosity Index Improvers
[0061] Polymethacrylate type polymers, ethylene-propylene
copolymers, styrene-isoprene copolymers, hydrogenated
styrene-isoprene copolymers, polyisobutylene, and dispersant type
viscosity index improvers.
I. Pour Point Depressants
[0062] Polymethyl methacrylate.
J. Foam Inhibitors
[0063] Alkyl methacrylate polymers and dimethyl silicone
polymers.
K. Metal Deactivators
[0064] Disalicylidene propylenediamine, triazole derivatives,
mercaptobenzothiazoles, thiadiazole derivatives, and
mercaptobenzimidazoles.
L. Dispersants
[0065] Alkenyl succinimides, alkenyl succinimides modified with
other organic compounds, alkenyl succinimides modified by
post-treatment with ethylene carbonate or boric acid, esters of
polyalcohols and polyisobutenyl succinic anhydride,
phenate-salicylates and their post-treated analogs, alkali metal or
mixed alkali metal, alkaline earth metal borates, dispersions of
hydrated alkali metal borates, dispersions of alkaline-earth metal
borates, polyamide ashless dispersants and the like or mixtures of
such dispersants.
Additive Packages
[0066] In another embodiment, the invention is directed to additive
concentrates for functional fluids that contain glycerol. The
glycerol-containing concentrate may be provided as an additive
package or concentrate which will be incorporated into a
substantially inert, normally liquid organic diluent such as, for
example, mineral oil, naphtha, benzene, toluene or xylene to form
an additive concentrate. These concentrates usually contain from
about 1% to about 99% by weight, and in one embodiment about 10% to
about 90% by weight of such diluent. Typically, a neutral oil
having a viscosity of about 4 to about 8.5 cSt at 100.degree. C.
and preferably about 4 to about 6 cSt at 100.degree. C. will be
used as the diluent, though synthetic oils, as well as other
organic liquids which are compatible with the additives and
finished lubricating oil can also be used.
EXAMPLES
[0067] The invention will be further illustrated by the following
examples, which set forth particularly advantageous method
embodiments. While the Examples are provided to illustrate the
present invention, they are not intended to limit it. This
application is intended to cover those various changes and
substitutions that may be made by those skilled in the art without
departing from the spirit and scope of the appended claims.
Example A
[0068] A baseline formulation was prepared which contained: [0069]
(i) 1.85 wt % of a 27 TBN oil concentrate of a Ca sulfonate
detergent; [0070] (ii) 1.89 wt % of a 320 TBN oil concentrate of a
Ca sulfonate detergent; [0071] (iii) 1.39 wt-% of an oil
concentrate of a zinc dithiophosphate derived from a primary
alcohol; and [0072] (iv) the balance, a Group II base oil.
Example B (Comparative)
[0073] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.5 wt. % of a
molybdenum dithiocarbamate (available commercially from Asahi Denka
Kogyo K.K. as ADEKA SAKURALUBE 505).
Example C (Comparative)
[0074] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.5 wt. % of a sodium
borate dispersion.
Example D (Comparative)
[0075] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.5 wt. % of a
diethoxylate of tallow amine (available commercially from Huntsman
as SURFONIC T-2).
Example E (Comparative)
[0076] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.5 wt. % of a glycerin
oleyl ether (available commercially from Asahi Denka Kogyo K.K. as
ADEKA FM-618C).
Example F (Comparative)
[0077] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.5 wt. % of a mixture
of C.sub.16 and C.sub.18 1,2-hydroxyalkanes (available commercially
from Asahi Denka Kogyo K.K. (Tokyo, Japan) as ADEKA ECOROYAL
FMD-168).
Example G (Comparative)
[0078] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 1.0 wt. % of ADEKA
ECOROYAL FMD-168, which may be purchased from Asahi Denka Kogyo
K.K. (Tokyo, Japan).
Example H (Comparative)
[0079] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.5 wt. % of glycerol
mono-oleate.
Example I (Comparative)
[0080] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.3 wt. % of ethylene
glycol.
Example J (Comparative)
[0081] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.5 wt. %
1,3-butanediol.
Example 1
[0082] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.3 wt. % of
glycerol.
Example 2
[0083] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example A with 0.15 wt. % of
glycerol.
Evaluation of Slow Speed Gear Performance
[0084] Slow speed gear performance is evaluated using ZF Group's ZF
V3 test. In this test, an FZG stand is operated for 120 hours under
controlled conditions of speed (9 rpm input speed, 13 rpm pinion
speed), load (tenth stage) and temperature (90.degree. C. for 40
hours, 120.degree. C. for 40 hours and 90.degree. C. for 40 hours).
The test gears are lubricated with the test oil. The gear and
pinion are weighed before and after the test. The gear weight loss
and pinion weight loss are used to evaluate the wear obtained with
the test fluid. In order to pass the test, the total weight loss
(gear weight loss+pinion weight loss) must be less than 30 mg.
[0085] Slow speed gear performance results are presented in Table
1. Test results from lubricating oil compositions containing a
variety of different friction modifiers are included for comparison
purposes. If the test resulted in a total weight loss of more than
30 mg at 80 hours, the test was discontinued at that point.
TABLE-US-00001 TABLE 1 S19-5 Slow Speed Gear Performance Results
Amount Total In Finished Weight Total Weight Oil Loss at 80 Loss at
120 Pass/ Friction Modifier (wt. %) hr (mg) hr (mg) Fail Ex. B
MoDTC 0.5 795 -- Fail Ex. C Sodium borate 0.5 403 -- Fail
dispersion Ex. D Tallow amine 0.5 239 -- Fail diethoxylate Ex. E
Glycerin oleyl ether 0.5 185 -- Fail Ex. F C.sub.16 & C.sub.18
1,2- 0.5 40 -- Fail alkanediols Ex. G C.sub.16 & C.sub.18 1,2-
1.0 31 36 Fail alkanediols Ex. H Glycerol mono-oleate 0.5 10 --
Pass Ex. I Ethylene Glycol 0.3 66 74 Fail Ex. J 1,3 Butanediol 0.5
346 471 Fail Ex. 1 Glycerol 0.3 9 12 Pass Ex. 2 Glycerol 0.15 5 9
Pass
[0086] The test results demonstrate that only glycerol and glycerol
mono-oleate were able to pass the S19-5 slow speed gear test
against a wide variety of friction modifiers thereby providing an
alternative friction modifier to glycerol mono-oleate.
Example K
[0087] A baseline formulation was prepared which contained: [0088]
(i) 2.00 wt % of a 114 TBN oil concentrate of a sulfurized Ca
phenate detergent; [0089] (ii) 1.50 wt % of a 150 TBN oil
concentrate of a Ca sulfonate detergent; [0090] (iii) 1.16 wt-% of
an oil concentrate of a zinc dithiophosphate derived from a primary
alcohol; and [0091] (iv) the balance, a Group II base oil.
Example L
[0092] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example K with 0.3 wt. % of glycerol
monooleate.
Example 3
[0093] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example K with 0.1 wt. % of
glycerol.
Example 4
[0094] A baseline formulation was prepared which contained: [0095]
(i) 1.00 wt % of an ethylene carbonate treated dispersant; [0096]
(ii) 1.67 wt % of an oil concentrate of a high overbased calcium
phenate detergent; [0097] (iii) 0.79 wt % of an concentrate of a
high overbased calcium sulfonate detergent [0098] (iv) 1.28 wt-% of
an oil concentrate of a zinc dithiophosphate derived from a primary
alcohol; [0099] (v) 1.00 wt % of a seal swell agent; [0100] (vi) 20
ppm of a foam inhibitor; [0101] (vii) 0.50 wt % of
polymethylacrylate and [0102] (viii) the balance, a Group II base
oil.
[0103] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example 4 with 0.05 wt % of
glycerol.
Example 5
[0104] A baseline formulation was prepared which contained: [0105]
(i) 3 ppm of a foam inhibitor; [0106] (ii) 1.88 wt % of a 425 TBN
oil concentrate of a Ca sulfonate detergent; [0107] (iii) 1.28 wt-%
of an oil concentrate of a zinc dithiophosphate derived from a
primary alcohol; and [0108] (iv) the balance, a Group II base
oil.
[0109] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example 5 with 0.1% of glycerol.
Example 6
[0110] A baseline formulation was prepared which contained: [0111]
(i) 0.1 wt % of an oil concentrate of a high overbased magnesium
sulfonate detergent; [0112] (ii) 2.52 wt % of an oil concentrate of
a high overbased calcium sulfonate detergent; [0113] (iii) 1.23 wt
% of an concentrate of a medium overbased calcium sulfonate
detergent [0114] (iv) 1.53 wt-% of an oil concentrate of a zinc
dithiophosphate derived from a primary alcohol; [0115] (v) 0.7 wt %
of a seal swell agent; [0116] (vi) 30 ppm of a foam inhibitor;
[0117] (vii) 0.035 wt % of thiadiazole and [0118] (viii) the
balance, a Group II base oil.
[0119] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example 6 with 0.05 wt % of
glycerol.
Example M
[0120] A baseline formulation was prepared which contained: [0121]
(i) 0.1 wt % of an oil concentrate of a high overbased magnesium
sulfonate detergent; [0122] (ii) 2.52 wt % of an oil concentrate of
a high overbased calcium sulfonate detergent; [0123] (iii) 1.23 wt
% of an concentrate of a medium overbased calcium sulfonate
detergent [0124] (iv) 1.53 wt-% of an oil concentrate of a zinc
dithiophosphate derived from a primary alcohol; [0125] (v) 0.7 wt %
of a seal swell agent; [0126] (vi) 30 ppm of a foam inhibitor;
[0127] (vii) 0.035 wt % of thiadiazole; [0128] (viii) 0.5 olelyl
amide and [0129] (ix) the balance, a Group II base oil.
[0130] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example M with 0.05 wt % of
glycerol.
TABLE-US-00002 TABLE 2 S19-5 Slow Speed Gear Performance Results
Amount Total In Finished Weight Total Weight Friction Oil Loss at
80 Loss at 120 Modifier (wt. %) hr (mg) hr (mg) Pass/Fail Ex. L
Glycerol 0.3 214 386 Fail mono-oleate Ex. 3 Glycerol 0.1 18 28 Pass
Ex. 4 Glycerol 0.1 14 18 Pass Ex 5 Glycerol 0.05 8 8 Pass Ex. 6
Glycerol 0.05 4 5 Pass Ex. M Glycerol 0.05 67 102 Fail
[0131] The lubricating oils of Examples 3 and 4 show that
lubricating oils containing glycerol and various detergent
additives results low total weight loss at 80 hours and 120 hours.
Based upon the results, an amount of glycerol less than glycerol
mono-oleate gives good friction modifying results.
Example N
[0132] A baseline formulation was prepared which contained: [0133]
(i) 0.05 wt % of an oil concentrate of a high overbased magnesium
sulfonate detergent; [0134] (ii) 2.52 wt % of an oil concentrate of
a high overbased calcium sulfonate detergent; [0135] (iii) 1.23 wt
% of an concentrate of a medium overbased calcium sulfonate
detergent [0136] (iv) 1.53 wt-% of an oil concentrate of a zinc
dithiophosphate derived from a primary alcohol; [0137] (v) 0.5 wt %
of a seal swell agent; [0138] (vi) 20 ppm of a foam inhibitor;
[0139] (vii) 0.04 wt % of thiadiazole; [0140] (viii) 0.5 olelyl
amide; [0141] (ix) 3.0 wt % viscosity index improver; [0142] (x)
0.2 wt % pour point depressant and [0143] (xi) the balance, a Group
II base oil.
Example 7
[0144] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example N with 0.2 wt % of glycerol and
0.25 wt % glycerol mono-oleate.
Example O
[0145] A lubricating oil composition was prepared by top-treating
the baseline formulation of Example N with 0.25 wt % glycerol
mono-oleate.
[0146] The lubricating oils in Examples 7 and O were evaluated
according JDQ-95 Spiral Bevel and Final Drive Gear Wear which
compared the lubricating oils of Examples 7 and O with a reference
oil. In particular, the scoring of the gears was evaluated to
determine wear. The test procedure duration is 50 hours. The test
may be may be performed at Southwest Research Institute, San
Antonio, Tex., U.S.A.
TABLE-US-00003 TABLE 3 Glycerol Glycerol mono- In oleate in
Finished Finished Friction Oil Oil Modifier (wt. %) (wt %) JDQ95
Pass/Fail Ex. 7 Glycerol/ 0.20 0.25 9.sup.1 Pass Glycerol
mono-oleate Ex. O Glycerol 0 0.25 4.sup.2 Fail mono-oleate
.sup.1Rating at 50 test hours. .sup.2Rating at 2 test hours.
[0147] Example 7 shows that an added amount of glycerol to a
lubricating oil composition that already comprises glycerol
mono-oleate results in passing JDQ95. By contrast, the lubricating
oil that only contained glycerol mono-oleate failed the JDQ95 test
after only two hours of the test. It is clear that a combination of
glycerol and glycerol mono-oleate provides good friction modifying
results.
* * * * *