U.S. patent application number 15/034348 was filed with the patent office on 2016-10-06 for epoxyamine alkoxylate motor oil dispersants.
The applicant listed for this patent is DOW GLOBAL TECHNOLOGIES LLC. Invention is credited to John B. Cuthbert, Brian A. Jazdzewski, Cynthia Pierre, Cynthia L. Rand, Daniel F. Zweifel.
Application Number | 20160289590 15/034348 |
Document ID | / |
Family ID | 51904257 |
Filed Date | 2016-10-06 |
United States Patent
Application |
20160289590 |
Kind Code |
A1 |
Pierre; Cynthia ; et
al. |
October 6, 2016 |
EPOXYAMINE ALKOXYLATE MOTOR OIL DISPERSANTS
Abstract
A composition comprising a base oil and a dispersant, the base
oil comprising a polyalkylene glycol and the dispersant being an
epoxy amine alkoxylate of Structure I is useful in a process
whereby the composition is used as a lubricant in a mechanical
device.
Inventors: |
Pierre; Cynthia;
(Naperville, IL) ; Rand; Cynthia L.; (Sanford,
MI) ; Jazdzewski; Brian A.; (Freeport, TX) ;
Cuthbert; John B.; (Midland, MI) ; Zweifel; Daniel
F.; (Horgen, CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DOW GLOBAL TECHNOLOGIES LLC |
Midland |
MI |
US |
|
|
Family ID: |
51904257 |
Appl. No.: |
15/034348 |
Filed: |
October 29, 2014 |
PCT Filed: |
October 29, 2014 |
PCT NO: |
PCT/US2014/062822 |
371 Date: |
May 4, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61904168 |
Nov 14, 2013 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2205/22 20130101;
C10M 2203/1006 20130101; C10N 2040/253 20200501; C10M 2209/1055
20130101; C10M 2215/042 20130101; C10M 2209/1045 20130101; C10M
2205/0285 20130101; C10N 2030/70 20200501; C10N 2030/04 20130101;
C10M 2203/045 20130101; C10N 2040/252 20200501; C10M 2203/024
20130101; C10N 2030/041 20200501; C10M 2203/1025 20130101; C10M
2205/223 20130101; C10M 2209/1075 20130101; C10N 2020/04 20130101;
C10M 169/04 20130101; C10M 2209/1055 20130101; C10M 2209/1085
20130101; C10M 2209/1045 20130101; C10M 2209/1055 20130101; C10M
2209/1055 20130101; C10M 2209/1065 20130101; C10M 2209/1055
20130101; C10M 2209/1065 20130101; C10M 2209/1085 20130101; C10M
2203/1025 20130101; C10N 2020/02 20130101; C10M 2203/1025 20130101;
C10N 2020/02 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04 |
Claims
1. A composition comprising a base oil and a dispersant wherein the
base oil comprises a polyalkylene glycol and the dispersant has the
following structure: ##STR00005## where A is homopolymer of
propylene oxide or a random copolymer of ethylene oxide and
propylene oxide and where the concentration of ethylene oxide
moieties in A is from zero to 30 weight percent based on total
weight of ethylene oxide and propylene oxide moieties and wherein
the dispersant has a molecular weight in a range of 5,000 grams per
mole and 7,500 grams per mole where the base oil contains more than
50 weight-percent of the polyalkylene glycol based on total base
oil weight.
2. The composition of claim 1, further characterized by the
concentration of dispersant being in a range of 3 to 12
weight-percent based on total weight of base oil and
dispersant.
3. The composition of claim 1, further characterized by the base
oil consisting of one or a combination of more than one
polyalkylene glycol.
4. The composition of claim 1, further characterized by the
dispersant having a molecular weight in a range of 6,000 grams per
mole and 7,000 grams per mole.
5. The composition of claim 1, further characterized by the base
oil comprising an alcohol initiated water-insoluble propylene oxide
polymer.
6. A process comprising the steps of providing the composition of
claim 1 into a mechanical device where parts move with respect to
one another such that the composition contacts at least a portion
of the area between the parts that move with respect to one
another.
7. The process of claim 6, further characterized by the mechanical
device being an engine and the parts that move with respect to one
another being a piston and piston shaft of the engine.
8. The process of claim 7, where the mechanical device is a diesel
engine.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a dispersant for motor oil.
In particular, an epoxyamine alkoxylate that serves as an effective
dispersant in polyalkylene glycol oil.
[0003] 2. Introduction
[0004] Motor oils provide lubrication in a demanding environment
that includes proximity to combustion reactions that produce
tremendous heat and combustion byproducts such as soot. Soot
detrimentally increases the viscosity of motor oil, thereby
reducing engine fuel efficiency, while also increasing engine wear.
Build-up of soot is especially problematic in diesel engines
because their design tends to introduce greater oil contamination
in return for reduced emissions.
[0005] Dispersant and detergents are included in fully formulated
motor oils to control soot and other deposits. A detergent
functions to neutralize the precursors that lead to oil degradation
whereas dispersants suspend soot and similar contaminants. The
suspension of these particles prevents an increase in engine oil
viscosity, soot induced wear, and filter blockage.
[0006] Polyalkylene glycol (PAG) motor oils are an attractive
alternative to hydrocarbon motor oil. PAG-based motor oils offer
desirable advantages over hydrocarbon--based motor oils such as
higher viscosity index, improved film formation, non-varnishing,
improved heat transfer, excellent shear performance and stability.
These inherent properties of PAGs allow them to be used as motor
oils without need for added viscosity modifiers typical in many
motor oils. Viscosity modifiers can break down during use and
contribute to motor oil contaminates and diminished
performance.
[0007] A challenge with PAG-based motor oils is identifying a
suitable dispersant. Many dispersants suitable for use in
hydrocarbon-based motor oils are not effective in PAG-based motor
oils. PAGs are generally more polar than hydrocarbon based motor
oil and, as a result, dispersants suitable for use in hydrocarbon
based motor oils tend to not be soluble in PAG-based motor oil.
Therefore, there is a need in the art to identify dispersants that
are soluble in PAG-based motor oil, and that are effective soot
dispersants especially in diesel motor oil applications.
BRIEF SUMMARY OF THE INVENTION
[0008] The present invention provides a solution to the need for a
dispersant that is soluble in PAG-based motor oil, even under the
demanding application of diesel motor oil applications.
[0009] Surprisingly, an epoxy amine alkoxylate has been found to be
soluble in PAG-based motor oil and successfully disperses soot in
the PAG-based motor oil even under stringent diesel motor testing.
The epoxy amine alkoxylate has the structure of Structure I:
##STR00001##
where A is a homopolymer of propylene oxide or a random copolymer
of ethylene oxide (EO) and propylene oxide (PO) and where the
concentration of EO moieties in A is from zero to 30 weight percent
(wt %) based on total weight of EO and PO moieties. The desirable
molecular weight of the epoxy amine alkoxylate is in a range of
5,000 grams per mole (g/mol) to 7,500 g/mol, most preferably 6,000
g/mol to 7,000 g/mol.
[0010] In a first aspect, the present invention is a composition
comprising a base oil and a dispersant wherein the base oil
comprises a polyalkylene glycol and the dispersant has the
following structure:
##STR00002##
where A is homopolymer of propylene oxide or a random copolymer of
ethylene oxide and propylene oxide and where the concentration of
ethylene oxide moieties in A is from zero to 30 weight percent
based on total weight of ethylene oxide and propylene oxide
moieties and wherein the dispersant has a molecular weight in a
range of 5,000 grams per mole and 7,500 grams per mole.
[0011] In a second aspect, the present invention is process
comprising the steps of providing the composition of the first
aspect into a mechanical device where parts move with respect to
one another such that the composition contacts at least a portion
of the area between the parts that move with respect to one
another.
[0012] The composition of the present invention is useful as motor
oil. The process of the present invention is useful for employing
the composition as a lubricant.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 shows an exemplary schematic for a two-step synthesis
process for preparing a dispersant for use in the present
invention.
[0014] FIGS. 2a and 2b illustrate shear stress sweep and time sweep
curves for indicating formulation viscosities for formulations
containing 5 wt % dispersant and 5 wt % carbon black.
[0015] FIGS. 3a and 3b illustrate shear stress sweep and time sweep
curves for indicating formulation viscosities for formulations
containing 5 wt % dispersant and 5, 6, 7 and 8 wt % loadings of
carbon black.
[0016] FIGS. 4a and 4b illustrate shear stress sweep and time sweep
for indicating formulation viscosities for formulations containing
6 wt % dispersant and 5, 6, 7 and 8 wt % loadings of carbon
black.
[0017] FIGS. 5a and 5b illustrate shear stress sweep and time sweep
curves for indicating formulation viscosities for formulations
containing 7 wt % dispersant and 5, 6, 7 and 8 wt % loadings of
carbon black.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Test methods refer to the most recent test method as of the
priority date of this document unless a date is indicated with the
test method number. References to test methods contain both a
reference to the testing society and the test method number. Test
method organizations are referenced by one of the following
abbreviations: ASTM refers to ASTM International (formerly known as
American Society for Testing and Materials); EN refers to European
Norm; DIN refers to Deutsches Institute fur Normung; and ISO refers
to International Organization for Standards.
[0019] "And/or" means "and, or as an alternative". "Multiple" and
"plurality" mean two or more. All ranges include endpoints unless
otherwise indicated.
[0020] "Polymer" refers generally to both homopolymers and
copolymers (that is, heteropolymers) without limitation unless
otherwise indicated. "Copolymer" refers to a molecule containing
multiple polymerized units of more than one monomeric species.
[0021] The composition of the present invention comprises a base
oil that comprises a polyalkylene glycol (PAG). The base oil
desirably is composed primarily of (that is, contains more than 50
weight-percent based on total base oil weight) and can consist of
one or a combination of more than one PAG.
[0022] Suitable PAGs normally have a viscosity at 40 degrees
Celsius (.degree. C.) that is within a range of from 18
centiStokes, preferably 20 centiStokes (cSt)(20 square millimeters
per second (mm.sup.2/s)), to 10,000 cSt (10,000 mm.sup.2/s) and a
viscosity at 100.degree. C. that is within a range of from 3 to
2,000 cSt (3 to 2,000 mm.sup.2/s).
[0023] Suitable PAGs include reaction products of a 1,2-oxide
(vicinal epoxide) with one or more material selected from a group
consisting of water, an alcohol, or an aliphatic polyhydric alcohol
containing from 2 hydroxyl groups to 6 hydroxyl groups and two or
more, preferably three or more, more preferably four or more while
at the same time 22 or fewer, preferably 16 or fewer and more
preferably 12 or fewer carbon atoms per molecule. Suitable
1,2-oxides (alkylene oxides) include lower alkylene oxides (that
is, alkylene oxides containing from two to eight carbon atoms).
Examples of suitable 1,2-oxides includes ethylene oxide, propylene
oxide, butylene oxide, cyclohexene oxide and glycidol as well as
any combination of more than one of these 1,2-oxides. The PAG can
be formed by known techniques in which an aliphatic polyhydric
alcohol or water or monohydric alcohol (often called an
"initiator") is reacted with a single 1,2-oxide or a mixture of two
or more 1,2-oxide. If desired, the initiator can be first
oxyalkylated with one type of 1,2-oxide followed by oxyalkylation
with a different 1,2-oxide or a mixture of 1,2-oxides. The
oxyalkylated initiator can be further oxyalkylated with a still
different 1,2-oxide.
[0024] For convenience, "mixture", when applied to a PAG containing
a mixture of 1,2-oxides, includes both random and/or block
polyethers such as those prepared by: (1) random addition obtained
by simultaneously reacting two or more 1,2-oxides with the
initiator; (2) block addition in which the initiator reacts first
with one 1,2-oxide and then with a second 1,2-oxide, and (3) block
addition in which the initiator first reacts with a first 1,2-oxide
followed by random addition wherein the initiator reacts with a
combination of the first 1,2-oxide and a second 1,2-oxide.
[0025] Any suitable ratio of different 1,2-oxides may be employed.
When a mixture of ethylene oxide (EO) and propylene oxide (PO) is
utilized to form polyethers by random and/or block addition, the
proportion of EO is generally three weight percent (wt %) or more,
preferably 5 wt % or more and at the same time typically 60 wt % or
less, preferably 50 wt % or less based on total mixture weight.
[0026] Aliphatic polyhydric alcohol reactants used in making the
PAG include those containing from two hydroxyl (OH) groups to six
OH groups and at the same time two or more, preferably three or
more, more preferably four or more while at the same time 22 or
fewer, preferably 16 or fewer and more preferably 12 or fewer
carbon atoms carbon atoms per molecule. Examples of suitable
aliphatic alcohol reactants include ethylene glycol, propylene
glycol, 2,3-butylene glycol, 1,2-butylene glycol, 1,2-butanediol,
1,3-propanediol, 1,5-pentane diol, 1,6-hexene diol, glycerol,
trimethylolpropanes, sorbitol, pentaerythritol, and mixtures
thereof. Cyclic aliphatic polyhydric compounds such as starch,
glucose, sucrose, and methyl glucoside may also be employed in PAG
preparation. Each of the aforesaid polyhydric compounds and
alcohols can be oxyalkylated with EO, PO, butylene oxide (BO),
cyclohexene oxide, glycidol, or mixtures thereof. For example,
glycerol can be first oxyalkylated with PO and the resulting PAG
oxyalkylated with EO. Alternatively, glycerol can be reacted with
EO and the resulting PAG reacted with PO and EO. Each of the
above-mentioned polyhydric compounds can be reacted with mixtures
of EO and PO or any two or more of the aforesaid 1,2-oxides, in the
same manner. Techniques for preparing suitable polyethers from
mixed 1,2-oxides are shown in U.S. Pat. Nos. 2,674,619; 2,733,272;
2,831,034; 2,948,575; and 3.036,118.
[0027] Monohydric alcohols typically used as initiators include the
lower acyclic alcohols such as methanol, propylene glycol methyl
ether (for example DOWANOL.TM. PM, DOWANOL is a trademark of The
Dow Chemical Company), ethanol, propanol, butanol, pentanol,
hexanol, neopentanol, isobutanol, and decanol as well as higher
acyclic alcohols derived from both natural and petrochemical
sources with 11 carbon atoms to 22 carbon atoms. As noted
previously, water can also be used an initiator.
[0028] Preferably, the PAG for use in the present invention is
selected from PAGs produced by the polymerization of PO or both EO
and PO onto an initiator. One desirable PAG is an alcohol initiated
water-insoluble PO polymer.
[0029] The base oil can contain up to less than 50 wt % based on
total base oil weight of other lubricating oils such as vegetable
oil, mineral oil, synthetic lubricants such as polyolesters,
alkylaromatics, polyethers, hydrogenated or non-hydrogenated
poly-alpha-olefins and similar substances of lubricating viscosity.
The base oil can also be free of any other lubricating oils.
[0030] PAGs are desirably selected from those having the following
formula:
R--[X--(CH.sub.2CH.sub.2O).sub.n(C.sub.yH.sub.2yO).sub.p--Z].sub.m
where R is hydrogen or an alkyl or an alkyl-phenyl group having
from one carbon atom to 30 carbon atoms; X is oxygen, sulfur, or
nitrogen; y is a single or combined integer from three to 30; Z is
hydrogen or a hydrocarbyl or hydrocarboxyl group containing from
one carbon atom to 30 carbon atoms; n+p is from six to 60 and the
distribution of n and p can be random or in any specific sequence;
m is one to 8; and polyether molecular weight is from 350 Daltons
to 3,500 Daltons.
[0031] A variety of suitable PAG products are currently available
commercially, including but not limited to those products sold
under the following brand names: PLURIOL.TM. A750E; PLURACOL.TM.
WS55; WS100, WS170, B11/25, B11/50, B32/50; BREOX.TM. A299;
BREOX.TM. 50A; PPG-33-series; UCON.TM. 50-HB series; SYNALOX.TM.
50-xxB series; SYNALOX.TM. 100-xxB series; D21/150; PLURONIC.TM.
450PR, PLURONIC.TM. 600PR; TERRALOX WA46; TERRALOX WA110;
SYNALOX.TM. 40-D150; polygycol B01/20, B01/40, B01/50, B15, B35;
UCON.TM. LB65, LB125, LB285, W1285, W1625, P41/200; PLURONIX
GENAPOL.TM.; WAKO TO1/15, TO1/35, TO1/60; LUPRANOL.TM. 9209 and
330; AND SELEXOL.TM.
[0032] PLURIOL is a trademark of BASF SE Societas Europae. PLURACOL
and PLURONIC are a trademarks of BASF Corporation. BREOX is a
trademark of BP p.l.c. UCON and SELEXOL are trademarks of Union
Carbide Corporation. SYNALOX is a trademark of The Dow Chemical
Company. GENAPOL is a trademark of Clariant Produkte GMBH. LUPRANOL
is a trademark of BASF Aktiengesellschaft Corporation.
[0033] The composition further comprises a dispersant that has the
following structure:
##STR00003##
where A is propylene oxide or a random copolymer of ethylene oxide
and propylene oxide and where the concentration of ethylene oxide
moieties in A is from zero to 30 weight percent based on total
weight of ethylene oxide and propylene oxide moieties and wherein
the dispersant has a molecular weight in a range of 5,000 grams per
mole and 7,500 grams per mole.
[0034] The dispersant is obtainable from a two-step synthesis
process where an initial epoxy resin reacts with di-butyl-amine
(DBA) in a first step and then the resulting product is alkoxylated
in a second step, as shown schematically in FIG. 1. Each step can
comprise any number of sub-steps. For example, the alkoxylation
step can comprise any number of feed steps and digestion steps. The
final product shown in FIG. 1 corresponds to Structure 1 where A of
Structure 1 is indicated by the following structure:
##STR00004##
where each occurrence of n is either a PO moiety or an EO moiety as
is indicated by the option of a pendant methyl or hydrogen
group.
[0035] The initial epoxy resin is a liquid reaction product of
epichlorohydrin and bisphenol A such as that which is commercially
available as DER.TM.-331 Liquid Epoxy Resin (DER is a trademark of
The Dow Chemical Company). The epoxy resin reacts with two mole
equivalents of DBA, with the DBA fed over 1.5 hours at 140.degree.
C. and then allowed to digest at 140.degree. C. for three
hours.
[0036] The second reaction step is the alkoxylation of the reaction
product of the first reaction step (intermediate product).
Alkoxylation can be accomplished via multiple epoxide feeds.
Alkoxylation includes reacting with PO or EO and PO to create an
alkoxy chain from the pendant hydroxyl (OH) groups of the
intermediate product. The alkoxy chain is either PO oxide or a
random copolymer of EO and PO. Conduct the alkoxylation by adding a
base catalyst (for example, potassium hydroxide) and removing water
by means of a vacuum. Slowly add alkylene oxide to the reactor as
125.degree. C. Once all of the alkylene oxide has been added, keep
the reactor at 125.degree. C. for five hours to allow the alkylene
oxide to react. Remove the catalyst remains by absorption on a
filter agent and filtration.
[0037] The alkoxylation step in preparing the dispersant is
sufficient to achieve a concentration of EO moieties that is from
zero to 30 weight percent based on the total weight of EO and PO
moieties. EO moieties correspond to the copolymerized components of
ethylene oxide in the resulting polymer. Similarly, PO moieties
correspond to the copolymerized components of propylene oxide in
the resulting polymer. Desirably, the concentration of EO moieties
is greater than zero, preferably three wt % or more, more
preferably five wt % or more, and can be ten wt % or more, 15 wt %
or more, 20 wt % or more and even 25 wt % or more but is 30 wt % or
less based on total weight of EO and PO moieties. If the
concentration of EO exceeds 30 wt % the material does not perform
as a desirable soot dispersant.
[0038] The alkoxylation step in preparing the dispersant is further
sufficient to achieve a dispersant molecule having a molecular
weight that is in a range of 5,000 to 7,500 grams per mole.
Desirably, the molecular weight of the dispersant is 5,500 g/mol or
more, preferably 6,000 g/mol or more, still more preferably 6,500
g/mol or more and can be 7,000 g/mol or more while at the same time
is 7,500 g/mol or less, preferably 7,000 g/mol or less. Determine
molecular weight of the dispersant by gel permeation chromatography
(GPC).
[0039] Preferably, the dispersant is of the structure of Structure
I where A is a random copolymer of EO and PO with a PO moiety
concentration that is 90 wt % or more, preferably 93 wt % or more,
still more preferably 95 wt % or more and less than 100 wt % based
on total combined weight of EO and PO moieties and where the
dispersant has a molecular weight of 6,000 g/mol or more,
preferably 6,500 g/mol or more and at the same time 7,000 g/mol or
less.
[0040] The concentration of dispersant in the base oil is desirably
one wt % or more, preferably three wt % or more, still more
preferably four wt % or more, even more preferably five wt % or
more and can be six wt % or more, seven wt % or more, eight wt % or
more, nine wt % or more, ten wt % or more and even 11 wt % or more
while at the same time is desirably 12 wt % or less, preferably 11
wt % or less and can be ten wt % or less, nine wt % or less, eight
wt % or less and even seven wt % or less. At concentrations below
one wt % the dispersant is generally too dilute to effectively
disperse soot particulates at a high enough concentration to be
valuable in a motor oil. At concentrations above 12 wt % the
dispersant can cause an increase in the composition viscosity and
that requires base oil modifications to compensate.
[0041] The dispersant of the present invention surprisingly has the
necessary properties to act as a soot dispersant in PAG-based oils.
The dispersant is soluble in PAGs. The dispersant demonstrates an
ability to disperse soot in PAGs, even under motor oil use
temperatures. The dispersant is thermally stable in motor oil
applications. By concomitantly possessing all of these
characteristics, the dispersant proves to be a surprisingly
effective dispersant in PAG-based motor oil.
[0042] The composition of the present invention can further
comprise other additives in addition to the dispersant and base
oil. Examples of suitable additives include extreme pressure (EP)
and anti-wear (AW) additives. Suitable additives include zinc
dialkyldithiophosphates, arylphosphate esters,
molybdenumdithiocarbamate, aminic antioxidants, phenolic
antioxidants, corrosion inhibitors, aminic phosphate esters,
anti-foaming agents, silicon oil, and total base number (TBN)
boosters.
[0043] The process of the present invention provides a method for
lubricating a mechanical device with the composition of the present
invention. The process of the present invention comprises providing
the composition of the present invention into a mechanic device
where parts move with respect to one another such that the
composition contacts at least a portion of the area between the
parts that move with respect to one another. A particularly
desirable mechanical device for this process is an engine where the
parts that move with respect to one another are a piston and piston
shaft of the engine. One particularly demanding application for
which the process of the present invention is suitable is where the
mechanical device is a diesel engine. Diesel engines produce more
soot in the motor oil lubricant than most engines so the dispersant
serves a particularly demanding role in diesel engine motor oil
compositions. Yet, the composition of the present invention has
proven to be successful in dispersing soot in diesel engine
applications.
Examples
[0044] The following examples serve to illustrate aspects of the
present invention including characteristics of the dispersant in
PAG motor oil compositions.
[0045] Dispersant
[0046] The following examples use a dispersant having the structure
of Structure I and are further characterized by "A" being a random
copolymer of EO and PO where the EO moiety concentration is five
weight percent of the combined weight of EO and PO moieties and the
average molecular weight of the dispersant is between 6,000 and
7,000 g/mol. Prepare the dispersant using the two-step synthesis as
described previously herein.
[0047] Base Oil
[0048] The base oils used are selected from those in Table 1.
TABLE-US-00001 TABLE 1 Name Descriptor Characterization Oil Type
UCON .TM. 50-HB- HB EO-PO random copolymer produced by V 100 random
condensation of a 1:1 mixture by weight of EO and PO with butanol;
kinematic viscosity at 100.degree. C. is 4.59 cSt. Fluid A
HB-capped [alpha]-butyl-omega- V
methylpoly(oxyethylene)poly(oxypropylene) produced by random
condensation of a 1:1 mixture by weight of EO and PO with butanol
Fluid B LB-PO [alpha]-butyl-omega- V hydroxypoly(oxypropylene)
Fluid C LB-capped [alpha]-butyl-omega- V methylpoly(oxypropylene)
UCON .TM. OSP 32 OSP PO/BO [alpha]-dodecyl-omega- V
hydroxypoly(oxypropylene)poly(oxybutylene) produced by random
condensation of a 1:1 mixture by weight of PO and 1,2-butylene
oxide with dodecanol Fluid D OSP capped [alpha]-dodecyl-omega- V
methylpoly(oxypropylene)poly(oxybutylene) produced by random
condensation of a 1:1 mixture by weight of PO and 1,2-butylene
oxide with dodecanol SYNESSTIC .TM. 5 Alkyl Monoalkylated
hexadecylnaphthalene V naphthalene SPECTRASYN .TM. PAO
polyalphaolefin IV PAO 4 SPECTRASYN .TM. PAO polyalphaolefin IV PAO
6 YUBASE .TM. 4 B&N base Group III mineral oil III oil YUBASE
.TM. 6 B&N Base Group II mineral oil III oil MO-Group II- Group
II oil combined with EHC base oil. II EHC 45 SPECTRASYN and
SYNESSTIC are trademarks of Exxon Mobil Corporation. YUBASE is a
trademark of SK Lubricants Co.
[0049] Dispersant Solubility in Base Oils
[0050] The solubility of the dispersant in the base oils was
characterized at concentrations up to 6 wt % based on composition
weight at 5.degree. C. and at 80.degree. C. Characterize the
solubility using Phase Identification and Characterization
Apparatus (PICA) II in combination with Epoch software PICA II
V10.0.5-current version as of priority date of this document. To
conduct the characterization, prepare compositions in one
milliliter glass vials and place in a 96 well aluminum plate in an
enclosed test space with a robotic gripper arm. An image of each
vial is collected with both standard white light and plane
polarized light using a Canon Rebel XTi camera. Determine the
clarity of each formulation as a dimensionless measurement in a
grayscale intensity of the pixels from 1-255. A formulation that is
cloudy possesses a clarity measurement of 20 or greater. Cloudy
formulations indicate lack of solubility. Therefore, clarity
measurement values below 20 correspond to formulations of soluble
components.
[0051] Tables 2 and 3 reveal clarity measurements for formulations
of the dispersant with the various base oils at different
concentrations. Table 2 is an evaluation at 5.degree. C. and Table
3 is an evaluation at 80.degree. C. The results reveal that the
dispersant is soluble in the full variety of base oils at both
temperatures.
TABLE-US-00002 TABLE 2 5.degree. C. Formulation Clarity Values (Wt
% Dispersant based on Formulation Weight) 0 0.5 1.0 2.0 3.0 4.0 5.0
6.0 Base Oil wt % wt % wt % wt % wt % wt % wt % wt % UCON 50- 3 3 2
3 2 3 4 3 HB-100 Fluid A 3 3 4 3 3 3 3 3 Fluid B 3 3 3 3 3 2 3 3
Fluid C 3 3 2 4 3 3 3 3 UCON OSP32 2 2 3 3 3 2 3 4 SPECTRASYN 2 2 2
2 2 2 2 2 PAO 6 SPECTRASYN 2 2 3 2 3 3 2 3 PAO 4 SYNESSTIC 5 6 6 7
8 9 7 8 8 YUBASE 4 2 2 2 3 3 3 2 3 YUBASE 6 2 2 2 3 3 3 2 3
MO-Group 4 4 4 4 3 4 3 4 II-EHC 45
TABLE-US-00003 TABLE 3 80.degree. C. Formulation Clarity Values (Wt
% Dispersant based on Formulation Weight) 0 0.5 1.0 2.0 3.0 4.0 5.0
6.0 Base Oil wt % wt % wt % wt % wt % wt % wt % wt % UCON 50- 2 3 3
2 3 3 3 3 HB-100 Fluid A 3 3 3 3 3 3 3 3 Fluid B 3 3 2 3 3 2 2 3
Fluid C 3 3 3 3 3 3 3 3 UCON OSP32 3 3 2 2 3 3 3 3 SPECTRASYN 2 2 2
2 2 2 2 2 PAO 6 SPECTRASYN 2 3 3 3 3 3 3 3 PAO 4 SYNESSTIC 5 5 4 5
5 5 5 5 5 YUBASE 4 3 2 3 3 3 3 3 3 YUBASE 6 3 3 3 2 3 4 4 3
MO-Group 3 4 4 3 3 4 4 3 II-EHC 45
[0052] Solubility was further characterized using a formulation
that includes common oil additives to confirm solubility in the
presence of the additives. Table 4 contains the additive package
used in the screening with concentration in wt % relative to total
formulation weight. Tables 5 and 6 present the clarity values for
the additive-containing formulations with the dispersant at
different concentrations. Table 5 is at 5.degree. C. and Table 6 is
at 80.degree. C. Notably, results are only shown for the oils that
the additive package itself was soluble in.
[0053] The data reveals that the dispersant is soluble in
formulations where the additive package is soluble in the oil.
TABLE-US-00004 TABLE 4 Concentration Component Function Description
(wt %) IRGANOX .TM. Aminic Octylated/butylated 1.125 L57
antioxidant diphenylamine IRGANOX .TM. Aminic Octylated phenyl-
1.875 L06 antioxidant alpha- naphthylamine Elco 103 Anti-wear Zinc
dialkyl 1.00 additive dithiophosphate DESMOPHEN .TM. Acid Aspartate
ester 0.80 NH-1420 scavenger Dow Corning Silicon oil 0.002 200
Fluid 12,500 cSt IRGANOX is a trademark of CIBA Specialty Chemicals
Corporation. DESMOPHEN s a trademark of Bayer Aktiengesellschaft
Corporation.
TABLE-US-00005 TABLE 5 5.degree. C. Formulation Clarity Values (Wt
% Dispersant based on Formulation Weight) 0 0.5 1.0 2.0 3.0 4.0 5.0
6.0 Base Oil wt % wt % wt % wt % wt % wt % wt % wt % UCON 50- 9 9 9
9 9 9 9 9 HB-100 Fluid A 10 10 10 10 10 10 10 10 Fluid B 9 9 9 9 9
9 9 9 Fluid C 9 9 9 9 10 10 10 10 UCON OSP32 9 9 9 9 9 9 9 9
TABLE-US-00006 TABLE 6 80.degree. C. Formulation Clarity Values (Wt
% Dispersant based on Formulation Weight) 0 0.5 1.0 2.0 3.0 4.0 5.0
6.0 Base Oil wt % wt % wt % wt % wt % wt % wt % wt % UCON 50- 9 9 9
9 9 9 9 9 HB-100 Fluid A 10 9 10 10 10 10 9 9 Fluid B 9 9 9 9 9 9 9
9 Fluid C 9 9 9 9 9 9 9 9 UCON OSP32 9 9 9 9 9 9 9 9
[0054] Dispersing Efficiency
[0055] Dispersing efficiency of the dispersant in a base oil was
characterized using carbon black in an oil formulation containing a
full set of additives. Carbon black was used to simulate soot. The
ability to disperse carbon black, which represents soot, was
characterized by measuring the viscosity of the formulations over
time and at different shear stresses. Better dispersibility is
represented by a more uniform viscosity over time and at various
shear stresses.
[0056] Testing was done using 5 wt %, 6 wt %, 7 wt % and 8 wt %
carbon black based on formulation weight. Formulations containing
dispersant loadings of 5 wt %, 6 wt % and 7 wt % were tested. The
general test formulation is shown in Table 7 with concentration in
wt % relative to total formulation weight. Base oil is a mixture of
UCON.TM. LB-165 and UCON LB-285 in a 72.5/27.5 weight ratio. UCON
is a trademark of Union Carbide Corporation
[0057] UCON LB-165 is a PAG characterized as an alcohol-initiated
base stock of oxypropylene groups with one terminal hydroxyl group.
It is water insoluble and has an average molecular weight of 740
g/mole and a viscosity of 34 cSt at 40.degree. C.
[0058] UCON LB-285 is a PAG characterized as an alcohol-initiated
base stock of oxypropylene groups with one terminal hydroxyl group.
It is water insoluble and has an average molecular weight of 1020
g/mole and a viscosity of 61 cSt at 40.degree. C.
TABLE-US-00007 TABLE 7 Concentration Component Function Description
(wt %) 1-napthaleneamine, Aminic 0.60 N-phenyl-(PANA) antioxidant
Irganox L57 Aminic Octylated/butylated 0.50 antioxidant
diphenylamine Additin RC 7115 Phenolic Methylene-bridged 0.950
antioxidant alkylated diphenol Phenothiazine Aminic 0.20
antioxidant IRGAMET .TM. 39 Corrosion Substituted 0.05 inhibitor
tolyltriazole derivative Desmophen NH- Acid Aspartate ester 0.80
1420 scavenger IRGALUBE .TM. Extreme Triphenyl 1.0 TPPT pressure
phosphorothionate and antiwear additive Dibenzyl Extreme 0.30
disulfide pressure additive Dispersant 5, 6 or 7 Base Oil Balance
to 100 IRGAMET and IRGALUBE are trademarks of BASF SE Company.
[0059] FIGS. 2a and 2b illustrate shear stress sweep and time sweep
curves for indicating formulation viscosities for formulations
containing 5 wt % dispersant and 5 wt % carbon black. The "aged"
sample was heat aged at 150.degree. C. for 100 hours to simulate
aged motor oil. The figures reveal that a 5 wt % loading of the
dispersant effectively disperses a 5 wt % loading of carbon black
in the PAG formulation, even upon heat aging.
[0060] FIGS. 3a and 3b illustrate shear stress sweep and time sweep
curves for indicating formulation viscosities for formulations
containing 5 wt % dispersant and 5, 6, 7 and 8 wt % loadings of
carbon black. The data reveals that 5 wt % loading of the
dispersant effectively dispersed up to 6 wt % carbon black equally
well but less well for 7 and 8 wt % carbon black loadings.
[0061] FIGS. 4a and 4b illustrate shear stress sweep and time sweep
for indicating formulation viscosities for formulations containing
6 wt % dispersant and 5, 6, 7 and 8 wt % loadings of carbon black.
The data in these figures reveals that increasing dispersant
concentration to 6 wt % improves dispersability of the carbon black
over 5 wt % loading of dispersant.
[0062] FIGS. 5a and 5b illustrate shear stress sweep and time sweep
curves for indicating formulation viscosities for formulations
containing 7 wt % dispersant and 5, 6, 7 and 8 wt % loadings of
carbon black. The data in these figures reveals that increasing
dispersant concentration to 7 wt % improves dispersability of the
carbon black over 6 wt % loading of dispersant.
[0063] Peugeot DV-4 Engine Test
[0064] The Peugeot DV-4 Engine Test (ACEA European Oil Sequences,
Dec. 2010, 2.6 Medium temperature dispersivity test CEC L-093-04
(DV4TD)) evaluates the ability of an engine lubricant to disperse
the combustion soot accrued during severe diesel engine operation.
The test consists of 240 thirty-minute cycles operated at 4000
revolutions per minute and 11.8 kilograms per hour of fuel flow and
includes brief periods of operation at idle. The test is conducted
at 120.degree. C. Oil performance is evaluated by determining the
viscosity increase of the oil at 100.degree. C. relative to the
viscosity of fresh oil. Oil performance is evaluated once the oil
achieves at least 6 wt % soot as determined by thermogravimetric
analysis (TGA). Piston merit is also assessed. The test is included
in the ACEA European Oil Sequences for the A, B and C categories
for both viscosity increase and piston merit. The Peugeot DV-4
Engine Test was performed by ISP, Grand-Couronne, France.
[0065] Table 8 indicates the formulation tested in the Peugeot DV-4
Engine Test. The base oil is the same as used in the carbon black
dispersion evaluation as described above.
TABLE-US-00008 TABLE 8 Concentration Component Function Description
(wt %) 1-napthaleneamine, Aminic 0.60 N-phenyl-(PANA) antioxidant
Irganox L57 Aminic Octylated/butylated 0.50 antioxidant
diphenylamine Additin RC 7115 Phenolic Methylene-bridged 0.950
antioxidant alkylated diphenol Phenothiazine Aminic 0.20
antioxidant Tolyltriazole 0.15 Desmophen NH- Acid Aspartate ester
0.80 1420 scavenger Irgalube TPPT Extreme Triphenyl 1.0 pressure
phosphorothionate and antiwear additive Dibenzyl Extreme 0.30
disulfide pressure additive Dispersant 5 Base Oil Balance to
100
[0066] FIG. 6 reveals that the test results showing viscosity of
the formulation as a function of soot concentration. A maximum
viscosity of 18.13 cSt is allowable to pass the test. The data in
FIG. 6 reveals that the formulation of the present invention
described in Table 8 passes the Peugeot DV-4 Engine Test with soot
concentrations in excess of 6 wt %.
* * * * *