U.S. patent application number 17/297425 was filed with the patent office on 2022-02-10 for antioxidant mixture for high viscous polyalkylene glycol basestock.
The applicant listed for this patent is BASF SE. Invention is credited to Marcel HARHAUSEN, David LEY, Frank RITTIG, Michael ROIDA, Wolfgang SCHROF.
Application Number | 20220041949 17/297425 |
Document ID | / |
Family ID | 1000005973892 |
Filed Date | 2022-02-10 |
United States Patent
Application |
20220041949 |
Kind Code |
A1 |
HARHAUSEN; Marcel ; et
al. |
February 10, 2022 |
ANTIOXIDANT MIXTURE FOR HIGH VISCOUS POLYALKYLENE GLYCOL
BASESTOCK
Abstract
The invention relates to a lubricant comprising a polyalkylene
glycol basestock, a phenol selected from an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with a
C.sub.1-18 aliphatic alcohol, and an aromatic amine of the formula
(I) as defined hereinafter. The invention further relates to a
method for preparing the lubricant comprising the step of
contacting the polyalkylene glycol basestock, the phenol, and the
aromatic amine of the formula (I); and to a method for reducing the
oxidative degradation of the polyalkylene glycol basestock
comprising the step of contacting the polyalkylene glycol
basestock, the phenol, and the aromatic amine of the formula
(I).
Inventors: |
HARHAUSEN; Marcel;
(Ludwigshafen am Rhein, DE) ; RITTIG; Frank;
(Ludwigshafen am Rhein, DE) ; LEY; David;
(Ludwigshafen am Rhein, DE) ; ROIDA; Michael;
(Ludwigshafen am Rhein, DE) ; SCHROF; Wolfgang;
(Ludwigshafen am Rhein, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
|
DE |
|
|
Family ID: |
1000005973892 |
Appl. No.: |
17/297425 |
Filed: |
November 14, 2019 |
PCT Filed: |
November 14, 2019 |
PCT NO: |
PCT/EP2019/081360 |
371 Date: |
May 26, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2209/1013 20130101;
C10M 129/70 20130101; C10N 2030/08 20130101; C10N 2020/02 20130101;
C10M 133/12 20130101; C10M 169/04 20130101; C10M 2215/064 20130101;
C10N 2020/04 20130101; C10M 107/34 20130101; C10M 2207/284
20130101 |
International
Class: |
C10M 107/34 20060101
C10M107/34; C10M 169/04 20060101 C10M169/04; C10M 129/70 20060101
C10M129/70; C10M 133/12 20060101 C10M133/12 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 2018 |
EP |
18208871.6 |
Claims
1.-15. (canceled)
16. A lubricant comprising a polyalkylene glycol basestock, a
phenol selected from an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with a
C.sub.1-18 aliphatic alcohol, and an aromatic amine of the formula
(I) ##STR00006## wherein R1 and R2 are H or together represent the
group A ##STR00007## and R3 and R4 are independently H or
C.sub.2-C.sub.30 alkyl.
17. The lubricant according to claim 16, where the phenol is an
ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
methanol, ethanol, n-octanol, isooctanol, octadecanol,
1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,
neopentyl glycol, diethylene glycol, triethylene glycol,
pentaerythritol, trimethylhexanediol, trimethylolpropane.
18. The lubricant according to claim 16, where the phenol is an
ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
isooctanol or 1,6-hexanediol.
19. The lubricant according to claim 16, where the polyalkylene
glycol basestock has a kinematic viscosity at 40.degree. C. in the
range from 500-3000 mm.sup.2/s.
20. The lubricant according to claim 16, where the polyalkylene
glycol basestock is an ethoxylated and propoxylated
C.sub.1-C.sub.20 alkanol or C.sub.2-C.sub.20 alkandiol.
21. The lubricant according to claim 16, where the polyalkylene
glycol basestock is an ethoxylated and propoxylated C.sub.2-C.sub.8
alkandiol.
22. The lubricant according to claim 16, where the polyalkylene
glycol basestock is an alkoxylated alcohol with a number average
molecular weight Mn in the range from 500 to 50 000 Da.
23. The lubricant according to claim 22, where the polyalkylene
glycol basestock is an alkoxylated alcohol with a number average
molecular weight Mn in the range from 1000 to 20000 Da.
24. The lubricant according to claim 23, where the polyalkylene
glycol basestock is an alkoxylated alcohol with a number average
molecular weight Mn in the range from 3000 to 10000 Da.
25. The lubricant according to claim 16, where R1 and R2 together
represent the group A, R3 is H, and R4 is C.sub.2-C.sub.30
alkyl.
26. The lubricant according to claim 25, where the phenol is an
ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
1,6-hexanediol or with isooctanol.
27. The lubricant according to claim 16, where R1 and R2 are H, and
R3 and R4 are independently C.sub.2-C.sub.30 alkyl.
28. The lubricant according to claim 27, where the phenol is an
ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
octadecanol.
29. The lubricant according to claim 16, where R3 and R4 are
indepen-dently H or n-propyl, isopropyl, n-, iso-, or tert.-butyl,
n-pentyl, isoamyl, neopentyl, 2-ethyl-butyl, n-hexyl,
1-methylpentyl, 1,3-dimethylbutyl, n-heptyl, isoheptyl, n-octyl,
1,4,4-trime-thyl-2-pentyl, 3,4-, 3,5- or 4,5-dimethyl-1-hexyl, 3-
or 5-methyl-1-heptyl, 1,1,3,3-tetra-methylbutyl, 2-ethylhexyl,
branched octyl, branched octyl as obtained from a dimer of
isobutylene, n-nonyl, 1,1,3-trimethylhexyl, branched nonyl as
obtained from a trimer of tripropylene, 1-methylundecyl,
2-n-butyl-n-octyl, branched dodecyl obtained from a trimer of
isobutylene or a tetramer of propylene, branched pentadecyl
obtained from a pentamer of propylene, 2-n-hexyl-n-decyl or
2-n-octyl-n-dodecyl.
30. The lubricant according to claim 16, where the weight ratio
between the phenol and the aromatic amine is from 1.5:1 to
1:1.5.
31. The lubricant according to claim 16, where the weight ratio
between the phenol and the aromatic amine is from 2:1 to 1:2.
32. The lubricant according to claim 16, where the weight ratio
between the phenol and the aromatic amine is from 5:1 to 1:5.
33. A method for preparing the lubricant as defined in claim 16
comprising the step of contacting the polyalkylene glycol
basestock, the phenol, and the aromatic amine of the formula
(I).
34. A method for reducing the oxidative degradation of the
polyalkylene glycol basestock as defined in claim 16 comprising the
step of contacting the polyalkylene glycol basestock, the phenol,
and the aromatic amine of the formula (I).
Description
[0001] The invention relates to a lubricant comprising a
polyalkylene glycol basestock, a phenol selected from an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with a 01-18
aliphatic alcohol, and an aromatic amine of the formula (I) as
defined hereinafter. The invention further relates to a method for
preparing the lubricant comprising the step of contacting the
polyalkylene glycol basestock, the phenol, and the aromatic amine
of the formula (I); and to a method for reducing the oxidative
degradation of the polyalkylene glycol basestock comprising the
step of contacting the polyalkylene glycol basestock, the phenol,
and the aromatic amine of the formula (I). Combinations of
preferred embodiments with other preferred embodiments are within
the scope of the present invention.
[0002] Lubricants with polyalkylene glycol basestock tend to
degradation upon prolonged heating.
[0003] Object was to find antioxidants to reduce the degradation of
polyalkylene glycol basestock at high temperatures.
[0004] The object was solved by a lubricant comprising a
polyalkylene glycol basestock, [0005] a phenol selected from an
ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
a C.sub.1-18 aliphatic alcohol, and [0006] an aromatic amine of the
formula (I)
##STR00001##
[0006] wherein R1 and R2 are H or together represent the group
A
##STR00002##
and R3 and R4 are independently H or C.sub.2-C.sub.30 alkyl.
[0007] The object was also solved by a method for preparing the
lubricant comprising the step of contacting the polyalkylene glycol
basestock, the phenol, and the aromatic amine of the formula
(I).
[0008] The object was also solved by a method for reducing the
oxidative degradation of the polyalkylene glycol basestock
comprising the step of contacting the polyalkylene glycol
basestock, the phenol, and the aromatic amine of the formula
(I).
[0009] The polyalkylene glycol basestock is usually an alkoxylated
alcohol, preferably an ethoxylated and propoxylated
C.sub.1-C.sub.20 alkanol, C.sub.2-C.sub.20 alkandiol, or
C.sub.3-C.sub.20 alkantriol, in particular an ethoxylated and
propoxylated C.sub.2-C.sub.8 alkandiol.
[0010] Suitable alkoxylated alcohols are ethoxylated, ethoxylated
and propoxylated, or ethoxylated and butoxylated. Preferably,
alkoxylated alcohols are ethoxylated and propoxylated.
[0011] The alkoxylated alcohols may have a number average molecular
weight Mn in the range from 500 to 50 000 Da, preferably from 1000
to 20 000 Da, and in particular from 3000 to 15 000 Da.
[0012] The alkoxylated alcohol may contain 20 to 80 wt.-% ethylene
oxide units, and 80 to 20 wt.-% of propylene oxide units. The
alkoxylated alcohol preferably contains 30 to 70 wt.-% ethylene
oxide units, and 70 to 30 wt.-% of propylene oxide units. In
particular, the alkoxylated alcohol contains 50 to 70 wt.-%
ethylene oxide units, and 50 to 30 wt.-% of propylene oxide units.
The wt.-% of the ethylene oxide and propylene oxide usually sum up
to 100 wt.-%
[0013] The alkoxy groups in the alkoxylated alcohol may be random
or in block sequence. Preferably the alkoxy groups (e.g. the ethoxy
and propoxy groups) in the alkoxylated alcohol are random
sequence.
[0014] The polyalkoxylate chain of the alkoxylated (e.g.
ethoxylated and propoxylated) alcohols may be terminated by a
hydroxy group or a C1 to C4 alkyl, wherein the hydroxy group is
preferred.
[0015] Suitable alcohol units in the alkoxylated alcohol are linear
or branched C.sub.1-C.sub.20 alkanol, C.sub.2-C.sub.20 alkandiol,
or C.sub.3-C.sub.20 alkantriol, preferably C.sub.1-C.sub.8 alkanol,
C.sub.2-C.sub.8 alkandiol, or C.sub.3-C.sub.8 alkantriol, and in
particular C.sub.1-C.sub.6 alkanol, C.sub.2-C.sub.6 alkandiol, or
C.sub.3-C.sub.6 alkantriol.
[0016] In another preferred form the alcohol units in the
alkoxylated (e.g. ethoxylated and propoxylated) alcohol are linear
or branched 02-C.sub.20 alkandiol, preferably C.sub.2-C.sub.12
alkandiol, and in particular C.sub.2-C.sub.8 alkandiol.
[0017] The alcohol units in the alkoxylated alcohol may be a
technical mixture of various chain lengths and isomers.
[0018] The polyalkylene glycol basestock may have a kinematic
viscosity at 40.degree. C. in the range from 500-3000 mm.sup.2/s,
preferably from 700-2000 mm.sup.2/s, and in particular from
900-1300 mm.sup.2/s.
[0019] The polyalkylene glycol basestock may have a kinematic
viscosity at 100.degree. C. in the range from 50-500 mm.sup.2/s,
preferably from 100-350 mm.sup.2/s, and in particular from 150-250
mm.sup.2/s.
[0020] The kinematic viscosity may be determined according to ASTM
D 445.
[0021] The polyalkylene glycol basestock may be water soluble (e.g.
at 20.degree. C.), such as at least 10 g/I, preferably at least 100
g/I.
[0022] The lubricant may comprise at least 50 wt %, preferably at
least 70 wt %, and in particular at least 90 wt % of the
polyalkylene glycol bases.
[0023] The phenol is selected from an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with a 01-18
aliphatic alcohol.
[0024] The phenol is commercially available, for example in the
Irganox.RTM. series from BASF SE, Germany.
[0025] Preferably, the phenol is an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with methanol,
ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
trimethylhexanediol, trimethylolpropane.
[0026] In particular, the phenol is an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
isooctanol, octadecanol, or 1,6-hexanediol. In particular, the
phenol is an ester of 3-(3,5-di-tertbutyl-4-hydroxyphenyl)
propionic acid with isooctanol or 1,6-hexanediol. In another
particular form the phenol is an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
isooctanol. In another particular form the phenol is an ester of
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
octadecanol. In another particular form the phenol is an ester of
3-(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid with
1,6-hexanediol.
[0027] The lubricant may comprise 0.05-5 wt %, preferably 0.1-3 wt
%, and in particular 0.5 1.0 wt % of the phenol.
[0028] The aromatic amine is of the formula (I)
##STR00003##
wherein R1 and R2 are H or together represent the group A
##STR00004##
and R3 and R4 are independently H or C.sub.2-C.sub.30 alkyl.
[0029] In one form of the aromatic amine R1 and R2 is H. In another
form of the aromatic amine R1 and R2 together represent the group
A.
[0030] R3 is usually in the 4-position of the phenyl ring.
[0031] In a preferred form R1 and R2 together represent the group
A, R3 is H, and R4 is C.sub.2-C.sub.30 alkyl.
[0032] In another preferred form R1 and R2 are H, and R3 and R4 are
independently C.sub.2-C.sub.30 alkyl.
[0033] Suitable R3 and R4 are independently H or n-propyl,
isopropyl, n-, iso-, or tert.-butyl, n-pentyl, isoamyl, neopentyl,
2-ethylbutyl, n-hexyl, 1-methylpentyl, 1,3-dimethylbutyl, n-heptyl,
isoheptyl, n-octyl, 1,4,4-trimethyl-2-pentyl, 3,4-, 3,5- or
4,5-dimethyl-1-hexyl, 3- or 5-methyl-1-heptyl,
1,1,3,3-tetramethylbutyl, 2-ethylhexyl, branched octyl, branched
octyl as obtained from a dimer of isobutylene, n-nonyl,
1,1,3-trimethylhexyl, branched nonyl as obtained from a trimer of
tripropylene, 1-methylundecyl, 2-n-butyl-n-octyl, branched dodecyl
obtained from a trimer of isobutylene or a tetramer of propylene,
branched pentadecyl obtained from a pentamer of propylene,
2-n-hexyl-n-decyl or 2-n-octyl-n-dodecyl.
[0034] Preferably, R3 and R4 are independently H or C8-C18 alkyl or
both C8-C18 alkyl.
[0035] In another preferred form R3 and R4 are independently H or
branched C8-C18 alkyl or both branched C8-C18 alkyl.
[0036] In another preferred form R3 and R4 are independently H or
branched octyl as obtained from a dimer of isobutylene, branched
nonyl as obtained from a trimer of tripropylene, branched dodecyl
obtained from a trimer of isobutylene or a tetramer of propylene,
or branched pentadecyl obtained from a pentamer of propylene.
[0037] In a preferred form the aromatic amine is of the formula
(Ia)
##STR00005##
[0038] Where R1, R2, R3 and R4 are as defined above.
[0039] The aromatic amine of the formula (I) are known and
commercially available, e.g. Irganox.RTM. L06 or Irganox.RTM. L57
from BASF SE, Germany.
[0040] The lubricant may comprise 0.05-5 wt %, preferably 0.1-3 wt
%, and in particular 0.5-1.0 wt % of the aromatic amine.
[0041] The weight ratio between the phenol and the aromatic amine
may be from 1.5:1 to 1:1.5, preferably from 2:1 to 1:2, and in
particular from 5:1 to 1:5.
[0042] In a particular form, R1 and R2 together represent the group
A, R3 is H, and R4 is C.sub.2-C.sub.30 alkyl and the phenol is an
ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
1,6-hexanediol.
[0043] In another particular form, R1 and R2 together represent the
group A, R3 is H, and R4 is C.sub.2-C.sub.30 alkyl and the phenol
is an ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid
with isooctanol.
[0044] In another particular form, R1 and R2 are H, and R3 and R4
are independently C.sub.2-C.sub.30 alkyl, and the phenol is an
ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
octadecanol.
[0045] Lubricants usually refers to composition which are capable
of reducing friction between surfaces (preferably metal surfaces),
such as surfaces of mechanical devices. A mechanical device may be
a mechanism consisting of a device that works on mechanical
principles. Suitable mechanical device are bearings, gears, joints
and guidances. The mechanical device may be operated at
temperatures in the range of -30 C to 80.degree. C. Lubricants are
usually specifically formulated for virtually every type of machine
and manufacturing process. The type and concentration of base oils
and/or lubricant additives used for these lubricants may be
selected based on the requirements of the machinery or process
being lubricated, the quality required by the builders and the
users of the machinery, and the government regulation. Typically,
each lubricant has a unique set of performance requirements. In
addition to proper lubrication of the machine or process, these
requirements may include maintenance of the quality of the
lubricant itself, as well as the effect of the lubricant's use and
disposal on energy use, the quality of the environment, and on the
health of the user.
[0046] Typical lubricants are automotive lubricants (e.g. gasoline
engine oils, diesel engine oils, gas engine oils, gas turbine oils,
automatic transmission fluids, gear oils) and industrial lubricants
(e.g. industrial gear oils, pneumatic tool lubricating oil, high
temperature oil, gas compressor oil, hydraulic fluids, metalworking
fluids).
[0047] Examples for lubricants are axel lubrication, medium and
heavy duty engine oils, industrial engine oils, marine engine oils,
automotive engine oils, crankshaft oils, compressor oils,
refrigerator oils, hydrocarbon compressor oils, very
low-temperature lubricating oils and fats, high temperature
lubricating oils and fats, wire rope lubricants, textile machine
oils, refrigerator oils, aviation and aerospace lubricants,
aviation turbine oils, transmission oils, gas turbine oils, spindle
oils, spin oils, traction fluids, transmission oils, plastic
transmission oils, passenger car transmission oils, truck
transmission oils, industrial transmission oils, industrial gear
oils, insulating oils, instrument oils, brake fluids, transmission
liquids, shock absorber oils, heat distribution medium oils,
transformer oils, fats, chain oils, minimum quantity lubricants for
metalworking operations, oil to the warm and cold working, oil for
water-based metalworking liquids, oil for neat oil metalworking
fluids, oil for semi-synthetic metalworking fluids, oil for
synthetic metalworking fluids, drilling detergents for the soil
exploration, hydraulic oils, in biodegradable lubricants or
lubricating greases or waxes, chain saw oils, release agents,
molding fluids, gun, pistol and rifle lubricants or watch
lubricants and food grade approved lubricants.
[0048] The lubricant has usually may have a kinematic viscosity at
40.degree. C. of at least 10, 50, 100, 150, 200, 300, 400, 500,
600, 900, 1400, or 2000 mm.sup.2/s. In another form the lubricant
has usually may have a kinematic viscosity at 40.degree. C. from
200 to 10 000 mm.sup.2/s (cSt), preferably from 500 to 3 000
mm.sup.2/s, and in particular from 1000 to 1500 mm.sup.2/s.
[0049] The lubricant has usually may have a kinematic viscosity at
100.degree. C. of at least 2, 3, 5, 10, 20, 30, 40, or 50
mm.sup.2/s. In another form the lubricant may have a kinematic
viscosity at 100.degree. C. from 10 to 5000 mm.sup.2/s (cSt),
preferably from 30 to 3000 mm.sup.2/s, and in particular from 50 to
2000 mm.sup.2/s
[0050] The lubricant may have a viscosity index of at least 50, 75,
100, 120, 140, 150, 160, 170, 180, 190 or 200.
[0051] The lubricant is usually a lubricating liquid, lubricating
oil or lubricating grease.
[0052] The lubricant usually further comprises [0053] a further
base oil in addition to the polyalkylene glycol basestock selected
from mineral oils, polyalphaolefins, polymerized and
interpolymerized olefins, alkyl naphthalenes, alkylene oxide
polymers, silicone oils, phosphate ester and carboxylic acid ester;
and/or [0054] a lubricant additive.
[0055] The lubricant usually contains up to 10 wt %, preferably up
to 5 wt %, and in particular up to 1 wt % of the further base oil.
In another form the lubricant is free of the further base oil.
[0056] The further base oil may selected from the group consisting
of mineral oils (Group I, II or III oils), polyalphaolefins (Group
IV oils), polymerized and interpolymerized olefins, alkyl
naphthalenes, alkylene oxide polymers, silicone oils, phosphate
esters and carboxylic acid esters (Group V oils). Preferably, the
base oil is selected from Group I, Group II, Group III base oils
according to the definition of the API, or mixtures thereof.
Definitions for the base oils are the same as those found in the
American Petroleum Institute (API) publication "Engine Oil
Licensing and Certification System", Industry Services Department,
Fourteenth Edition, December 1996, Addendum 1, December 1998. Said
publication categorizes base oils as follows: [0057] a) Group I
base oils contain less than 90 percent saturates (ASTM D 2007)
and/or greater than 0.03 percent sulfur (ASTM D 2622) and have a
viscosity index (ASTM D 2270) greater than or equal to 80 and less
than 120. [0058] b) Group II base oils contain greater than or
equal to 90 percent saturates and less than or equal to 0.03
percent sulfur and have a viscosity index greater than or equal to
80 and less than 120. [0059] c) Group III base oils contain greater
than or equal to 90 percent saturates and less than or equal to
0.03 percent sulfur and have a viscosity index greater than or
equal to 120. [0060] d) Group IV base oils contain
polyalphaolefins. Polyalphaolefins (PAO) include known PAO
materials which typically comprise relatively low molecular weight
hydrogenated polymers or oligomers of alphaolefins which include
but are not limited to C2 to about C32 alphaolefins with the C8 to
about C16 alphaolefins, such as 1-octene, 1-decene, 1-dodecene and
the like being preferred. The preferred polyalphaolefins are
poly-1-octene, poly-1-decene, and poly-1-dodecene. [0061] e) Group
V base oils contain any base oils not described by Groups I to IV.
Examples of Group V base oils include alkyl naphthalenes, alkylene
oxide polymers, silicone oils, and phosphate esters.
[0062] Synthetic base oils include hydrocarbon oils and
halo-substituted hydrocarbon oils such as polymerized and
interpolymerized olefins (e.g., polypropylenes,
propylene-isobutylene copolymers, chlorinated polybutylenes,
poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes
(e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,
di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls,
terphenyls, alkylated polyphenols); and alkylated diphenyl ethers
and alkylated diphenyl sulfides and derivative, analogs and
homologs thereof.
[0063] Alkylene oxide polymers and interpolymers and derivatives
thereof where the terminal hydroxyl groups have been modified by
esterification, etherification, etc., constitute another class of
known synthetic base oils. These are exemplified by polyoxyalkylene
polymers prepared by polymerization of ethylene oxide or propylene
oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers
(e.g., methyl-polyisopropylene glycol ether having a molecular
weight of 1000 or diphenyl ether of polyethylene glycol having a
molecular weight of 1000 to 1500); and mono- and polycar-boxylic
esters thereof, for example, the acetic acid esters, mixed C3-C8
fatty acid esters and C13 oxo acid diester of tetraethylene
glycol.
[0064] Silicon-based oils such as the polyalkyl-, polyaryl-,
polyalkoxy- or polyaryloxysilicone oils and sili-cate oils comprise
another useful class of synthetic base oils; such base oils include
tetraethyl silicate, tetraisopropyl silicate,
tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)
silicate, tetra-(p-tert-butyl-phenyl) silicate,
hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl) siloxanes and
poly(methylphenyl)siloxanes. Other synthetic base oils include
liquid esters of phosphorous-containing acids (e.g., tricresyl
phosphate, trioctyl phosphate, diethyl ester of decylphosphonic
acid) and polymeric tetrahydrofurans.
[0065] Suitable lubricant additives may be selected from viscosity
index improvers, polymeric thickeners, corrosion inhibitors,
detergents, dispersants, anti-foam agents, dyes, wear protection
additives, extreme pressure additives (EP additives), anti-wear
additives (AW additives), friction modifiers, metal deactivators,
pour point depressants.
[0066] The viscosity index improvers include high molecular weight
polymers that increase the relative viscosity of an oil at high
temperatures more than they do at low temperatures. Viscosity index
improvers include polyacrylates, polymethacrylates,
alkylmethacrylates, vinylpyrrolidone/methacrylate copolymers, poly
vinylpyrrolidones, polybutenes, olefin copolymers such as an
ethylene-propylene copolymer or a styrene-butadiene copolymer or
polyalkene such as PIB, styrene/acrylate copolymers and polyethers,
and combinations thereof. The most common VI improvers are
methacrylate polymers and copolymers, acrylate polymers, olefin
polymers and copolymers, and styrenebutadiene copolymers. Other
examples of the viscosity index improver include polymethacrylate,
polyisobutylene, alpha-olefin polymers, alpha-olefin copolymers
(e.g., an ethylenepropylene copolymer), polyalkylstyrene, phenol
condensates, naphthalene condensates, a styrenebutadiene copolymer
and the like. Of these, polymethacrylate having a number average
molecular weight of 10000 to 300000, and alpha-olefin polymers or
alpha-olefin copolymers having a number average molecular weight of
1000 to 30000, particularly ethylene-alpha-olefin copolymers having
a number average molecular weight of 1000 to 10000 are preferred.
The viscosity index increasing agents can be added and used
individually or in the form of mixtures, conveniently in an amount
within the range of from 0.05 to 20.0% by weight, in relation to
the weight of the base stock.
[0067] Suitable (polymeric) thickeners include, but are not limited
to, polyisobutenes (PIB), oligomeric co-polymers (OCPs),
polymethacrylates (PMAs), copolymers of styrene and butadiene, or
high viscosity esters (complex esters).
[0068] Corrosion inhibitors may include various oxygen-, nitrogen-,
sulfur-, and phosphorus-containing materials, and may include
metal-containing compounds (salts, organometallics, etc.) and
nonmetal-containing or ashless materials. Corrosion inhibitors may
include, but are not limited to, additive types such as, for
example, hydrocarbyl-, aryl-, alkyl-, arylalkyl-, and
alkylarylversions of detergents (neutral, overbased), sulfonates,
phenates, salicylates, alcoholates, carboxylates, salixarates,
phosphites, phosphates, thiophosphates, amines, amine salts, amine
phosphoric acid salts, amine sulfonic acid salts, alkoxylated
amines, etheramines, polyetheramines, amides, imides, azoles,
diazoles, triazoles, benzotriazoles, benzothiadoles,
mercaptobenzothiazoles, tolyltriazoles (TTZ-type), heterocyclic
amines, heterocyclic sulfides, thiazoles, thiadiazoles,
mercaptothiadiazoles, dimercaptothiadiazoles (DMTD-type),
imidazoles, benzimidazoles, dithiobenzimidazoles, imidazolines,
oxazolines, Mannich reactions products, glycidyl ethers,
anhydrides, carbamates, thiocarbamates, dithiocarbamates,
polyglycols, etc., or mixtures thereof.
[0069] Detergents include cleaning agents that adhere to dirt
particles, preventing them from attaching to critical surfaces.
Detergents may also adhere to the metal surface itself to keep it
clean and prevent corrosion from occurring. Detergents include
calcium alkylsalicylates, calcium alkylphenates and calcium
alkarylsulfonates with alternate metal ions used such as magnesium,
barium, or sodium. Examples of the cleaning and dispersing agents
which can be used include metal-based detergents such as the
neutral and basic alkaline earth metal sulphonates, alkaline earth
metal phenates and alkaline earth metal salicylates
alkenylsuccinimide and alkenylsuccinimide esters and their
borohydrides, phenates, salienius complex detergents and ashless
dispersing agents which have been modified with sulphur compounds.
These agents can be added and used individually or in the form of
mixtures, conveniently in an amount within the range of from 0.01
to 1.0% by weight in relation to the weight of the base stock;
these can also be high total base number (TBN), low TBN, or
mixtures of high/low TBN.
[0070] Dispersants are lubricant additives that help to prevent
sludge, varnish and other deposits from forming on critical
surfaces. The dispersant may be a succinimide dispersant (for
example N-substituted long chain alkenyl succinimides), a Mannich
dispersant, an ester-containing dispersant, a condensation product
of a fatty hydrocarbyl monocarboxylic acylating agent with an amine
or ammonia, an alkyl amino phenol dispersant, a hydrocarbyl-amine
dispersant, a polyether dispersant or a polyetheramine dispersant.
In one embodiment, the succinimide dispersant includes a
polyisobutylene-substituted succinimide, wherein the
polyisobutylene from which the dispersant is derived may have a
number average molecular weight of about to about 5000, or of about
950 to about 1600. In one embodiment, the dispersant includes a
borated dispersant. Typically, the borated dispersant includes a
succinimide dispersant including a polyisobutylene succinimide,
wherein the polyisobutylene from which the dispersant is derived
may have a number average molecular weight of about 400 to about
5000. Borated dispersants are described in more detail above within
the extreme pressure agent description.
[0071] Anti-foam agents may be selected from silicones,
polyacrylates, and the like. The amount of anti-foam agent in the
lubricant compositions described herein may range from 0.001 wt.-%
to 0.1 wt.-% based on the total weight of the formulation. As a
further example, an anti-foam agent may be present in an amount
from about 0.004 wt.-% to about 0.008 wt.-%.
[0072] Suitable extreme pressure agent is a sulfur-containing
compound. In one embodiment, the sulfur-containing compound may be
a sulfurised olefin, a polysulfide, or mixtures thereof. Examples
of the sulfurised olefin include a sulfurised olefin derived from
propylene, isobutylene, pentene; an organic sulfide and/or
polysulfide including benzyldisulfide; bis(chlorobenzyl) disulfide;
dibutyl tetrasulfide; di-tertiary butyl polysulfide; and sulfurised
methyl ester of oleic acid, a sulfurised alkylphenol, a sulfurised
dipentene, a sulfurised terpene, a sulfurised Diels-Alder adduct,
an alkyl sulphenyl N'N-dialkyl dithiocarbamates; or mixtures
thereof. In one embodiment, the sulfurised olefin includes a
sulfurised olefin derived from propylene, isobutylene, pentene or
mixtures thereof. In one embodiment the extreme pressure additive
sulfur-containing compound includes a dimercaptothiadiazole or
derivative, or mixtures thereof. Examples of the
dimercaptothiadiazole include compounds such as
2,5-dimercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof. The
oligomers of hydrocarbyl-substituted
2,5-dimercapto-1,3,4-thiadiazole typically form by forming a
sulfur-sulfur bond between 2,5-dimercapto-1,3,4-thiadiazole units
to form derivatives or oligomers of two or more of said thiadiazole
units. Suitable 2,5-dimercapto-1,3,4-thiadiazole derived compounds
include for example 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole or
2-tert-nonyldithio-5-mercapto-1,3,4-thiadiazole. The number of
carbon atoms on the hydrocarbyl substituents of the
hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole typically
include 1 to 30, or 2 to 20, or 3 to 16. Extreme pressure additives
include compounds containing boron and/or sulfur and/or phosphorus.
The extreme pressure agent may be present in the lubricant
compositions at 0 wt.-% to about 20 wt.-%, or at about 0.05 wt.-%
to about 10.0 wt.-%, or at about 0.1 wt.-% to about 8 wt.-% of the
lubricant composition.
[0073] Examples of anti-wear additives include organo borates,
organo phosphites such as didodecyl phosphite, organic
sulfur-containing compounds such as sulfurized sperm oil or
sulfurized terpenes, zinc dialkyl dithiophosphates, zinc diaryl
dithiophosphates, phosphosulfurized hydrocarbons and any
combinations thereof.
[0074] Friction modifiers may include metal-containing compounds or
materials as well as ashless compounds or materials, or mixtures
thereof. Metal-containing friction modifiers include metal salts or
metal-ligand complexes where the metals may include alkali,
alkaline earth, or transition group metals. Such metal-containing
friction modifiers may also have low-ash characteristics.
Transition metals may include Mo, Sb, Sn, Fe, Cu, Zn, and others.
Ligands may include hydrocarbyl derivative of alcohols, polyols,
glycerols, partial ester glycerols, thiols, carboxylates,
carbamates, thiocarbamates, dithiocarbamates, phosphates,
thiophosphates, dithiophosphates, amides, imides, amines,
thiazoles, thiadiazoles, dithiazoles, diazoles, triazoles, and
other polar molecular functional groups containing effective
amounts of O, N, S, or P, individually or in combination. In
particular, Mo-containing compounds can be particularly effective
such as for example Mo-dithiocarbamates, Mo(DTC),
Mo-dithiophosphates, Mo(DTP), Mo-amines, Mo (Am), Mo-alcoholates,
Mo-alcohol-amides, and the like.
[0075] Ashless friction modifiers may also include lubricant
materials that contain effective amounts of polar groups, for
example, hydroxyl-containing hydrocarbyl base oils, glycerides,
partial glycerides, glyceride derivatives, and the like. Polar
groups in friction modifiers may include hydrocarbyl groups
containing effective amounts of O, N, S, or P, individually or in
combination. Other friction modifiers that may be particularly
effective include, for example, salts (both ash-containing and
ashless derivatives) of fatty acids, fatty alcohols, fatty amides,
fatty esters, hydroxyl-containing carboxylates, and comparable
synthetic long-chain hydrocarbyl acids, alcohols, amides, esters,
hydroxy carboxylates, and the like. In some instances, fatty
organic acids, fatty amines, and sulfurized fatty acids may be used
as suitable friction modifiers. Examples of friction modifiers
include fatty acid esters and amides, organo molybdenum compounds,
molybdenum dialkylthiocarbamates and molybdenum dialkyl
dithiophosphates.
[0076] Suitable metal deactivators include benzotriazoles and
derivatives thereof, for example 4- or 5-alkylbenzotriazoles (e.g.
triazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole
and 5,5'-methylenebisbenzotriazole; Mannich bases of benzotriazole
or triazole, e.g. 1-[bis(2-ethylhexyl) aminomethyl) triazole and
1-[bis(2-ethylhexyl) aminomethyl)benzotriazole; and
alkoxyalkylbenzotriazoles such as 1-(nonyloxymethyl)benzotriazole,
1-(1-butoxyethyl) benzotriazole and 1-(1-cyclohexyloxybutyl)
triazole, and combinations thereof. Additional non-limiting
examples of the one or more metal deactivators include
1,2,4-triazoles and derivatives thereof, for example 3-alkyl(or
aryl)-1,2,4-triazoles, and Mannich bases of 1,2,4-triazoles, such
as 1-[bis(2-ethylhexyl) aminomethyl-1,2,4-triazole;
alkoxyalkyl-1,2,4-triazoles such as
1-(1-butoxyethyl)-1,2,4-triazole; and acylated
3-amino-1,2,4-triazoles, imidazole derivatives, for example
4,4'-methylenebis(2-undecyl-5-methylimidazole) and
bis[(N-methyl)imidazol-2-yl]carbinol octyl ether, and combinations
thereof. Further non-limiting examples of the one or more metal
deactivators include sulfur-containing heterocyclic compounds, for
example 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thia-diazole
and derivatives thereof; and 3,5-bis[di(2-ethylhexyl)
aminomethyl]-1,3,4-thiadiazolin-2-one, and combinations thereof.
Even further non-limiting examples of the one or more metal
deactivators include amino compounds, for example
salicylidenepropylenediamine, salicylami-noguanidine and salts
thereof, and combinations thereof. The one or more metal
deactivators are not particularly limited in amount in the
composition but are typically present in an amount of from about
0.01 to about 0.1, from about 0.05 to about 0.01, or from about
0.07 to about 0.1, wt.-% based on the weight of the composition.
Alternatively, the one or more metal deactivators may be present in
amounts of less than about 0.1, of less than about 0.7, or less
than about 0.5, wt.-% based on the weight of the composition.
[0077] Pour point depressants (PPD) include polymethacrylates,
alkylated naphthalene derivatives, and combinations thereof.
Commonly used additives such as alkylaromatic polymers and
polymethacrylates are also useful for this purpose. Typically, the
treat rates range from .gtoreq.0.001 wt.-% to 1.0 wt.-%, in
relation to the weight of the base stock.
[0078] Demulsifiers include trialkyl phosphates, and various
polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, or mixtures thereof.
EXAMPLES
[0079] PAG Basestock: random ethoxylated and propoxylated
1,4-butandiol, 60 wt.-% ethylene oxide units, Mn about 6500 g/mol
(based on OH number), KV40 about 1100 mm.sup.2/s, KV100 about 200
mm.sup.2/s. [0080] Amine Antioxidant B: aromatic amine of the
formula (I), where R1 and R2 together represent the group A, R3 is
H, and R4 is branched octyl, CAS [51772-35-1]. [0081] Phenol
Antioxidant A: ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)
propionic acid with isooctanol. [0082] Phenol Antioxidant C: ester
of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with
1,6-hexanediol.
Example 1
[0083] The lubricants samples (each 30 g) contained the PAG
basestock and 0.75 wt % of the Phenol Antioxidant and the 0.75 wt %
of the Amine Antioxidant as described in Table 1.
TABLE-US-00001 TABLE 1 Composition of lubricant (data in wt %)
Lubricant A Lubricant B PAG Basestock 98.75 98.75 Amine Antioxidant
B 0.75 0.75 Phenol Antioxidant A 98.75 -- Phenol Antioxidant C --
98.75
Example 2
[0084] The lubricants samples (each 30 g) from example 1 were
stored for several weeks at 150.degree. C. in an open flask without
stirring in the presence of a round copper blank (1 mm thick, 16 mm
diameter, about 2 g). The KV40 was determined and the results
summarized in Table 2. The KV40 before heating was set as 100%.
TABLE-US-00002 TABLE 2 Evaluation of the KV40 [%] on storage at
150.degree. C. Weeks Lubricant A Lubricant B 0 100 100 2 97 96 4 93
94 8 86 88 10 81 81
[0085] The data showed, that there was no increase and only a low
decrease in viscosity due to decomposition of the polyalkylene
glycol basestock.
* * * * *